Journal of Molecular Liquids 248 (2017) 911–919

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Dyeability of recycled electrospun polyethylene terephthalate (PET)

nanofibers: Kinetics and thermodynamic study
Faraz Khan Mahar a, Mujahid Mehdi a, Umair Ahmed Qureshi a, Khan Mohammad Brohi b, Bilal Zahid c,
Farooq Ahmed a, Zeeshan Khatri a,⁎
a
Nanomaterials Research Group, Department of Textile Engineering, Mehran University of Engineering and Technology, Jamshoro 76062, Pakistan
b
Institute of Environmental Engineering and Management, Mehran University of Engineering and Technology, Jamshoro 76062, Pakistan
c
Department of Textile Engineering, NED University of Engineering and Technology, Karachi, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: Herein, we report for the very first time dyeing of recycled polyethylene terephthalate (r-PET) electrospun nano-
Received 1 September 2017 fibers from waste bottles using two different disperse dyes i.e. C.I Disperse Blue 56 (DB-56) and C.I Disperse Red
Received in revised form 14 October 2017 167:1 (DR 167:1). Since PET exhibit greater mechanical strength and is abundant in occurrence, therefore it was
Accepted 24 October 2017
selected for dyeing purpose. The thermodynamic, standard affinities and kinetic parameters were also evaluated
Available online xxxx
for the very first time. The dyeing process was found endothermic in nature based on positive values of enthalpy.
Keywords:
The standard affinity and diffusion coefficient of DB-56 towards r-PET were found greater than DR-167:1. The
Nanofibers proposed r-PET nanofibers offer many advantages such as excellent color fastness, good mechanical strength,
Dyeing low processing temperature and minimum dyeing time compared to other conventional nanofibers.
Thermodynamics © 2017 Elsevier B.V. All rights reserved.
Recycled PET
Electrospinning

1. Introduction
Nanofibers have emerged as versatile one dimensional
nanomaterials in all fields. The most wide applications of nanofibers
include biosensors [1,2], filtration [3], tissue engineering scaffolds [4],
protective clothing [5,6], wound dressings [7], drug delivery systems
[8,9], and nanofibrous composites [10].
The excellent processability and transparency properties in the poly-
ethylene terephthalate (PET) are to make sure to utilize as barriers,
nanofibers, sheets, and films. PET has been utilized for medical applica-
tions in cardiovascular implants like artificial heart valve, artificial blood
vessels and sewing rings [11]. Antimicrobial property in PET products,
have been focused as a target for improving the functionality and in-
creasing importance of medical textiles. Also, this antibacterial property
increases the worth of PET textiles to be used in daily life like clothing,
shoes, bedding, and interior materials for automobiles [12,13]. General-
ly, plastics are manufactured form PET solution; which is mostly used to
the manufacture numerous kinds of packaging specially soft drink bot-
tles. The total annual world's consumption of PET is around 13 million
tons [14]. Due to increasing consumption of PET based products and
their waste disposal issue, increasing environmental concerns have led
many researchers to transform these waste into valuable products
⁎ Corresponding author at: Nanomaterials Research Group, Department of Textile
Engineering, Mehran University of Engineering and Technology, Jamshoro, Pakistan.
E-mail address: zeeshan.khatri@faculty.muet.edu.pk (Z. Khatri).
[15]. Nicole E. Zander et al. [16] successfully utilized recycled PET into
nanofibers form for water filtrations applications.
Nanofibers products are the unique products, a few patents and
papers have been recently introduced for their apparel applications.
Nanofibers have been produced on production scale for apparel applica-
tions [17,18]. The results showed that nanofibers have excellent dura-
bility, without deteriorating mechanical properties when treated to
laundering. Nanofibers also show very good comfort, thermal and
water transfer properties [17]. Yoon and Lee et al. [19] have analyzed
that nanofibers gained much better waterproofing and breathability as
compared to conventional fabric. Z Khatri et al. [20,21,22,23] successful-
ly developed cellulose, cationic-cellulose & cellulose acetate based
nanofibers for apparel application and improved color yield through dif-
ferent techniques. One of our group fellow successfully developed cellu-
lose based nanofibers using ultrasonic technique in order to save energy
in same color yield of nanofibers [24]. A W Jatoi et al. [25] successfully
developed nylon-6 based nanofibers for apparel application and
compared effects of conventional and ultrasonic technique. Although,
an increased number of work has been devoted to dyeing of nanofibers
during past few decades but their thermodynamic and kinetic studies
were not investigated in detail. The literature study also lacks actual
binding capacity and mechanism of dye with nanofibers during dyeing
applications [26,27]. Therefore, we aim to develop r-PET nanofibers as
a novel scaffold for dyeing application compared with conventional
methods. Researchers are concerned with the development and imple-
mentation of new techniques in order to fulfill improvement in

