RJTA Vol. 10 No.

2 2006

No-Salt Dyeing Behaviour of Cationized Linen Fabrics

A. Hebeish1, M. Hashem1, M. EL-Hosamy2 and S. Abass2
Textile Division, National Research Centre, Dokki, Cairo, Egypt
2
Faculty of Applied Arts, Helwan University, Cairo, Egypt.
Correspondence author: (mhashem22@yahoo.com - mhashem22@hotmail.com)
1

ABSTRACT
Linen fabrics were cationized using 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in
alkaline medium. The cationized linen fabrics were dyed independently, with different dyestuffs,
namely reactive, direct and acid dyes in absence of salt (no-salt dyed). Factors affecting the nosalt dyeing process of cationized linen fabrics were investigated. These factors included dye
concentration, pH of the dyeing bath, dyeing temperature and time as well as the chemical nature
of the dyes used. The dyed samples were monitored for color strength (K/S) after soaping and
after DMF extraction as well as fastness properties. It was found that for all dyestuffs used, the
magnitude of K/S of the dyed samples depends on the nature of the dyes and the conditions used
in each case. It was also seen that for no-salt dyeing of cationized linen fabrics, the maximum
K/S was achieved at dye shade 2.5 % (ows) and dye baths pH 7-9, at 60C for 20 minutes. In
addition to this, the color strength was much higher in case of cationized and no-salt dyed samples
compared with the uncationized and traditionally salt-dyed linen fabrics; meanwhile, the overall
fastness properties were comparable. Microscopic examination of the cationized and no-salt dyed
linen fabrics showed an excellent dye penetration and no evidence for the ring dye phenomena
was observed.
Keywords: Acid dye, Cationization, Cellulose, Linen fabric, No-salt dyeing, Reactive dye, direct
dye

1.

chemicals, dyes and equipment, which is likely to

involve significant capital investment.

Introduction

In current practice, cellulosic fibre is predominantly

dyed with reactive dyes in the presence of a
considerable amount of salt and fixed under alkaline
conditions. However, fixation efficiency on
cellulosic fibre is generally low (varying from 50 90 %) (Evan et. al, 1984). This, in turn, results in a
highly colored dye effluent, which is unfavourable
to environmental grounds (Cai et. al, 1990).
Furthermore, the high concentrations (40 - 100 g/l)
of electrolyte and alkali (5 - 20 g/l) required in
cellulose fibre dyeing might create additional
effluent problems. In combination with this, the
ever-increasing popularity of reactive dyeing of
cellulose fibre has made the matter increasingly
aggravating.

Enhancement cotton reactivity via its chemical

modification represents another promising route that
can overcome lower affinity of cotton to anionic
dyes. Cationization of cotton cellulose has been
reviewed by a number of authors (Lewis and Lei,
1991; Rupin, 1976; Evan et. al, 1984). Rosemarie
(1987) reported that cationized cellulose having
ether linkages could be synthesized by first reacted
with epoxide incorporating halogen atoms such as
epichlorohydrin or chlorobutylene oxide and then
with nitrogen compounds such as ammonia or
amines. These cellulose derivatives not only had
improved substantivity for direct dyes but could also
be dyed with acid dyes, which resulted in improved
fastness.

It was postulated (Shaeppi et. al, 1998) that through

the optimization of the dyeing process, dye bath reuses and equipment changes, the problem could be
solved. Though these ideas are valid for reducing
effluent problems, all involve replacing existing

Recently, studies have been carried out to improve

the dyeing properties of cotton fabrics via its
cationization using epoxy quaternary ammonium
compounds (Rupin, 1976), choline chloride and
cross-linking agents (Harper, 1986), compounds
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RJTA Vol. 10 No. 2 2006

with s-triazine ring (Clipson and Roberts, 1989), a

polyepichlorohydrin dimethylamine (Wu and Chen,
1993) and 3-chloro-2-hydroxypropyl trimethyl
ammonium chloride commercially known as Quat188. The latter has received considerable attention in
recent years (Lei and Lewis, 1990; Lewis and Lei,
1991; Wu and Chen, 1992, 1993; Hauser, 2000;
Hauser and Tabba, 2001, 2002; Tabba and Hauser,
2000; Draper et al, 2002; Hashem et. al, 2003).

2.

Experimental

2.1

Materials

The grey 100 % linen fabric (plain weave, 180 g/m2,

20 yarns /cm2, in warp and 23, yarns/cm2 in weft)
was used. The fabric was mill scoured and bleached
as detailed below.
Sodium hydroxide, sodium sulphite, sodium
hydrosulphite, sodium sulphide, sodium sulphate,
sodium chloride, acetic acid, sodium carbonate,
boric acid, hydrochloric acid, copper sulphate and
potassium sulphate were of laboratory grade

chemicals. Hydrogen peroxide (35%) and Egyptol

(non-ionic wetting agent based on ethylene oxide
condensate) were of technical grade chemicals. 3Chloro-2-hydroxypropyl trimethyl ammonium
chloride (65 % aqueous solution under a
commercial name Quat-188), which was kindly
supplied by DOW Chemical Company, USA, was
of technical grade chemicals. Table 1 lists the names
of the reactive dyes, direct dyes and acid dyes used
in our study, along with their color indexes and
function groups.

