Global Journal of Researches in Engineering: C

Chemical Engineering
Volume 18 Issue 1 Version 1.0 Year 2018
Type: Double Blind Peer Reviewed International Research Journal
Publisher: Global Journals
Online ISSN: 2249-4596 & Print ISSN: 0975-5861

Natural Dyeing of Silk with Eucalyptus Leaves Extract

By Nivea Taìs Vila
Federal University of Technology Owerri
Abstract- This study aimed to evaluate the process of silk dyeing with the extract of eucalyptus leaves.
pH, temperature, initial extract concentration was investigated. The initial extract concentration of 20 g L-1,
pH 3 and temperature of 90 °C were the conditions which yielded the best results from dyeing. The
pseudo-second order model was the one that best represented the kinetic mechanism of dyeing,
indicating that chemisorption was the main mechanism involved. The equilibrium data were adjusted to
the Langmuir-Freundlich model indicating significant contribution from the chemisorption process. Dyeing
with the extract of eucalyptus leaves is a spontaneous and endothermic process with a high degree of
disorder. The notes washing fastness of dyed fabrics were 3-4 for the color change and 4 for staining on
cotton and wool.
Keywords: adsorption, coloration, washing fastness, langmuir-freundlich model.
GJRE-C Classification: FOR Code: 090499

NaturalDyeingofSilk withEucalyptusLeavesExtract

Strictly as per the compliance and regulations of:

© 2018. Nivea Taìs Vila. This is a research/review paper, distributed under the terms of the Creative Commons Attribution-
Noncommercial 3.0 Unported License http://creativecommons.org/ licenses/by-nc/3.0/), permitting all non commercial use,
distribution, and reproduction in any medium, provided the original work is properly cited.
 Natural Dyeing of Silk with Eucalyptus Leaves
Extract
Nivea Taìs Vila

Abstract- This study aimed to evaluate the process of silk In the last years, the dyestuffs in dustry has
dyeing with the extract of eucalyptus leaves. pH, temperature, been increasingly forced to reducetoxic effluents and
initial extract concentration was investigated. The initial extract stop the production of potentially azardous dyes and
concentration of 20 g L-1, pH 3 and temperature of 90 °C were
pigments(Mirjalili, Nazarpoor, & Karimi, 2011).Moreover,
the conditions which yielded the best results from dyeing. The
due to the in creased perception of environmental and

2018
pseudo-second order model was the one that best
represented the kinetic mechanism of dyeing, indicating that health risks associated with the synthesis, processing,

Year
chemisorption was the main mechanism involved. The and use of synthetic dyes, interest in natural dyes has in
equilibrium data were adjusted to the Langmuir-Freundlich creased worldwide. Therefore, a new market that value
model indicating significant contribution from the sproducts originated from natural raw materials is 1
chemisorption process. Dyeing with the extract of eucalyptus growing, with huge advantages to the environment(Ali,

Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

leaves is a spontaneous and endothermic process with a high 2007; Becht old & Mussak, 2009). Natural dyes are
degree of disorder. The notes washing fastness of dyed environmentally compatible, biodegradable, nontoxic,
fabrics were 3-4 for the color change and 4 for staining on
free of allergic effects, as well as available from a wide
cotton and wool.
range of sources that includes coloring from plants,
Keywords: adsorption, coloration, washing fastness,
insects, fungi and minerals(Ibrahim, El-Gamal, Gouda, &
langmuir-freundlich model.
Mahrous, 2010).
I. Introduction Among such a wide range of natural dyes,

T
eucalyptus deserves special attention because this tree
he art of applying color in fabrics has been known
may be found in many countries. The main components
for a long time. Historical records of the use of
of eucalyptus leaves that are responsible for the color
natural dyesextracted from vegetables, fruits,
given to textile materials are tannins (gallic acid and
flowers, insects and also fish date back to3500 BC.
ellagic acid) and flavonoids (rutin and quercetin). These
However, the importance of natural dyes disappeared
substances are considered very use fulduring the
since the advent of synthetic dyes, which have a wide
dyeing processdue to their ability to fix the dye within
range of colors and shades as their main
fabrics. Figure 1 shows the structures of the
advantages(Gurley, 1996; Kant, 2012).
components responsible for color found in eucalyptus
The generation of liquid effluents isa significant
leaves(Mongkholrattanasit, Kryštůfek, & Wiener, 2011).
environmental problem, since mostsynthetic dyesare
In all molecules there are hydroxyl groups and oxygen
complex aromatic molecular structures, which make
atoms that may be related to hydrolysis or partial
them inert with difficulty inbiode grading when
charges, which are probably responsible for attraction to
discharged into the environment(Khouni, Marrot, Moulin,
the silk residual groups.
& Ben Amar, 2011; Samanta & Agarwal, 2009).