https://doi.org/10.1016/j.molliq.2017.10.116
0167-7322/© 2017 Elsevier B.V. All rights reserved.
912 F.K. Mahar et al. / Journal of Molecular Liquids 248 (2017) 911–919

dyeability of polyester. For this purpose, variety of studies have been

devoted including: physical methods; chemical methods, and blending
of PET with different compounds in fiber production to enhance dye-
ability. However, some of these methods often damage the otherwise
excellent mechanical and bulk properties of PET fibers and make stable
production thereof difficult. They may result in increased costs of pro-
duction, which are not offset by the improvements in dyeability. Other
alternates offered to improve dyeability of PET polymers are developing
PET based composites such as nanoclay dispersed PET, silica loaded PET
but their preparation procedures were either energy or time consum-
ing. The extensive literature survey reveals that PET in nanofibers
form have not been tested for dyeability till to date. The kinetic behavior
and thermodynamic aspects also need to be explored to better under-
stand dyeing mechanism [28–31].
Study of nanofiber dyeing is challenging compared to conventional
dyeing due to greater surface area and low K/S values. It is also well
known that disperse dyes have affinity towards polyester polymer
[32]. Therefore, on the basis of the facts like good mechanical stability, Fig. 1. Chemical structures of (a) DR167:1 and (b) DB 56 dyes.

greater affinity and higher surface area; r-PET nanofibers were used as
a novel scaffold for disperse dyeing.
Additionally, other materials discussed above are costly, mechani-
cally weak, energy and time consuming. We, therefore, tried to develop
such material that should reduce energy, time as well as cost through
electrospinning of r-PET drinking bottle. These r-PET nanofibers dyeing
for apparel application will help reduce waste disposal issue and conse-
quently generate clean environment. In this report, the dyeing proper-
ties of r-PET nanofibers web with disperse dyes have been examined
to produce colored nanofibers for apparel use. PET polymer was
recycled from PET based drinking bottles and nanofibers were prepared
through electrospinning technique and were dyed with two disperse
dyes using exhaust dyeing method. The mechanical and chemical prop-
erties of dyed webs such as color yield, light fastness, washing fastness,
hot pressing and tensile strength were characterized using FTIR, SEM,
and XRD.
2. Experimental
2.1. Materials
Polyester polymer was obtained from the recycled PET bottles and
used directly without further purification. Foron Blue E-BL (CI-Disperse
Blue-56, low energy level) commercial disperse dyes and Foron Rubine
S-GFL 150 (CI-Disperse Red-167:1; high energy level) were collected
from Archroma Ltd. (Pakistan) which were used for dyeing and the
dye structures are shown in Fig. 1. The purpose to choose these dyes in-
cluded process stability, commercial treatment, range of energy levels
and color. Dispersing agent Lycol was used during dyeing.
achieve optimum time, temperature and L: R. dyeing of nanofibers
webs were carried out to examine the effect of dyeing temperatures
(50–110 °C), effect of dyeing times (1–60 min) and effect of dye concen-
trations (0.5–5% on mass of nanofibers web, omw) on color yields of
dyed nanofibers webs. After dyeing, each dyed sample were finally
given a gentle wash with tape water separately until no dye bleeding
was noticed.
The dye concentration before and after dyeing in the bath was ana-
lyzed using UV–vis spectrophotometer (Perkin Elmer USA). The total
amount of dye decrease in the dye bath was noted as the amount of
dye fixed on the nanofibers.
2.3.1. Dye sorption isotherm
25 mg of r-PET nanofibers were individually dyed in the solutions
containing 50 ppm, 100 ppm, 200 ppm, 300 ppm and 500 ppm of
both dyes (CI Disperse Red 167:1 & CI Disperse Blue 56) at optimum
temperature (90 °C) for 30 min. For dyeing the nanofibers, the liquor-
to-goods ratio was fixed at 100:1. Finally, the partition coefficients
(K) of dye between the bath Cb (mg/L) and the nanofibers Cf (mg/L)
in equilibrium were determined according to relation.
Cf
K¼ ð1Þ
Cb
2.3.2. Standard affinity
Eq. (2) shows that the standard affinity (−Δμ°) can be calculated by
using the partition coefficient (K) obtained from Eq. (1).