The quaternary ammonium groups act as dye sites.

Therefore, with blended fabrics or mixed fabrics
using cationized cellulosic fibre and uncationized
cellulosic fibre, two-tone effects can be obtained in
one-bath dyeing. Moreover, since the ammonium
group is expected to form ionic bonds with anionic
water-soluble groups of reactive dyes, the dyeability
of the cationized cellulosic fibre with reactive dyes
can be improved. The ammonium group is also
expected to exhibit antimicrobial activity through a
blocking mechanism (Seong and Ko, 1998).
However, to the author's knowledge, no work has
yet been published on the cationization of linen
fabrics and the no-salt dyeing behaviour. In our
previous work (Hebeish et. al, 2006), we have
studied the process parameters in the cationization
of linen fabrics with 3-chloro-2-hydroxypropyl
trimethyl ammonium chloride (CHATC). As a
continuation of the work, the purpose of the present
paper is to investigate the no-salt dyeing behaviour
of cationized linen fabrics. The cationized linen
fabrics were separately dyed with direct, reactive
and acid dyes under varieties of conditions. The
latter included pH of the dye bath, dyeing
temperature and dyeing time as well as the chemical
nature of each kind of dyes. In parallel, and for
comparison, uncationized linen samples were
conventionally dyed the same concentration of the
identical dyes. The term no-salt will be used to
designate those linen samples that were cationized
then dyed in absence of salt (in case of direct or acid
dyes) or in absence of alkali and salt (in case of
reactive dyes). Also, the expression conventionally
salt-dyeing will be used to designate those
uncationized samples dyed in presence of salt in
case of direct dyes or in presence of salt and alkali in
case of reactive dyes using the procedures
recommended by the dye manufacturer. Both dyed
samples (cationized followed by no-salt dyeing and
un-cationized followed by conventionally salt
dyeing) were evaluated for K/S after soaping and
after DMF extraction. Microscopic examination and
overall fastness properties were also investigated.

2.2

Scouring and Bleaching of Linen Fabrics

The grey linen fabric was mill scoured and bleached

using Jigger machine as follows: the fabric was
introduced into the Jigger along with water. The
amount of water was adjusted to give a liquor ratio
of 1:20. Addition of 40 g/l sodium hydroxide, 10 g/l
sodium hydrosulphite, 5 g/l Egyptol (non-ionic
wetting agent) were added and the temperature was
raised to 95C for 30 minutes. The sample was then
washed several times with boiling water and finally
with cold water.
The scoured fabric was bleached using the same
Jigger machine using the following recipe: H2O2, 10
g/l; sodium silicate, 4 g/l; NaOH, 2 g/l; Egyptol, 2
g/l; organic stabilizer, 2 g/l; MgSO4, 2 g/l, at 95C
for 45 min. The fabric was washed several times
with boiling water, then with cold water and finally
squeezed and dried at ambient conditions.
2.3

Cationization of Linen Fabrics Through

Reaction with 3-Chloro-2-Hydroxy-Propyl
Trimethyl Ammonium Chloride (Quat188)

The cold pad-batch method was used for preparing

the cationized linen fabrics under investigation
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RJTA Vol. 10 No. 2 2006

Table 1. Reactive, direct and acid dyes used in our study

Dye names and C.I

Function groups

Sunzol Brilliant Red BB (Reactive Red 21)

Vinyl sulphone

Sunfunvion Blue HEGN (Reactive BL. 198)

Monochlorotriazine

Reactobond Red 6BX (Reactive R. 255)

Bi- functional

Diamin Supra Blue FFRL (Direct Blue 108)

Oxazine

Red Scarlet 4 BS (Direct Red 16 )

Diazo

Orange S (Direct Orange 10)

Diazo

Black EX 150 % (Direct Black 1)

Triazo

Alphanol Fast Turquoise Blue GGL (Acid Blue 189)

Phthalocyanine

Fast red EG (Acid Red 1)

Monoazo

Fast yellow GW (Acid Yellow 61)

Monoazo

(Hebeish et al, 2006). The experimental procedures

were as follows: calculated amounts of Quat-188
and NaOH were mixed at room temperature. The
bleached linen fabric was padded through this
mixture, and then squeezed to wet pick up of 100 %.
The sample was then batched at room temperature
in a plastic package for 24 hours. At this end, the
cationized sample was washed with cold water and
acetic acid, then washed several times with cold
water and finally dried at ambient conditions.
2.4

The experimental techniques were described as

follows:
A- Reactive dyes
The dyeing procedures with Sunzol Brilliant Red
BB (C.I: Reactive Red 21) and Sunfunvion Blue
HEGN (C.I: Reactive BL 198) were as follows:
Calculated amount of dye was dissolved in water
along with half amount of salt. Material to liquor
(LR) ratio was adjusted at 1:50. The bleached linen
fabric was introduced in this solution with
continuous stirring. After 10 minutes, the second
half of salt was added. The temperature was then
raised gradually to 60C in 10 minutes in case of
using Sunzol Brilliant Red BB, or to 80C when
using Sunfunvion Blue HEGN. During 30 minutes,
the required amount of sodium carbonate was added
in three doses (each after 10 minutes). The dyeing
process was continued for another 45 minutes. The
samples were washed in an aqueous solution
containing 5 g/l soap at 100C for 15 minutes.
Finally, the sample was washed with cold water and
dried at ambient conditions.

