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Procedia Engineering 200 (2017) 309–316

3rd International Conference on Natural Fibers: Advanced Materials for a Greener World, ICNF
2017, 21-23 June 2017, Braga, Portugal

Dyeing of cotton and polyester blended fabric previously cationized

with synthetic and natural polyelectrolytes
Fernando Ribeiro Oliveria1(*), Diego Alves J. De Oliveira2, Fernanda Steffens1, José
Heriberto O. do Nascimento2, Kesia Karina O. S. e Silva2, and António Pedro Souto3
1 Department of Engineering, Federal University of Santa Catarina, Campus Blumenau, Brazil
2 Department of Textile Engineering, Federal University of Rio Grande do Norte, Natal, Brazil
3 Department of Textile Engineering, University of Minho, Guimarães, Portugal
(*)Email: oliveira.fernando@ufsc.br

Abstract

In this work, a plain weave composed by 50% polyester and 50% cotton (PES/CO) was functionalized by using two
polyelectrolytes, in order to modify its surface to provide a dyeing with an uncommon dye class for cotton and polyester fibers.
Several techniques of characterization were used to study the effects caused by the interaction between polyelectrolytes (Chitosan
and PDDACl) and PES/CO fabric, such as: X-ray Photoelectronic Spectroscopy (XPS), dye solution drop absorption, Scanning
Electron Microscopy (SEM) and whiteness by Berger degree. Good results of dyebath exhaustion with excellent values of color
strength were obtained for the samples previously treated with PDDACl and Chitosan polyelectrolytes. These promising results
mean the possibility of obtaining distinct and solid colors that cannot be obtained with the use of dispersed/reactive dyes, besides
generating a lower energetic cost with the use of lower times and temperatures than those normally used to PES/CO dyeing
process.
© 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 3rd International Conference on Natural Fibers: Advanced
Materials for a Greener World.

Keywords: cotton; polyester; blending; polyelectrolytes; dyeing; functionalization

1. Introduction

The approval of polyester/cotton blended fabrics is increasing day by day because of their ease of use. Polyester

1877-7058 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the scientific committee of the 3rd International Conference on Natural Fibers: Advanced Materials for a
Greener World.

1877-7058 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the scientific committee of the 3rd International Conference on Natural Fibers: Advanced
Materials for a Greener World
10.1016/j.proeng.2017.07.044
310 Fernando Ribeiro Oliveria et al. / Procedia Engineering 200 (2017) 309–316
Author name / Procedia Engineering 00 (2017) 000–000 2

has performance qualities, like wicking and quick-dry properties, so may be added to make the cotton absorb sweat
better. On the flip side, polyester is not breathable and cotton is, so by blending the two materials, you can get a
fabric that is both breathable and sweat-resistant. Thus, the selection of such fibers offer sufficient comfort level and
better resistance due to the different properties of materials. However, the presence of both polyester/cotton
substrates in textile causes difficulties in the dyeing process [1]. Polyester/cotton blends are dyed mainly by two
dyeing bath methods using appropriate dyes and chemical auxiliaries. This dyeing method is relatively long and
complex. Polyester and cotton are dyed under completely different parameters. Cotton is dyed by employing
alkaline conditions at 60 ºC or 80 °C and using reactive, direct or vat dyes whereas polyester is dyed using disperse
dyes in an acidic medium at 120 °C or 130 ºC. This two bath processes, despite offering high levels of shade
reproducibility, are time consuming, often taking 12 - 14 hours [2]. The attractiveness of the application of new
fibrous materials and functionalities has not stopped growing in recent years. Currently, various techniques and
products have been used in order to modify the surface of textiles to create materials with new properties and there
are numerous scientific works that show this reality [3-6].
The continuous search for new solutions has created great opportunities to enhance the value of traditional textile
substrates, through the increment of different functionalities, development of new fibers [4] structures [5], finishes
[6] or even by surface modification by use of physical or chemical processes [7-9]. Despite its undeniable
importance, the textile industry is known for being extremely polluting, mainly due to chemical procedures in the
finishing processes (bleaching, dyeing, printing, among others), which generate higher wastewater rates. Therefore,
it is essential to find solutions that result in the reduction of pollution load or even diminish the cost with energy and
chemical products of the previously cited textile processes. Among the causes for the high rate of effluent are the
enormous finishing processes and low dye absorption into the fibers. Thus, modifications of fibrous substrates aims
at decreasing the time and temperature of procedures or even to increase the dyebath exhaustion are extremely
important. Using polyelectrolytes agents might be an interesting alternative allowing the modification the fibers’
surface without altering their bulk properties.
In this paper, polyester/cotton (PES/CO) plain fabric was functionalized by applying two polyelectrolyte, with the
main objective to dye the substrate using only one type of anionic dye and lower temperature process than the
conventional one.