Figure 1: Color composition of eucalyptus leaves extract.

Author: e-mail: nivea980@hotmail.com

© 2018 Global Journals

 Natural Dyeing of Silk with Eucalyptus Leaves Extract

The silk is composed of a protein called fibroin containing about 400 amino acid residues with the
surrounded by a gum called silk sericin, removed in the structure of the general type as shown in Figure 2
degumming process. Therefore, the silk fabric is (Iqbal, 2008).
basically fibroin. Fibroin consists of a long parallel chain

Figure 2: General structure of the fibroin.

2018

The residues are derived mainly from the amino applied in the fastness to washing procedure.
acids glycine (R = H), alanine (R = CH3), serine (R = Concentration of 2 g L-1 was used.
Year

CH2OH) and tyrosine (R = - CH2 --- OH), but there are

many others in small amounts (Iqbal, 2008; Needles, b) Dyeing process
2 1986). Influence of temperature, pH and initial
In the dyeing process, the colorants in solutions concentration of extract solutions was studied through
Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

hould adsorb, diffuse in to the fiber and finally, establish a23 complete factorial design composed of eleventrials,
with it physicochemical linter actions (Alcântara & Dalt three trialsas the central point. Dyeing of each sample
in, 1996; Salem, 2010). Unfortunately, such mechanisms lasted 60 minin AT1-SW Kimak equipment with a liquor
are not well understood as the process is stillempirical. ratio 1:100.The response variable was the amount of
The dyeing procedure and mainly the adsorption extract adsorbed in the fabrics. Table 1 lists the
mechanism have been scarcely reported. variables and levels for dyeing. Design-Expert software
In this context, the objective of this work was to version 7 was used.
study the ideal conditions for silk dyeing with eucalyptus
Table 1: Factorial design for dyeing of silk fabrics
leaves extract. Parameters such as initial concentration,
pH and temperature were investigated. The amount of
eucalyptus extract retained and color fastness to Numeric variables Levels Central
washing were the response parameters. The dyeing
-1 1 0
mechanism was investigated through kinetic and
T (°C) 80 90 85
isotherm models. Thermodynamic parameters were also
pH 3.0 4.0 3.5
obtained.
Initial concentration of 10 20 15
II. Material and Methods extract (gL -1)

a) Materials After dyeing, the samples were subjected to

Eucalyptus leaves (Eucalyptusgrandis) were washing with the non-ionic detergent solution at 60 °C
used in this work. Initially, the fresh eucalyptus leaves for 10 min., rinsed in cold water and dried at room
were dried in the open air for fifteen days and crumbled temperature.
in a blender.
The amount of extract adsorbedper gram of silk
Solutions of the eucalyptus leaves extract were
(q) (mgg-1) was determined through a mass balance as
prepared adding 10, 15 or 20 g of crumbled leaves in
described in Equation(1):
1000 mL of distilled water. Samples were then heated
with stirring at90 °C for 60 min and then filtered. The
filtrated solution was used in the dyeing process. q = (C0 − C f )V (1)
Concentration of the dyeing solutions was W
analyzed through spectro photometry. At first, the
where Vis the volume of the solution(L), W is the weight
wavelength of maximum absorption (λmax) of the filtrated of the silk (g), C0 is the initial concentration of
solution was obtained through the 1601DCS himadzue extract(mgL-1)and Cfis the extract concentration after
quipment. Biospectro SP 22 spectrophoto meter was dyeing(mgL-1).
calibrated with λmax to obtain the extract concentration
in solution. c) Kinetic of the dyeing process
Pure silk fabric ready for dyeing (70 gm-2) was Silk fabrics were put in contact with eucalyptus
used. The non-ionic detergent Nionlab CELM was extract in AT1-SW Kimak equipment in the