No-salt Dyeing of Cationized Linen Fabrics

The cationized linen fabric samples were dyed

independently with reactive, direct and acid dyes
using the no-salt dyeing method. The method was
used as follows: the samples were introduced in an
aqueous solution containing the reactive dyes with
continuous stirring; the temperature was raised to 25
- 90C for 5 - 60 minutes. The samples were then
boiled in an aqueous solution containing 5 g/l soap

(Egyptol ) for 15 minutes. Finally, the samples were

washed with cold water, and dried at ambient
conditions. The un-exhausted dyeing molecules
were extracted by treating the samples with an
aqueous solution containing DMF/water (50/50) at
100C for 15 minutes.
2.5

The dyeing procedures with Reactobond Red 6 BX

(C.I: Reactive R. 255) were as follows: Calculated
amount of dye was dissolved in water along with the
required amount of salt. Material to liquor (LR) ratio
was adjusted to 1:50 using water. The bleached
linen fabric was introduced in this solution with
continuous stirring. After 20 minutes, half amount
of sodium carbonate was added. The dyeing process

Conventional Salt-dyeing Processes

Methods and recipes of conventional dyeing

processes were employed as given by the supplier.

45

RJTA Vol. 10 No. 2 2006

was continued for another 10 minutes; then the

second half amount of sodium carbonate was added
and the temperature was raised gradually during 15
minutes to 60C. The dyeing process was continued
for another 45 minutes, and then the sample was
washed in an aqueous solution containing 5 g/l soap
(Egyptol) at 100C for 15 minutes. Finally, the
sample was washed with cold water. The
unexhausted dyeing molecules were extracted by
treating the samples with an aqueous solution
containing DMF/water (50/50) at 100C for 15
minutes.

Microscopic examination of the bleached fabrics,

cationized, traditionally dyed and cationized
followed by no-salt dyeing linen fabrics was carried
out using the Video Microscope system. The
microscope system was supplied with a CCD
camera, 2-meter fiber optic and contact/non-contact
lens with magnification value up to 1000.

B- Direct dyes
Linen fabric samples were introduced in an aqueous
solution containing the direct dye with continuous
stirring. During 30 minutes, the required amount of
salt was added in three doses and the temperature
was raised gradually to 95C. The dyeing process
was continued for another 30 minutes. The samples
were then washed in an aqueous solution containing
3 g/l soap (Egyptol) at 100C for 15 minutes.
Finally, the samples were washed with cold water
and dried at ambient conditions. The unexhausted
dyeing molecules were extracted by treating the
samples with an aqueous solution containing
DMF/water 50/50 at 100C for 15 minutes.
2.6

3.

Result and Discussion

3.1

No-Salt Dyeing of Cationized Linen

Fabrics with Reactive, Direct and Acid
Dyes:

Effect of Dye Concentration

The cationized linen fabrics were subject to reactive
dyeing using different concentrations from Sunzol
Brilliant Red BB (Reactive Red 21). The dyeing
process was carried out without salt and alkali. In
parallel, uncationized linen samples were
conventionally dyed with different concentrations
from the same dye in presence of 50 g/l, NaCl and
20 g/l, Na2CO3.

Testing and Analysis

Nitrogen content, expressed as N % of the linen

fabrics before and after cationization, was
determined by the Kjeldhal method (Vogel, 1975).
The color strength expressed as K/S value of the
dyed fabrics after soaping and after DMF extraction
was measured using Spectrophotometer type MM
3000 ICS-Texicon (Newbury, Berkshire, UK). K/S
was calculated by the Kubelka-Munk equation
(Kubelka and Munk, 1931). Dry and wet colour
fastness to crocking was determined according to
the AATCC standard test method (AATCC
Standard Test Method 8-1972). The color fastness to
washing was determined according to the AATCC
test method (AATCC Standard Test Method 161972). Color fastness to perspiration was
determined according to ISO 105/ E -1978. Two
artificial perspiration solutions were made as
follows:
-

distilled water. The pH was adjusted to 8 by the

NaOH solution (0.1N).
Acidic
solution:
L-Histidine
mono
hydrochloride monohydrate (0.5 g/l), sodium
chloride (5 g/l), sodium dihydrogen phosphate
(2.2 g/l) were dissolved in distilled water. The
pH was adjusted to 5.5 by the acetic acid
solution (10 %). The evaluation was established
using the grey scale as reference of color
change.

In our discussion, the expression no-salt will be

used to designate those linen samples that were
cationized then dyed in absence of salt (in case of
direct or acid dyes) or in absence of alkali and salt
(in case of reactive dyes). Also, the conventional
expression salt-dyeing will be used to designate
those uncationized samples dyed in presence of salt
in case of direct dyes or in presence of salt and alkali
in case of reactive dyes using the procedures
recommended by the dye manufacturer and detailed
in the experimental part.
Dyed samples (cationized followed by no-salt
dyeing and uncationized followed by traditionally
salt-dyeing) were evaluated for K/S after soaping
and after DMF extraction. Results obtained are set
out in Figures 1-3.