2.2. Electrospinning

Cf
−Δμ ° ¼ RT ln ¼ RT ln K ð2Þ
Cb
r-PET nanofibres were fabricated through electrospinning
technique. For that purpose, r- PET bottles were cut into small pieces
where, −Δμ° is the affinity of dye molecules to the nanofibers (cal/mol),
(approximately 1 × 1 cm2) followed by dissolution in TFA/Chloroform
R and T are the gas constant (1.9872 cal/mol K) and the absolute tem-
with 1:3 to make 15% w/w composition. Electrospinning was performed
perature (K), respectively.
via high-voltage power supply (Har - 100 ∗ 12, Matsusada Co.; Japan).
The prepared solution was put into a syringe attached with capillary
2.3.3. Enthalpy change
tip having internal diameter of 0.6 mm (tip to collector distance
According to the Clausius-Clapeyron equation, Eq. (2), the slope of
19 cm) and supplied voltage of 15–20 kV. After electrospinning, r-PET
Eq. (3) shows the dyeing enthalpy (ΔH°), and could be simply deter-
nanofibers were peeled off and dried overnight. The average nanofibers
mined by plot of −Δμ° /T versus 1/T.
thickness was found to be 140 μm.
!
°
−Δμ ΔH °
2.3. Nanofibers dyeing and adsorption ¼− þC ð3Þ
T T
The nanofibers webs were dyed by exhaust dyeing (100:1 liquor
ratio) on a laboratory HT dyeing machine. Five samples of r-PET nanofi- where, ΔH° and C are the heat of dyeing (cal/mol) known as enthalpy
bers, weighing 25 mg each, were dyed in five separate even baths to and the integration constant, respectively.
 F.K. Mahar et al. / Journal of Molecular Liquids 248 (2017) 911–919 913

2.3.4. Entropy change (ISO 105 - B02) [22–24].

The entropy change (Δ S°) of dyeing bath was calculated from the
experimental plot that shows the relationship between −Δμ° and T as K ð1−RÞ2
is shown by Eq. (4). ¼ ð6Þ
S 2R

In this equation, R shows reflectance decimal fraction dyed r-PET

−Δμ ° ¼ TΔS ° −ΔH ° ð4Þ
nanofibers and K represents the co-efficient of absorption, whereas S
is scattering co-efficient.

2.5. Characterizations
2.3.5. Dyeing rate parameters
In this work, the Hill's equation was employed to determine the
Scanning electron microscopy (S-3000N; Hitachi, Japan) with a high
diffusion coefficient of dye into different nanofibers. According to Hill's
voltage of 30 kV was used to observe the physical morphology of the
equation, the diffusion coefficient (D) was calculated by plotting.
dyed and undyed nanofibers webs. FTIR spectroscopy (IR Prestige-21
Ct/Cn versus t1/2 for the early stage of dyeing, using Eq. (5).
by Shimadzu, Japan) was used to analyze the chemical structure of
dyed and undyed nanofibers webs. XRD was used to analyze the crystal-

1=2 linity of dyed and undyed nanofibers webs.
Ct Dt
¼4 ð5Þ Universal testing machine (Titan Universal Tester 3-910 Company
C∞ πr2
Ltd., Germany) was used to observe the mechanical strengths of nanofi-
bers (dyed and undyed webs) by ASTM D-638 method. The crosshead
where, r is the radius of the cylindrical nanofibers in centimeter. speed on universal testing machine was set at 5.0 mm/min.

2.4. Measurement 3. Results and discussion

Color yield (K/S) values were measured using spectrophotometer X-
Rite (USA), CE-7000A. Final color yield (K/S) was obtained from nanofi-
bers samples after dyeing and calculated using Eq. (6). Before color
measurement, the nanofibers webs were folded such as to make four
(4) times thicknesses when placed on spectrophotometer. The
optimized dyed nanofibers webs were tested for color fastness to hot
pressing (ISO 105 - X11), washing (ISO 105 - C10: 2006) and light
3.1. Effect of dyeing temperature
As r- PET nanofibers were dyed very first time, it was therefore im-
portant to optimize dyeing conditions such as temperature, time &
dye concentration. First of all, influence of temperature was observed
at fixed time (30 min) and concentration of dye (2% shade on weight
of nanofibers) respectively during dyeing. Fig. 2(a) displays color yield

0.8
a 4 Blue Dyed NF
Red Dyed NF b Blue Dyed NF
Red Dyed NF

0.6
Partition coefficient

0.4
K/S

1 0.2

0 0.0
0 20 40 60 80 100 120 320 330 340 350 360 370

Temperature ,oC T (K)

c Blue Dyed NF d -200

-1 Red Dyed NF Blue Dyed NF
-400 Red Dyed NF

-2 -600

-800
Δμ°/Τ (cal/g.K)

-3
Δμ° (cal/g)

-1000

-1200
-4
-Δμ°

-1400
Δμ°/

-5 -1600

-1800
-6 -2000
2.7 2.8 2.9 3.0 3.1
320 330 340 350 360 370
-3
1/T (1/Kx10 ) T (K)

Fig. 2. (a) Effect of dyeing temperature on color yield, (b) Partition coefficient against dyeing temperature for both dyes, (c) relationship between Δ μ/ΔT and 1/T, (d) relationship
between −Δμ and T.
914 F.K. Mahar et al. / Journal of Molecular Liquids 248 (2017) 911–919