© 2018 Global Journals

 Natural Dyeing of Silk with Eucalyptus Leaves Extract

experimentally optimized conditions given by the adsorption processes, including dyeing(Arora, Gupta,
response variable of Table1. Rastogi, & Gulrajani, 2012; Kong kachuichay,
The fabrics were fast removed after dyeing at Shitangkoon, & Hirunkitmonkon, 2010; Lagergren,
different times. After cooling, all effluents were subjected 1898). A basic assumption of the Langmuir theory is that
to spectro photometric reading and extract adsorption takes place at specific homogeneous sites
concentrations determined. within the adsorbent. It is then assumed that once a dye
The amount of extract adsorbed per gram of molecule occupies a site, no further adsorption can take
fabric (qt) (mg g-1), at any time t, was calculated using place at that site. Theoretically, a saturation value is
Equation (1), where Cf takes the value of the reached when no further adsorption can take place. The
concentration at time t (Ct). saturated monolayer curve can be represented by the
Experimental data was modeled through the Equation (6):
pseudo-first order and pseudo-second order kinetic
qmax bCe
models. The pseudo-first order kinetic equation is the qe = (6)

2018
well-known Lagergren Equation(Lagergren, 1898). It 1 + bCe

Year
may be expressed as:
where in the equation, qmax (mg g-1) is the maximum
amount of the eucalyptus extract per unit weight of silk
3
= k1 (qe − qt )
dqt to form complete monolayer coverage of the surface. It
(2)
dt represents a practical limiting adsorption capacity when

Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

the surface is fully covered with dye molecules; b is the
where qe (mg g-1) stands for the amount of eucalyptus Langmuir constant related to the affinity of binding sites
extract when equilibrium is reached and k1 is the (L mg-1)(Arora et al., 2012; Lagergren, 1898; Langmuir,
pseudo-first order rate constant (min-1). 1918).
For the integration of Equation (2) with The Freundlich model assumes a
boundary conditions at t = 0, qt = 0, and at t = t, qt = heterogeneous adsorption surface with sites that have
qt, the nonlinear form of the equation becomes: different energies of adsorption and are not equally
available. Besides being more applicable, the
1 Freundlich isotherm provides no information on the
qt = qe (1 − ) (3)
monolayer adsorption capacity. It predicts a multilayer
e k1t
adsorption process and is written by Equation (7):
The pseudo-second order equation is: qe = k F Cen (7)

= k 2 (qe − qt )
dqt 2 where kF is the adsorption equilibrium constant of
(4)
dt Freundlich (L g-1) and n is the heterogeneity. In general,
as the kF value increases, the adsorption capacity
where k2 is the pseudo-second order rate constant increases. Values of n between 1 and 10 show favorable
(g mg-1min-1) (Ho, 2006). adsorption. If n < 1 and n→0, the silk fabric is saturated
Integration of Equation (4) generate: with the eucalyptus extract since adsorption energies
2
decreases with surface density (Dávila-Jiménez,
k 2 qe t Elizalde-González, & Peláez-Cid, 2005; Freundlich,
qt = (5) 1906).
1+ qe k 2t
The experimental data may be also fitted to the
The pseudo-second order rate expression is three-parameter model of Langmuir-Freundlich when the
used to describe chemisorption involving valence forces two-parameter models of Langmuir and Freundlich do
through the sharing or exchange of electrons between not provide reasonable results. The Langmuir-Freundlich
the eucalyptus extract and the fabric as covalent forces model is able to describe both the adsorptive behavior
(Ho, 2006). characteristic of the Langmuir type as the Freundlich.
Normally this model fits better in cases where the
d) Equilibrium of the dyeing process
adsorbent has heterogeneous surface, as it is the case
The equilibrium data was carried out using
of silk,(Iqbal, 2008; Needles, 1986) and is commonly
solutions of extract with different concentrations at 70,
expressed by the Equation (8):
80 and 90 ºC and the best pH given by results of the
factorial design. Solutions were put in contact with the [qm ( K LF Ce ) n ]
silk samples up to the equilibrium time obtained in the qe = (8)
[1 + ( K LF Ce ) n ]
previous section.
The Langmuir adsorption isotherm has been Where KLF is the adsorption constant of
successfully applied to a wide range of aqueous Langmuir-Freundlich (L mg-1), qmaxis the maximum

© 2018 Global Journals

 Natural Dyeing of Silk with Eucalyptus Leaves Extract

adsorption capacity (mg g-1), and n is the parameter of f) Color fastness to washing
heterogeneity (Chiou & Li, 2003). Sample dyed in the experimental optimized
conditions provided by results of Table 1 was submitted
e) Thermodynamic parameters
to color fastness to washing.
Gibbs free energy (ΔGº), enthalpy (ΔHº) and
The wash fastness test followed the procedures
entropy (ΔSº) were calculated by the Equations (9), (10)
of ISO 105-C06: 2006 A1S cycle - Tests for color
and (11) in 70, 80 and 90 ºC.
fastness: Part C-06: Color fastness to domestic and
C ad ,e commercial laundering(ISO, 2006).Evaluation of the
Kc = (9) transfer and change of color of the samples was
Ce performed using 550 Data color spectrophotometer.