Alkaline
solution:
L-Histidine
monohydrochloride monohydrate (0.5 g/l),
sodium chloride (5 g/l), sodium di- hydrogen
phosphate (5 g/l) were dissolved in a litre of
46

RJTA Vol. 10 No. 2 2006

immobile and their reaction relies on the presence of

dye molecules in their proximity, a situation which
can be accomplished at higher dye concentration.
On the other hand, the superiority of K/S in case of
the no-salt dyeing of the cationized samples vis-vis that uncationized and traditionally dyed with the
same reactive dye is owing to the higher fixation of
reactive dye molecule by electrostatic attraction to
the cationic site in cationized linen fabrics.

It is seen from Figure 1 that in case of cationized

then no-salt dyed linen samples, increasing the
concentration of the reactive dye from 0.5 % to 2.5
% (ows) was accompanied by increasing K/S from
16.38 to 22.72 after soaping and from 16.17 to
22.65 after DMF extraction. Further increase in the
concentration of the reactive dye was accompanied
by levelling off in K/S. The same was also true for
conventionally salt-dyeing of uncationized linen
fabrics using the same reactive dye but with the
certainty that the K/S value of cationized and no-salt
dyed samples was much higher than those of
uncationized and conventionally dyed samples
whatever the dye concentration used. Obviously, the
maximum color strength was achieved at reactive
dye concentration which was equal to 2.5 % (ows)
for cationized- no-salt dyed samples. On the other
hand, for traditionally dyed samples, the colour
strength increased as the concentration of reactive
dye increased and no maximum was attained within
the concentration of reactive dyes used in this study.

Figure 2 shows the effect of direct dye concentration

(Diamin Supra Blue FFRL, C.I: Direct Blue 108) on
K/S of both cationized followed by no-salt dyeing
and uncationized followed by conventionally saltdyeing linen fabrics. It is seen from Figure 2 that
increasing the dye concentration from 0.5 % to 2.5
% (ows) was accompanied by increasing K/S values
of cationized samples from 11.57 to 23.68 after
soaping and from 11.17 to 23.59 after DMF
extraction. Further increase in the concentration of
direct dyes was accompanied by a marginal increase
in the K/S value. The same held true for
conventionally dyeing linen fabrics using the same
direct dye, but with certainty that the K/S values of
cationized and no-salt dyed samples were much
higher than those of the uncationized and
conventionally dyed samples.

Enhancement of the K/S values as the concentration

of reactive dyes increased could be interpreted in
terms of greater availability of reactive dye
molecules in the vicinity of hydroxyl groups in linen
cellulose or Quaternary ammonium groups in the
cationized linen cellulose. It is understandable that
cellulose hydroxyls or tertially ammonium group are
40

No- salt dyeing after soaping

No- salt dyeing after DMF

35

Traditionally dyeing after soaping

Traditionally dyeing after DMF

30

25

K/S

20

15

10

0
0

0.5

1.5

2.5

3.5

Dye concentration (% ows)

Fig. 1. Effect of reactive dye concentration on K/S of no-salt dyed and conventionally dyed linen fabrics

47

RJTA Vol. 10 No. 2 2006

40

No- salt dyeing after soaping

No- salt dyeing after DMF

35

Traditionally dyeing after soaping

Traditionally dyeing after DMF

30

K/S

25

20

15

10

0
0

0.5

1.5

2.5

3.5

Dye conc. (% ows)

Fig. 2. Effect of direct dye concentration on K/S of no-salt dyed and conventionally dyed linen fabrics
Similar results were obtained when the cationized
linen fabrics were dyed with different concentration
of acid dyes (Alphanol Fast Turquoise Blue GGL,
C.I: Acid Blue 189). It should be noted here that the
bleached uncationized linen fabrics had no affinity
for acid dyes under our experimental conditions
used. Therefore, our study will focus on no-salt
dyeing of cationized linen fabrics with acid dyes.
Figure 3 shows that increasing the dye concentration
from 0.5 % to 2.5 % (ows) was accompanied by
increasing K/S values of cationized and no-salt acid
dyed linen samples from 16.78 to 27.73 after

soaping and from 16.75 to 27.72 after DMF

extraction. Further increase in the concentration of
acid dyes was accompanied by a marginal increase
in the K/S value. Obviously, the maximum K/S
value was achieved at acid dye concentration equal
to 2.5 % (ows).
Results obtained in Figures 2 and 3 (direct dye and
acid dye respectively) are similar to those obtained
in Figure 1 (reactive dye) and could be explained on
similar bases.

40
K/S after soaping
35

K/S after DMF

30

K/S

25
20
15
10
5
0
0

0.5

1.5

2.5

3.5

Dye conc. (% ows)

Fig. 3. Effect of acid dye concentration on K/S of no-salt dyed linen fabrics
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RJTA Vol. 10 No. 2 2006

3.2

direct dye molecules are attached to the linen

molecules most probably via chemical bonding.

No-salt Dyeing of Cationized Linen Fabrics

with Reactive, Direct and Acid Dyes:
Effect of Process Parameters

Table 2 shows also the effect of pH on K/S of precationized and no-salt dyed linen fabrics with acid
dyes (Alphanol Fast Turquoise Blue; Acid Blue
198). Results obtained are in accordance with the
results of reactive dyes and direct dyes discussed
above.