2. Materials and methods

A plain weave fabric (50%PES+50%CO) with 98 g.m-2 was used in this study. The poly
(diallyldimethylammonium) chloride (PDDACl) applied to functionalize the fabric is a polyelectrolyte with low to
medium molecular weight, between 200.000 – 350.000 (average), has neutral pH and is soluble in water (Technical
data: Textilchemie Dr. Petry GmbH .
Chitosan with a degree of 70% deacetylation was supplied by SelachiiInd.com.ImpE.Exp.Ltda (Fortaleza-CE,
Brazil), solutions with concentration of 10g.L-1 were prepared to be used to functionalize the fabric. Fig. 1 illustrates
the chemical structure of the natural and synthetic polyelectrolytes used.

Fig. 1: Chemical structures of Chitosan and PDDACl.

The functionalization with different parameters (time, temperature and concentration) and the dyeing processes
were performed through the use of BMA-B MATHIS equipment with automatic heating system.
Fig. 2 shows the scheme used for the cationization process and the graphic used to dye the PES/CO substrates.
 Fernando
AuthorRibeiro
name /Oliveria
ProcediaetEngineering
al. / Procedia00Engineering 200 (2017) 309–316
(2017) 000–000 311
3

60

Temperature (ºC)
40

20

0
0 20 40 60 80
Time (min)

Fig. 2: Cationization parameters and graphic used to dye PES/CO samples.

For the dyeing process, three acid dyes with different concentrations 0,1%, 0,25%, 0,5%, 1,0%, 2,0% and 4,0%
over weight fiber (owf) were used with the bath ratio 1:200 and pH between 4-5 (acid acetic 10%). The chemical
structure of the dyes applied in this work can be observed in fig. 3.

b)

a)

c)

Fig. 3 – Chemical structure of the dyes: (a) Erionyl Red A-3G; (b) Marine Blue A-R ; (c) Yellow A-R (CI).

Chemical analysis of the fabrics before and after treatment with polyelectrolytes was performed by X-ray
Photoelectron Spectroscopy on a VG Scientific ESCALAB 200A equipment with PISCES software for data
acquisition and analysis.
In order to evaluate the wettability of the fabrics, the water drop test was applied to measure the time of complete
absorption. For a better visualization of the absorption mechanism, a drop with a dye solution (acid red dye - 2 g.L-1)
was used.
Scanning Electron Microscopy (SEM), Hitachi Tabletop Microscope TM – 3000, was used to verify the
morphological structure and the uniformity of the cationized fabric.
The whiteness index (ºBerger) after polyelectrolyte application and colorimetric coordinates (L*,a*,b*) after
dyeing processes were spectrophotometrically obtained by KONICA MINOTA, Model CM – 2600D apparatus at
standard illuminant D65 and observer 10° combinations.
The washing fastness of the samples was performed according to Norm ISO 105 C06 - No. A1S.

3. Results and discussion

According to fig. 4, the chemical and physical effects of previously treated PES/CO substrate with Chitosan and
PDDACl contributed to the best results obtained in dyebath exhaustion and color strength (K/S), using different
conditions of time and temperature with 2% owf of Eronyl Red acid dye.
312 Fernando Ribeiro Oliveria et al. / Procedia Engineering 200 (2017) 309–316
Author name / Procedia Engineering 00 (2017) 000–000 4

Fig. 4: Graphics of color strength of the PES/CO fabric functionalized in different conditions and dyed with acid dye (2%owf).

One the best result of color strength was obtained for the PES/CO samples functionalized with PDDACl (K/S:
43,02) with the following conditions – 10 minutes, 50ºC and 5% of cationizer agent, approximately 20% higher
than samples pre-treated with Chitosan and nearly three times more intense than untreated sample. Fig. 5 shows the
samples dyed with Erionyl Red Acid Dye and a graphic comparing the values of color strength (K/S) obtained for
the samples untreated and functionalized with chitosan and PDDACl.

50 43.02
Color Strenght (K/S)

40 35.08

30
20 15.31

10
0
Untreated Chitosan PDDACl

Untreated Chitosan PDDACl

Fig. 5: K/S Values of the samples untreated and cationized with Chitosan and PDDACl (Best condition).