∆G° = − RT ln K c (10) III. Results and Discussion

a) Wavelength of Maximum Absorption
2018

∆S ° ∆H °
ln K c = − (11) The UV-Vis wavelength range is show in Figure
Year

R RT 3.The extracts were able to absorb UV-C (wavelength

below 280 nm), UV-B (280-315) and UV-A (315-400)
4 where Kc is the equilibrium constant, and Cad,e and Ce regions (Feng et al., 2007).The highest absorbance was
are the eucalyptus extract concentration adsorbed at found at 197 nm
equilibrium with the concentration in the fluid phase
Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

(mg L-1), respectively.

Figure 3: UV-Vis spectrum of eucalyptus leaf extract.

Although there has not been any kind of the Biospectro SP22 UV-Visible spectrophotometer, with
isolation of the substances responsible for dyeing with a range of 300-1000 nm.
the aqueous extract of eucalyptus leaves, the absorption
in the region 190-210 nm can be attributed to various b) Silk Dyeing with Eucalyptus Extract
All samples of the dyeing process showed
chromophores, including the C = C bond of various
compounds, carbonyl compound bonding (C = O) and different yellowish-brown coloration, according to the
the benzene ring, probably from aromatic compounds. amount of extract adsorbed.
Absorption in the region of 250-270 nm can be Results of the factorial design are shown in Table 2.
attributed to electronic transitions of benzene and its
derivatives, which may include various aromatic
compounds such as phenolics (Pretsch, Buhlmann, &
Badertsscher, 2009). Absorption in the regions of 240-
285 nm and 300-550 nm, in turn, are characteristic of
flavonoid compounds(Lombard, Geoffriau, & Peffley,
2002).
The wavelength of 380 nm was used in all
concentration analysis due to experimental limitations of

© 2018 Global Journals

 Natural Dyeing of Silk with Eucalyptus Leaves Extract

Table 2: Results of the 23 factorial design used in evaluating the influence of the variables on the response (q) for the
silk dyeing with eucalyptus extract

Concentration
Test Temperature (°C) pH q (mg g-1) Color
(mg L-1)

1 - - - 149
2 + - - 290
3 - + - 197
4 + + - 350
5 - - + 86

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6 + - + 237

Year
7 - + + 102
8 + + + 274 5

9 0 0 0 210

Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

10 0 0 0 220
11 0 0 0 207

It was seen that the initial concentration of such as ion-ion forces and H-bonding, with van der
extract had a huge influence in the amount of Waals forces and hydrophobic interaction. Although not
eucalyptus extract retained in the silk fabric. Actually, knowing all molecular structures presented in the
concentration of 20 g L-1 promoted higher values of q eucalyptus extract, probably π - π could not be
than the diluted concentration of 10 g L-1. It happened neglected as well(Tang, Tang, & Yang, 2010).
due to the increase of the concentration gradient. Then, Specifically, the attraction between the
it may be concluded that initial concentration of extract eucalyptus extract and the fiber may have occurred
played an important role in the adsorption capacity of primarily by the large amount of tannins in the
eucalyptus extract onto silk, which is in total agreement eucalyptus leaves, since tannins contain phenolic
with results already reported(Chairat, Rattanaphani, compounds that can form hydrogen bonds with the
Bremner, & Rattanaphani, 2005; Farizadeh, Montazer, carboxyl groups of silk. There are two other possibilities
Yazdanshenas, Rashidi, & Malek, 2009; Lagergren, of interaction involved: (a) anionically charged phenolic
1898; Septhum, Rattanaphani, Bremner, & groups form an ionic bond with cationic (amino groups)
Rattanaphani, 2009). in the silk, and (b) a covalent bond may also form
Increasing temperatures also favored the through an interaction between any quinine or
adsorption process. It may be seen that 90 oC semiquinone groups present in the tannins and suitable
originated higher values of q if compared to 80 oC. It reactive groups on the silk(Mongkholrattanasit,
emphasizes that chemisorption is very important in the Kryštůfek, & Wiener, 2011). Such mechanism may
dyeing process. The positive influence of temperature emphasize the main contribution of chemisorption
may reflect an increase in the mobility of large extract although physisorption could be also present (Tang et
molecules. If so, an increase in the number of molecules al., 2010).
interacting with the active sites at the silk fabric was Considering the dyeing parameters studied
expected(Lagergren, 1898). herein, the highest response value was found in test 4,
Lower pH values provided higher q values. As in which the initial concentration of 20 g L-1, pH 3 and 90
the isoeletric point of silk filber varies between pH 3.6 ºC promoted the highest amount of 350 mg of
and 5.2(Sashina, Bochek, Novoselov, & Kirichenko, eucalyptus extract per g of silk. The effect and the
2006) at pH 3 the fiber was more positively charged. In contribution percentage on the response variable (q) are
this case, the acidic and, especially the protonated shown in Table 3.
amino groups of the silk fiber are of prime importance in
the uptake of anionic dyestuffs presented in the
eucalyptus extract (Lagergren, 1898). In such a case,
adsorption occurred as a result of electrostatic forces,