3.2.1 Effect of pH
Cationized linen fabrics were dyed using 2.5 %
(ows) reactive dye, Sunzol Brilliant Red BB (C.I:
Reactive Red 21) at different pH's. Acidic pH was
adjusted using 5 % aqueous acetic acid solution,
whereas alkaline pH was adjusted using 1.0 %
aqueous NaOH solution. The so obtained dyed
samples were evaluated for K/S after soaping and
after DMF extraction. Results obtained are set out in
Table 2.

3.2.2 Effect of Dyeing Temperature

Table 2 shows the effect of the dyeing temperature
on the extent of no-salt dyeing of cationized linen
fabrics using reactive, direct and acid dyes, namely
Sunzol Brilliant Red BB (Reactive Red 21), Diamin
Supra Blue FFRL (Direct Blue 108) and Alphanol
Fast Turquoise Blue (Acid Blue 198) respectively.
The dyed fabrics were monitored for K/S after
soaping and after DMF extraction.

It is seen from Table 2 that as the pH of reactive dye

bath increased from 5 to 9, the K/S values of the
dyed fabrics increased from 16.78 to 23.6 after
soaping and from 16.54 to 22.77 after DMF
extraction. Further increase of pH was accompanied
by a sharp decrease in the K/S values of the dyed
samples. This suggests that the built- in basic
catalyst and the role played by the quaternary
ammonium groups introduced in the molecular
structure of linen are diminished under relatively
high alkaline pH's. The alkaline seems to react with
these groups and- in so doing- impedes their
function as built-in catalyst as well as provision of
additional sites for dye reaction. It is also shown in
the table that the maximum colour strength of nosalt reactive dyed linen fabrics was obtained at a pH
range of 7-9.

It is seen from Table 2 that with all the three kinds

of dyes used, increasing the dyeing temperature
from room temperature to 60C brought about an
increase in the K/S values of the dyed samples after
soaping and after DMF extraction. Further increase
in the temperature had practically no effect on the
K/S values of the dyed samples. Higher K/S at up to
60C could be associated with the favourable effects
of temperature on swelling of cationized linen
fabrics, diffusion of dye molecules, mobility of the
dye molecules and their collision with cationized
linen fabrics.

Similar results were obtained when the cationized

linen fabrics were dyed using 2.5 % (ows) direct
dye, Diamin Supra Blue FFRL (C.I: Direct Blue
108) at different pH's. As the pH of direct dye bath
increased from 5 to 9, the K/S values of the direct
dyed fabric increased from 21.11 to 24.60 after
soaping and from 22.09 to 24.58 after DMF
extraction. Further increase in pH was accompanied
by a sharp decrease in the K/S values of the dyed
samples. This is rather similar to the results of
reactive dyes presented above and, therefore, can be
discussed on similar lines.

3.2.3 Duration of No-salt Dyeing

Table 2 shows also the effect of the dyeing time on
the K/S of cationized and no-salt dyed linen fabrics
using reactive, direct and acid dyes, namely Sunzol
Brilliant Red BB (Reactive Red 21), Diamin Supra
Blue FFRL (Direct Blue 108) and Alphanol Fast
Turquoise Blue (Acid Blue 198) respectively.
Results of Table 2 indicate that a 20-minute duration
was enough for attaining the maximum K/S value.
Further increase in the dyeing time had practically
no effect on the K/S. Needless to say, cationized
linen fabric is characterized by strikingly shorter
dyeing time and much higher K/S values as
compared with the conventional dyeing of
uncationized linen fabrics at the same dye
concentration.

The maximum K/S value was achieved within the

pH range of 7-9 when no-salt dyeing of direct dyes
was applied to cationized linen fabrics. It is as well
to emphasize that although the dyes used belonged
to the class of direct dyes, their extraction with DMF
detracted very little from their color strength on the
cationized linen. The implication of this is that the
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RJTA Vol. 10 No. 2 2006

Table 2. No-salt dyeing of cationized linen fabrics with reactive, direct and acid dyes: Effect of process
parameters
K/S
Process parameter

Reactive dye

(a)

Direct dye (b)

Acid dye (c)

Soaping

DMF

Soaping

DMF

Soaping

DMF

16.78

16.54

22.11

21.09

26.16

26.01

23.79

23.70

24.62

24.57

27.17

27.10

23.6

22.77

24.60

24.58

27.48

27.40

11

15.83

15.17

21.32

21.86

23.10

23.01

14

3.41

3.04

5.85

2.96

16.33

16.05

25

15.83

13.66

13.14

12.12

22.46

20.82

40

21.13

19.91

22.68

22.60

26.83

26.80

50

21.73

21.37

22.68

23.41

26.99

26.95

60

23.62

23.60

24.64

24.60

27.70

27.70

70

23.61

23.37

24.44

24.23

27.71

27.70

80

23.67

23.62

24.31

24.30

27.69

27.66

90

23.60

23.60

24.46

24.40

27.72

27.70

20.16

19.1

13.53

13.42

21.68

21.60

10

21.17

20.30

20.20

19.82

26.94

26.93

20

23.68

23.55

24.64

24.64

27.72

27.70

30

23.68

23.57

24.62

24.60

27.73

27.71

40

23.59

23.55

24.65

24.63

27.70

27.69

50

23.59

23.50

24.62

24.61

27.71

27.70

60

23.60

23.59

24.64

24.60

27.72

27.70

pH

Temperature (C)