The XPS results indicate that the polyelectrolyte was adsorbed by the fibers, as can be observed with the increase
of oxygen, the decrease of carbon and the appearing of nitrogen atoms in the fabric after functionalization with
PDDACl (concentration: 5% owf, time: 10 minutes and temperature: 50ºC) (Figure 6a).
Fig. 6b shows the graphic obtained for the whiteness degree before and after treatment with polyelectrolytes. A
slight decrease in this property can be observed when the PDDACl and Chitosan are applied. The difference
between the untreated sample and the treated samples with polyelectrolytes is only 2,15 and 7,80 values of
whiteness by ºBerger for PDDACl and Chitosan, respectively. These results demonstrated that the cationization
 Fernando Ribeiro Oliveria et al. / Procedia Engineering 200 (2017) 309–316 313
Author name / Procedia Engineering 00 (2017) 000–000 5

applied did not cause significant influence on the whiteness degree of the samples under study, which means that
this treatment modified the chemical surface of the substrate without changing the base color of the fabrics
significantly.

100 (b) 150

(a) 85.4
114.65 112.50
Atomic Percentage (%)

70 106.85
100

ºBerger
50
26.3
50
14.6
0 3.7
0 0
Carbon Oxygen Nitrogen Untreated
Sem PDDACl Quitosana
Chitosan
tratamento
Untreated Cationized

Fig. 6. XPS results (a) and Berger Degree (b) of the samples before and after cationization.

SEM images of the samples before and after functionalization with polyelectrolytes indicate that the cationizer
agent is well distributed on the surface of the fabric, without formation of agglomerates (Fig. 7).

(a) (b) (c)

Fig. 7 - PES/CO fabrics with magnification of 300X: (a) untreated ; (b) treated with PDDACl; (c) treated with Chitosan.

In order to study the wettability/hydrophilicity of the PES/CO fabrics, complete adsorption of the Erionyl Red
dye aqueous solution drops was carried out. Fig. 8 shows the adsorption time of dye solution drop from untreated
and modified fabrics pre-treated with PDDACl and Chitosan. The complete adsorption time of the untreated sample
was 2.0 minutes. These values increased considerably for 5.0 and 10.0 minutes after functionalization with PDDACl
and Chitosan respectively, indicating surface changes for PES/CO fibers.

Control – T0 Treated – PDDACl Treated – Chitosan Control – 2min Treated – PDDACl – Treated – Chitosan –
– T0 – T0 5min 10min

Fig. 8 – Dye solution drop adsorption on the PES/CO fabrics before and after treatment with polyelectrolyte, time 0 and after complete drop
adsorption.

No significant differences can be observed when the initial contact of the dye solution drop with the fabrics
occurs. The results revealed a higher hydrophobicity of the fabrics previously treated with PDDACl and Chitosan.
Despite higher hydrophobicity, it may be also observed that the color is more intense in the functionalized fabrics,
probably due the surface interaction between the dye and polyelectrolytes preventing the dye diffusion into the fiber.
The chemical and physical effects of the previously treated PES/CO substrate with Chitosan and PDDACl
314 Fernando Ribeiro Oliveria et al. / Procedia Engineering 200 (2017) 309–316
Author name / Procedia Engineering 00 (2017) 000–000 6

contributed to the best results obtained in color strength (K/S) as can be detected in the fig. 9, 10 and 11, using
different concentrations of Erionyl Marine Blue A-R, Erionyl Red A-3G and Erionyl Yellow A-R acid dyes, in
different concentrations, at the temperature of 50 ºC with a dyeing time of 50 minutes.
The results of color strength presented evince that when dye concentration increases, dye adsorption also
increases for all fabrics studied (untreated and treated), although this increase is more accentuated on a previously
functionalized sample. The reason for this is that with the increase of dye molecules in solution, these tend to
aggregate and increase the chemical potential of the solution and consequently its interaction with the fabric
previously functionalized with Chitosan and or PDDAC1(negative groups of the dyes (SO3-) with positive group of
the polyelectrolytes (NH3+, N+, respectively)) . For the red acid dye, the addition of the K/S value between the
samples are on average 3 and 5 times higher for fabrics treated with Chitosan and PDDACl, respectively. With
marine blue acid dye, the color strength ratio of the previously treated samples (Chitosan and PDDACl) with
untreated one is approximately 2 and 3 respectively.
Similar results are observed with yellow acid dye. PES/CO treated with Chitosan and PDDACl presented
respectively around twice to 3 times and 3 to 4 times higher color intensity than control sample.
It has furtherly been found that in solution with 0.1% and 0.5% owf the total dye bath exhaustion after dyeing is
visible, showing that the groups from the polyelectrolytes present in the fabrics are able to absorb completely the
dye from the bath in that concentrations. At higher concentrations, groups from the polyelectrolytes are still capable
of capturing more dye from the dye bath, which doesn’t satisfactorily occur on the untreated fabric. These results
indicate that the acid dyes are not conventionally used for the dyeing of cellulosic fibers. It is also verified that the
increase of color strength with 2% and 4% owf does not become so evident, because the increase of dye
concentration twice does not provoke a significant increase of K/S values.
These results are quite interesting, since they indicate that with cationization process it is possible to obtain unique
and more intense colors with the use of lower amounts of dyes.