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 Natural Dyeing of Silk with Eucalyptus Leaves Extract

Table 3: Main effect and interaction between variables and the percentage contribution of the effects on the
response variable for silk dyeing with eucalyptus extract

Term Effects Contribution (%)

-1
A – Initial Concentration of extract (mg L ) 154.57 77.10
B – Temperature (°C) 39.75 5.10
C – pH -71.76 16.62
Interaction AB 8.28 0.22
Interaction AC 7.18 0.17
Interaction BC -13.80 0.61
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Interaction ABC 2.21 0.02

Year

Curvature 6.70.10-3
15.85
6 Lack of fit - 0.00
Pure error
Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

- 0.15

It was seen that the initial concentration of in the optimum contact time of 60 min. The same
eucalyptus extract had the greatest contribution in behavior was observed in the work of Septhum et al.
increasing the response variable (q), followed by pH and (2009) and Samanta & Konar (2011). Hence,
the temperature. Furthermore, the effect of pH on subsequent equilibrium experiments took into account
response variable was negative. It means that an such contact time. The higher dyeing rate in the early
increase in that variable decreased the value of q, which stages is possibly due to a large number of available
is in agreement with the experimental data. sites of adsorption in the silk. Decrease in the
adsorption rate was a consequence of decrease in the
c) Adsorption Kinetics
concentration gradient due to the increased number of
Figure 3a shows that the kinetic data carried out
sites already occupied by the extract molecules.
under the optimal conditions of 20 mg L-1, 90 oC and
pH 3 given by test 4. It may be seen that adsorption was The nonlinear fit of pseudo-first–order and
very fast in the early stages of contact time and pseudo-second-order models is shown in Figure 3b and
gradually decreased with time until it remained constant c, respectively.

Figure 4: Dyeing kinetics a) Effect of contact time of the kinetic adsorption of the eucalyptus extract on silk. b)
Graphic model of pseudo first-order. c) Graphic model of pseudo second-order.

© 2018 Global Journals

 Natural Dyeing of Silk with Eucalyptus Leaves Extract

It was observed experimental data was better R2 occurred in the pseudo-second-order model.
described by the pseudo-second order model. Indeed, Moreover, the amount of eucalyptus extract
Table 4 presents the quantitative results of the experimentally retained in the equilibrium was very
adjustments. It can be seen that higher correlation factor similar to the value estimated through the model.

Table 4: Comparison of kinetic models pseudo-first and second-order

qe,exp
(mg g-1) Pseudo first-order model
k1 (min-1) qe,cal (mg g-1) R2
0.10091 ± 0.015 355 ± 12 0.946
372 Pseudo second-order model
k2 (g mg-1 min-1) qe,cal (mg g-1) R2

2018
0.00034 ± 0.000r06 399 ± 12 0.978

Year
These data suggested that pseudo-second isotherms, mainly with increasing temperatures, which is
order kinetics model was predominant and that the characteristic of endothermic processes. This result may
overall rate of adsorption of eucalyptus extract on silk reflect an increase in the mobility of the dye ionic 7
was likely controlled by the chemisorption charges with temperature as already discussed. In the

Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

process(Lagergren, 1898). Adsorption of dyes in very beginning of the isotherm it was seen an induction
specific sites of silk was already reported(De Giorgi & period, which means that the dye molecules had nearly
Cerniani, 1991) and this is in agreement with the the same affinity for more dye molecules as the initial
influence of temperature and the possible attraction of sites of the silk fabric, characteristic of cooperative
the molecules to the positively charged silk at pH 3. adsorption. The rise and the pronounced plateau was
d) Adsorption Isotherm attributed to the development of the monolayer as a new
Equilibrium data and adjustments to Langmuir, surface where chemisorption could also occur. Then,
Freundlich and Langmuir-Freundlich isotherm models this plateau represented the saturation of such new
are shown in Figure 4a, b and c, respectively. At first, it surface. These isotherms may be classified as type S2
should be emphasized the favorable shape of the according to Giles, MacEwan, Nakhwa, & Smith(1960).

Figure 5: Adsorption isotherms models a) Langmuir. b) Freundlich. c) Langmuir-Freundlich.

It is well known that the Langmuir model may et al., 2005; Vinod, Puttaswamy, Gowda, & Sudhakar,
represent equilibrium data where chemisorption process 2011; Wei, Chen, Chen, Tang, & Zhang, 2013).
is involved, forming a dye monolayer in the silk (Chairat

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 Natural Dyeing of Silk with Eucalyptus Leaves Extract

Possibly, the monolayer occurred with the 70, 80 and 90 ºC were visually better adjusted to such
interaction between the hydroxyl groups of the dye and model.
the amino groups of the silk protein,(Vinod et al., 2011) Regression parameters for the model of
as already seen. On the other hand, the Freundlich Langmuir, Freundlich and Langmuir-Freundlich are
model is related to a multilayer process and may shown in Table 5. Actually, neither Langmuir nor
represent some dyeing process as well(Chairat et al., Freundlich single models provided reasonable
2005; Sawada & Ueda, 2003). Therefore, the Langmuir- adjustments according to the low correlation factor R2
Freundlich model that emphasizes the importance of and high deviations of the parameters. As already
both phenomena comes naturally as the model that may expected, equilibrium data was better fitted to the
represent the equilibrium data of the eucalyptus extract Langmuir-Freundlich model, which is in total agreement
in the silk fabric. In fact, experimental data obtained at with the isotherm shape.

Table 5: Model parameters of Langmuir, Freundlich and Langmuir-Freundlich isotherm

2018

Parameters 70 ºC 80 ºC 90 ºC
Year

Isotherm
qmax exp. (mgg-1) 376 402 428
qmax (mg g-1) 640 ± 77 721 ± 102 661 ± 68
8 Langmuir B 0.00008 ± 0.00002 0.00008 ± 0.00002 0.00012 ± 0.00003
R2 0.974 0.971 0.972
Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

kF 0.81 ± 0.65 0.68 ± 0.57 1.68 ± 1.31

Freundlich N 1.58 ± 0.22 1.52 ± 0.21 1.74 ± 0.26
R2 0.929 0.928 0.913
qmax. (mgg-1) 414 ± 11 440 ± 14 458 ± 8.7
kLF 0.00019 ± 8.22.10-6 0.00019 ± 9.17.10- 0.00024 ± 7.48.10-6
Langmuir- 6
Freundlich
N 1.87 ± 0.12 1.96 ± 0.15 1.96 ± 0.11
R2 0.998 0.997 0.998

The Langmuir-Freundlich model may predict includes contribution of physisorption and

qmax close to the experimental value qmax.exp at 70, chemisorption, with n equal to unity.
80 and 90 ºC. The heterogeneity parameter, n, assumes
values slightly greater than unity, indicating an e) Thermodynamic parameters
approximation to Langmuir isotherm, with the formation The results of the thermodynamic parameters,
of a homogeneous monolayer. Similar results can be ΔG°, ΔH° and ΔS° of eucalyptus extract adsorption are
seen in Tang et al.(2010) where adjustments to shown in Table 6.
Langmuir-Freundlich model were obtained. Such model

Table 6: Thermodynamic parameters for the adsorption of eucalyptus extract onto silk

Temperature (°C) Kc ΔG° (J mol-1) ΔH° (J mol-1) ΔS° (J mol-1K-1)