Time (min)

(a)

Sunzol Brilliant Red BB (Reactive Red 21)

(b)

Diamin Supra Blue FFRL (Direct Blue 108)

(c)

Alphanol Fast Turquoise Blue GGL (Acid Blue 189)

Dye shad used with all dye is 2.5 % (ows)

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3.3

much higher than those values obtained after

conventional dyeing.
b) The percentage change in the K/S values
between conventionally dyed linen fabrics and
the K/S obtained for no-salt dyed linen fabrics
after cationization depends on the nature of
reactive dyes used. Percentage change in K/S
was amounted to 122.8 % on using Sunzol
Brilliant Red BB (Reactive Red 21) which has
vinyl sulphone reactive group. Whereas the
percentage change in K/S amounted to 61.4 %
for Sunfunvion Blue HEGN (Reactive BL 198)
which has monochloro-triazine reactive group.
The percentage change in the K/S value
amounted to 192.8 % in case of Reactobond
Red 6BX (Reactive R 255) which has
bifunctional reactive group.
c) Results in Table 3 show that the percentage
change in the K/S values between conventionally
salt-dyed and those cationized then no-salt dyed
linen fabrics depend on the reactive dye structure.
The percentage change in the K/S values follows
the following order:

Effect of Nature and Chemistry of Dye

A study was made to look at the effect of reactive,

direct and acid dye chemistry on the dyeing
properties of cationized linen fabrics. In order to
determine how the structure of reactive dyes affects
the color yields of the no-salt dyed cationized linen
fabrics, three commercially available fiber reactive
dyes having a variety of reactive groups were
chosen. The names and color indexes as well as the
reactive function groups of these reactive dyes are
set out in Table 3. Table 3 shows also the K/S
values of the conventionally dyed linen fabrics and
those obtained when cationized linen fabrics were
no-salt dyed. The dyeing process was carried out
using the same dye shade for all the reactive dyes
used. The K/S values were determined after soaping
and after DMF extraction. Percentage change in the
K/S values between conventionally dyed and no-salt
dyed samples were calculated based on the values
obtained after DMF extraction.
It is seen from Table 3 that:
a) For all reactive dyes used, the K/S values of the
cationized and no-salt dyed linen fabrics were

Bifunctional > vinyl sulphone > monochlorotriazine

Table 3. Effect of reactive dye chemistry on K/S of no-salt dyed linen fabrics
and conventionally dyed linen fabrics
K/S
Dye names and its C.I

(a)

Reactive groups

Conventionally
dyeing
After
After
soaping DMF

No- salt dyeing

After
soaping

After
DMF

Change in K/S (%)(a)

Sunzol Brilliant Red BB

(Reactive Red 21)

Vinyl sulphone

10.80

10.62

23.70

23.67

122.90

Sunfunvion Blue HEGN

(Reactive BL. 198)

Monochlorotriazine

15.80

14.46

24.34

23.34

61.41

Reactobond Red 6BX

(Reactive R. 255)

Bi-functional

7.80

7.89

23.59

23.10

192.80

% Change in K/S values were calculated from those values obtained after DMF extraction as follows:

% Change of K/S

K/S of cationized and nosalt dyed - K/S of conventionally dyed

100
K/S of conventionally dyed

51

RJTA Vol. 10 No. 2 2006

A similar study was carried out using four

commercially available direct dyes having different
molecular structures: substituents, configuration,
molecular weight, etc. The names and colour
indexes as well as the function groups of these direct
dyes are shown in Table 4. Results in Table 4
feature the following points:

function group, the

amounted to 1898.6 %.

percentage

change

Results obtained in Table 4 indicate that the

percentage change in the K/S values between the
conventionally salt-dyed and those obtained with
cationized then no-salt dyed linen fabrics depend on
the nature of the direct dyes.

a) For all direct dyes used, the K/S values of

cationized and no-salt dyed linen fabrics were
much higher than those values obtained after
traditional dyeing using the same dye shade.
b) Percentage change in K/S was equal to 1001.3
% on using Diamin Supra Blue FFRL (Direct
Blue 108) which has oxazine function group.
Whereas on using Red Scarlet 4BS (Direct Red
16) which has diazo function group, the
percentage change amounted to 1444.5 %. In
case of Orange S (Direct Orange 10) which has
diazo function group, the percentage change in
K/S amounted to 1407.1 %. On using Black EX
150 % (Direct Black 1) which has triazo

Table 5 shows the effect of structures and function

groups of acid dyes on the colour strength of the
cationized and no-salt dyed linen fabrics. Results of
Table 5 depict that the colour strength of no-salt
acid dyed line fabrics depends on the structural and
functional groups of acid dyes. Moreover, it was
found that although both Acid Red 1 and Acid
Yellow 61 have the same functional groups, namely
monoazo, they gave rise to different K/S values at
the same dye shade. This indicates that both
structural and functional groups play an important
role in the no-salt dying of cationized linen fabrics.