(a) 80 (b) 80 (c) 80 71.0

78.4

56.9 57.9
60 60 52.4 60
46.7
37.6 40.2 39.9
K/S

K/S
40 40 31.2 40
22.6 26.7
14.7 17.7 18.9
K/S

14.7
20 7.2 10.7 20 20

0 0 0
0.1 0.25 0.5 1 2 4 0.1 0.25 0.5 1 2 4 0.1 0.25 0.5 1 2 4
Concentration (% o.w.f.) Concentration (%o.w.f.) Concentration (% o.w.f.)

Fig. 9. Graphics of color strength of the PES/CO fabric dyed in different concentrations with Blue Acid Dye: (a)
untreated; (b) treated with Chitosan; (c) treated with PDDACl.

(a) 45 (b) 45 (c) 45

43.7
35.0 36.7
30.0 31.1
30 30 24.2 30 22.6
18.4
16.0 17.0
K/S
K/S
K/S

15 9.6 15 9.5 15 10.1

5.5 6.0 7.5
3.2 3.3
0 0 0
0.10% 0.25% 0.50% 1% 2% 4% 0.10% 0.25% 0.50% 1% 2% 4% 0.10% 0.25% 0.50% 1% 2% 4%

Concentration (% o.w.f.) Concentration (% o.w.f.) Concentration (% o.w.f.)

Fig. 10. Graphics of color strength of the PES/CO fabric dyed in different concentrations with Red Acid Dye:
(a) untreated; (b) treated with Chitosan; (c) treated with PDDACl.
 Fernando Ribeiro Oliveria et al. / Procedia Engineering 200 (2017) 309–316 315
Author name / Procedia Engineering 00 (2017) 000–000 7

(a) 50 (b) 50 (c) 50 43.5

36.5
40 40 40
30.2 28.0
30 30 25.4 30
20.3
K/S

K/S

K/S
17.9
20 20 20 14.7
12.1
7.4 9.3 8.3
5.3 6.6 6.5
10 2.7 4.0 10 3.9 10

0 0 0
0.1 0.25 0.5 1 2 4 0.1 0.25 0.5 1 2 4 0.1 0.25 0.5 1 2 4

Concentration (% o.w.f.) Concentration (% o.w.f.) Concentration (% o.w.f.)

Fig. 11. Graphics of color strength of the PES/CO fabric dyed in different concentrations with Yellow Acid Dye:
(a) untreated; (b) treated with Chitosan; (c) treated with PDDACl.

The washing fastness results of the samples functionalized were considered good, with values of 3/4 and 4, to the
PES/CO+Chitosan and PES/CO+PDDACl, respectively. These results indicate an effective interaction, probably
ionic bonding, between cationizer agents with the PES/CO fabric and between the PDDACl and Chitosan reagents
with the acid dyes applied in this study.
The dyeing processes proposed with different concentrations, using three different acid dye can offer great
opportunities for the development of new products using PES/CO blended fabrics with excellent properties, such as,
better dyebath exhaustion, different range of color and may generate more energetically favorable, economical, and
environmentally friendly solutions to textile industry.

4. Conclusions

This research shows that an elementary functionalization process with natural and synthetic polyelectrolytes can
effectively modify the surface of PES/CO fibers.
The dye solution drop adsorption time values were found to depend on the cationization applied, the increase of
hydrophobicity was obtained after functionalization with Chitosan and PDDACl.
It is clearly demonstrated the presence of the cationizer agent by the significant increase in the ratios O/C and
N/C obtained by XPS analysis. SEM images show that the topography of the PES/CO fibers was uniformly altered
without agglomerate formation.
The whiteness degree results obtained showed that the surface modification performed did not alter significantly
the Berger Degree values of the substrates after cationization.
The color strength values increase considerably after functionalization with natural (chitosan) and synthetic
(PDDACl) polyelectrolytes.
These promising results imply the possibility of obtaining unique and solid colors to PES/CO samples using a
faster dyeing process, with only one dyebath, and lower temperature than conventional ones, which are normally
performed at around 130ºC. Consequently, it is possible to reduce the use of water, chemical products and the
energy necessary to dye this important textile substrate (PES/CO Blend).

Acknowledgments

The authors gratefully acknowledge the financial support of the CNPq, Project Universal MCTI/CNPQ/Universal
14/2014, Number 459857/2014-2.

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