70 45.76 -10934
80 49.78 -11283 10258 61.61
90 55.76 -12166

The highest value of K c was obtained at 90 °C, each other, it confirmed the small and positive
indicating the most favorable equilibrium among the contribution of temperature (5.10%) in the dyeing
temperatures studied herein. Such results were in process. In confirmed that the dyeing process was
agreement with isotherm experimental data and the endothermic (ΔH°>0) as also previously
factorial design. ΔG°values were all negative, indicating observed(Vinod et al., 2011).
that the process was spontaneous. Moreover, the The positive value of ΔS° suggests an increase
increase in the temperature provided a slightly decrease of randomness at the solid-solution interface, originated
in the free energy. Such phenomenon may indicate that: of some structural changes in both adsorbent and
firstly, it is possibly related to the contribution of the adsorbate. These high values ΔS° are typical of
chemisorption in the process of retaining the eucalyptus endothermic processes(Hill Jr., 1977).
extract in the fiber(Komboonchoo & Bechtold, 2010) and
secondly, as the numerical values were very close to

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 Natural Dyeing of Silk with Eucalyptus Leaves Extract

f) Color Fastness to Washing 5. Chairat, M., Rattanaphani, S., Bremner, J. B., &
The indices of wash fastness in the optimized Rattanaphani, V. (2005). An adsorption and kinetic
conditions (initial concentration of extract of 20 g L-1, pH study of lac dyeing on silk. Dyes and Pigments,
3.0 at 90 °C) were considerable as acceptable. The 64(3), 231–241. https://doi.org/10.1016/j.dyepig.
color change was 3-4, while the staining on cotton and 2004.06.009
wool presented note 4. 6. Chiou, M. S., & Li, H. Y. (2003). Adsorption behavior
The good fastness properties of dyed silk fabric of reactive dye in aqueous solution on chemical
can be a consequence of the covalent bonds of tannins cross-linked chitosan beads. Chemosphere, 50(8),
with the fiber, as seen previously(Mongkholrattanasit, 1095–1105. https://doi.org/10.1016/S0045-6535 (02)
Kryštůfek, & Wiener, 2011). 00636-7
7. Dávila-Jiménez, M. M., Elizalde-González, M. P., &
IV. Conclusion Peláez-Cid, a. a. (2005). Adsorption interaction
between natural adsorbents and textile dyes in

2018
From this study it can be concluded that the silk
aqueous solution. Colloids and Surfaces A:
fabrics can be easily dyed with eucalyptus extract

Year
Physicochemical and Engineering Aspects, 254
yielding a yellowish-brown color. The best result was
(1–3), 107–114. https://doi.org/10.1016/j.colsurfa.
achieved using a dyeing temperature of 90 °C at pH 3
2004.11.022 9
and 20 gL-1 as extract initial concentration.
8. De Giorgi, M. R., & Cerniani, A. (1991).
By the way, concentration of the initial solution

Global Journal of Researches in Engineering ( C ) Volume XVIII Issue I Version I

Thermodynamic affinity of acid dyes on silk. Dyes
was the most relevant parameter of dyeing, followed by and Pigments, 15(1), 47–55. https://doi.org/
pH and temperature. 10.1016/0143-7208(91)87006-9
The pseudo-second order model best 9. Farizadeh, K., Montazer, M., Yazdanshenas, M. E.,
represented the kinetic data whereas equilibrium data Rashidi, A., & Malek, R. M. A. (2009). Extraction,
was adequately modeled with Langmuir-Freundlich identification and sorption studies of dyes from
equation. This adjustment may indicate that madder on wool. Journal of Applied Polymer
chemisorption has a huge importance in the dyeing Science, 113(6), 3799–3808. https://doi.org
mechanism. Probably the first monolayer based on ionic /10.1002/app.30051
bonds acted as another adsorption sites for a multilayer 10. Freundlich, H. M. F. (1906). Over the adsorption in
formed by hydrogen and covalent bonds. solution. The Journal of Physical Chemistry, 57,
The thermodynamic parameters ΔH°, ΔG° and 385–471.
ΔS° showed that the silk dyeing is an endothermic and 11. Giles, C. H., MacEwan, T. H., Nakhwa, S. N., &
spontaneous process with increased randomness at the Smith, D. (1960). Studies in adsorption. Part XI. A
solid-solution interface. System of classification of solution adsorption
The good fastness to washing probably isotherms, and its use in diagnosis of adsorption
occurred due to the presence of tannins in the mechanisms and in measurement of specific
eucalyptus extract that acted as mordant. surface areas of solids. Journal of the Chemical
Society, 3973–3993.
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