Table 4. Effect of direct dye chemistry on K/S of no-salt dyed and

conventionally dyed linen fabrics
K/S
Dye names and its C.I

Reactive groups

Diamin Supra Blue FFRL

(Direct Blue 108)
Red Scarlet 4BS
(Direct Red 16)
Orange S
(Direct Orange 10)
Black EX 150 %
(Direct Black 1)
(a)

Oxazine

Conventionally
dyeing
After
After
soaping DMF
12.97
2.25

No- salt dyeing

Change in K/S (%)(a)

After
soaping
24.97

After
DMF
24.78

1001.3

Diazo

20.63

1.75

27.82

27.03

1444.5

Diazo

14.04

1.40

22.08

21.10

1407.1

Triazo

9.43

0.73

22.81

21.89

2898.6

% Change in K/S values were calculated from those values obtained after DMF extraction as follows:

% Change of K/S

K/S of cationized and nosalt dyed - K/S of conventionally dyed

100
K/S of conventionally dyed

52

RJTA Vol. 10 No. 2 2006

Table 5. Effect of acid dye chemistry on K/S of no-salt dyed linen fabrics

Dye name and its C.I

Alphanol Fast Turquoise Blue GGL
(Acid blue 198)
Fast Red EG
(Acid Red 1)
Fast yellow GW
(Acid Yellow 61)

3.4

Reactive group

K/S of no-salt dyed fabric

After soaping

After DMF

Phthalocyanine

27.90

27.57

Monoazo

20.59

20.52

Monoazo

14.35

14.03

Table 7 summarizes the fastness properties of four

types of direct dyes, namely Diamin Supra Blue
FFRL (Direct Blue 108), Red Scarlet 4BS (Direct
Red 16), Orange S (Direct Orange 10) and Black
EX (Direct Black 1) Results in Table 6 show clearly
that the color fastness of the cationically modified
linen fabrics followed by no-salt direct dyed was
higher or sometimes comparable to the
conventionally dyed linen fabrics. This was
observed regardless the kinds of direct dyes used.

Fastness Properties of Cationized and NoSalt Dyed Linen Fabrics Vis--Vis

Uncationized and Conventionally Dyed
Fabrics

Table 6 shows the fastness properties of cationized

followed by no-salt dyeing linen fabrics with
reactive dyes vis--vis conventionally dyed linen
fabrics. Three types of reactive dyes were used to
investigate the fastness properties, namely Sunzol
Brilliant Red BB (Reactive Red 21), Sunfunvion
Blue HEGN (Reactive BL 198) and Reactobond
Red 6 BX (Reactive R 255). The fastness properties
examined included wash fastness at 95C, staining
on linen and wool and changing on linen, as well as
rubbing fastness and perspiration fastness. Rubbing
fastness was examined for wet and dry samples and
perspiration fastness was carried out on acidic and
alkaline perspiration. The K/S values obtained for
the no-salt reactive dyed samples and the
conventionally dyed samples are set out in Table 6.

The fastness properties of the cationized linen

fabrics dyed separately with three types of acid
dyes, namely Alphanol Fast Turquoise Blue GGL
(Acid Blue 198), Fast Red EG (Acid Red 1) and
Fast Yellow GW (Acid Yellow 61) are set out in
Table 8. It should be mentioned here that
uncationized linen fabric had no affinity to any
kinds of acid dyes even at high salt concentration.
Therefore, only the fastness properties of the
cationized and acid dyed linen fabrics are given in
Table 8. A salient feature of Table 8 is the higher
washing and rubbing fastness properties
encountered with all acid dyes under investigation.
High attractive interaction between the anionic
groups of the acid dye and the cationic groups in
CHTAC modified linen fabrics would explain the
higher washing and rubbing fastness. However, both
alkaline and acidic perspiration fastness were
moderate.

It is clear (Table 6) that with all kinds of reactive

dyes used, the overall fastness properties for the
conventionally dyed and those obtained with no-salt
dyed linen fabrics were comparable. This indicates
that the addition of cationic sites to the linen fabrics
has no adverse effect on the overall fastness
properties of dyed linen fabrics. However, the color
strength, expressed as K/S, was much greater with
the cationic linen than the unmodified linen. This
was observed irrespective of the kinds of reactive
dyes used.

53

Rubbing
fastness
Wet
Dry

Washing fastness
Dye names and its C.I
Sunzol Brilliant Red BB
(Reactive Red 21)
Sunfunvion Blue HEGN
(Reactive BL. 198)
Reactobond Red 6BX
(C.I: Reactive R. 255)

Functional groups

Vinyl sulphone
Monochlorotriazine
Bi-functional

K/S
23.7
(10.8)
23.3
(15.8)
23.1
(7.8)

St. L

St. W

Chang

4
(4)
4
(3)
4-5
(4-5)

3-4
(4)
5
(4)
5
(5)

4
(4)
4-5
(4)
4
(4)

3-4
(4)
3-4
(3)
3-4
(3-4)

4
(4)
4-5
(3-4)
4
(4)

St. L
4
(4)
3
(2)
3
(3)

Aci
St
(
(
3
(3

Values in brackets represent the fastness properties of the conventionally dyed linen fabrics
St L = Staining on linen, St. W = Staining on wool, Chang = changing

54

Table 7. Colour strength and fastness properties of no-salt direct dyed linen fabrics vis--vis conve
Dye names and its C.I
Functional
groups
Diamin Supra Blue FFRL
(Direct Blue 108)
Red Scarlet 4BS
(Direct Red 16)
Orange S
(Direct Orange 10)
Black EX 150%
(Direct Black 1)

Oxazine
Diazo
Diazo
Trisazo

Rubbing
fastness

Washing fastness
K/S
24.9
(12.9)
27.8
(20.6)
22.1
(14.1)
22.8
(9.4)

St. L

St. W

Chang

Wet

Dry

3
(2)
3
(4)
4
(4)
3
(2)

4
(2-3)
4
(3)
3
(3)
3
(2)

4
(3)
4
(4)
4
(4)
3
(2)

3
(3)
3
(3)
4
(4)
2-3
(3)

4-5
(4)
4
(4)
4
(4)
4-3
(4)

Values in brackets represent the fastness properties of conventionally dyed linen fabric
St L = Staining on linen, St. W = Staining on wool, Chang = changing

St. L
3
(1)
3-4
(2-3)
4
(3-4)
2-3
(1-2)

Acidic
St. W
3
(1-2)
4
(3)
4
(3)
3
(1-2)

RJTA Vol. 10 No. 2 2006

Table 6. Colour strength and fastness properties of no-salt reactive dyed linen fabrics vis--vis conve

Dye names
Alphanol Fast Turquoise Blue
GGL (Acid blue 198)
Fast Red EG
(Acid Red 1)
Fast yellow GW
(Acid Yellow 61)

Functional
groups

Washing fastness
K/S
St. L

Rubbing
fastness

St. W

Chang

Wet

Dry

St. L

Acidi
St. W

Phthalocyanine

27.9

2-3

Monoazo

20.6

4-5

4-5

Monoazo

14.4

4-5

St L = Staining on linen, St. W = Staining on wool, Chang = changing

55

Fig. 4a. Cross-section of bleached linen fabrics

Fig. 4b. Cross-sectio

RJTA Vol. 10 No. 2 2006

Table 8. Colour strength and fastness properties of no-salt acid dyed linen fabric

RJTA Vol. 10 No. 2 2006

3.5

section of traditionally dyed linen fabrics. The figure

depicts excellent dye penetration indicating
homogeneous dye distribution all over the fibre. The
same result was obtained for cationically modified
and no-salt dyed linen fabrics shown in figure 34d.
The latter depicts also an excellent dye penetration
indicating homogenous dye distribution all over the
fibre. Exceptional observation was noted with
cationically modified and no-salt dyed fabric which
was higher dye shade compared with traditionally
dyed linen fabrics.

Microscopic Examination of Bleached,

Conventionally Dye, Cationized, and NoSalt Reactive Dyed Linen Fabrics

A study was made to investigate the fiber crosssection of bleached linen fabrics, cationized,
conventionally dyed bleached fabrics and no-salt
dyed of cationized linen fabrics. Figures 4a, b, c and
d show the fiber cross-section of these fabrics
respectively dyed using the reactive dye Sunzol
Brilliant Red BB (C.I: Reactive Red 21).
Figure 4a shows a typical hexagonal cell structure of
linen fiber cross-section whereas figure 4b shows
the same hexagonal cell structure of the fiber crosssection but with some degree of swelling due to the
effect of NaOH (50 g/l) used during the
cationization reaction. Figure 4c shows the cross-

Based on the above observations, it may be

concluded that cationically modified linen fabrics
exhibit an excellent dye penetration indicating the
uniform distribution of cationic dye sites provided
by treatment with Quat-188.

Fig. 4c. Cross-section of conventionally reactive dyed linen fabrics

Fig. 4d. Cross-section of cationized and no-salt reactive dyed linen fabrics

56

RJTA Vol. 10 No. 2 2006

4.

[7]

Conclusion

[8]

The colour strength (K/S) of cationized and no-salt

dyed linen fabrics depends on the nature of dye and
the conditions used in the dyeing process. This was
observed with all dyestuffs used: reactive dyes,
direct dyes and acid dyes. Regardless the kinds of
dyes used, the maximum K/S was obtained when
the cationized samples were dyed at pH 7-9, and 2.5
% (ows) dye shade at 60C for 20 minutes. It was
also found that the color strength was much higher
in case of cationized and no-salt dyed samples
compared with the uncationized and conventionally
dyed linen fabrics; meanwhile, the overall fastness
properties were comparable. In case of reactive
dyes, the increase in K/S between conventionally
dyed samples and the cationized and no-salt dyed
amounted to 61.4 %- 192.8 % whereas in direct
dyes, it was 1000- 2898 %. Dyeing of cationized
linen fabrics with acid dyes is another important
phenomenon. The K/S values of acid dyed
cationized fabrics amounted to 14.35- 27.9 on using
2.5 % (ows) dye shade. Microscopic examination of
cationized and no-salt dyed linen fabrics depict that
no evidence of the ring dye phenomena was
observed and the same time there was an excellent
dye penetration.

[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]

[17]

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