Table 1 3.1.2. Enthalpy and entropy changes

The partition coefficient (K) and the standard affinity (−Δ μ) of DB-56 and DR-167:1 The adsorption of dyes on nanofibers is an endothermic process and
on r-PET nanofibers.
absorb heat energy [20,25]. Obviously, the dyeing conditions, such as
Temperature (°C) DB-56 DR 167:1 types of nanofibers, dyes and the dyeing media affect the amount of
K −Δμ° (cal/mol) K −Δμ°(cal/mol) absorbed heat of dyeing. In fact, the enthalpy change in the dyeing sys-
tem shows the amount of energy required for interaction between the
50 0.06 −1805.83 0.0573 −1835.35
70 0.192 −1122.41 0.1153 −1471.93 polymeric chains of nanofibers and dyes. Consequently, the enthalpy
90 0.7 −257.28 0.36 −723.736 change is primarily considered as the measure of the adsorption
strength of dyes. Fig. 2(c) demonstrates the linear relationship between
Δμ/ΔT and 1/T on enthalpy change ΔH. The enthalpy changes for both
dyes are summarized in Table 2 According to this table, the enthalpy
Table 2 change of dye bath containing DB-56 is greater than the DR-167:1; i.e.
The enthalpy change (ΔH) and the entropy change (ΔS) of DB-56 and DR-167:1 on r-PET the bond strength of DB-56 dye was greater than DR-167:1. It is con-
nanofibers.
cluded that DB-56 molecules are more embedded to r-PET nanofibers
Parameters DB-56 DR-167:1 than the DR-16 7:1 because of their smaller molecular size [22].
ΔH° (cal/mol) 14,280 10,748 The Fig. 2(d) demonstrates, the linear relationship between -Δμ and
ΔS° (cal/mol. K) 38.71 27.71 T of DR-167:1 and DB −56 and according to Table 2, the entropy change
of DR-167:1 is lower than the DB-56. It means the DR-167:1 molecules
are less restrained in r-PET nanofibers than the DB-56 molecules be-
of nanofibers dyed due to influence of temperature during dyeing with cause, the DR-167:1 molecules are larger in size than the DB-56
DR-167:1, high energy level and DB-56, low energy level. The color yield molecules.
of both dyes gradually increased with increasing dyeing temperature
from 50 °C to 90 °C & thereafter decrease slowly. As increasing dyeing
temperature lowers the substantivity ratio of dye which reduced final 3.2. Effect of dyeing time and co-efficient of diffusion
color yield [23]. The temperature of dyeing was optimized at 90 °C in
both dyes. In order to gain higher color yield and observe the optimum dye-
ing time, dyeing of r-PET nanofibers was carried out at optimum
3.1.1. Standard affinity and partition coefficient temperature 90 °C using 2% shade of both dyes. The change in K/S
As shown in the Fig. 1(b), the partition coefficient is affected by dye- values was determined after every interval to reach the optimum
ing temperature. As the temperature increased, the partition coefficient time for maximum dyeing. The trend of optimum dyeing time is
of both dyes also increased. Since the adsorption of dyes on nanofibers is shown in Fig. 3. In case of both dyes, it was observed that color
an endothermic reaction process, the thermodynamic adsorption or the yield increased with increase in time and beyond 30 min no color in-
partition coefficient was increased by using higher temperature. As the crement was achieved. In Fig. 3, DB-56 shows rapid increased color
Fig. 1(b) shows, the rate of partition coefficient is greater for DB-56 dye yield as compared to DR-167:1 and this is because disperse blue
than the DR-167:1 dye. The differences originate from the different have low energy level and smaller molecular size [22]. In both
morphological properties of both dyes and their interaction with r-PET dyes, it was observed that the highest color yield was obtained at
nanofibers. 30 min and was chosen as optimum time for both dyes.
The difference between the driving forces of both dye molecules to- To compare the diffusion of DB-56 and DR-167:1 on r-PET nanofi-
wards r- PET nanofibers were studied by determination of the standard bers, the dyeing rates were obtained at 90 °C. Fig. 3(b) shows the dyeing
affinities of both dyes. Eq. (2) was used to calculate the values of affini- rate of DB-56 was greater than the DR-167:1.
ties. By using the isotherm data, K, at different temperature, the values According to Eq. (4), the Ct/Ce should be linearly proportional to the
of standard affinities were calculated and are shown in Table 1. t1/2 and diffusion coefficient could be obtained from the slop of the rela-
As the Table 1 shows, the standard affinity increases with increasing tionship. The diffusion coefficients of DB-56 is 0.154 and DR-167:1 has
temperature for both dyes. The standard affinity of DB-56 dye is higher 0.089. This represents that the smaller size of DB-56 makes it diffuse
than DR-167:1 dye. This finding reveals that the tendency of Blue dye is more rapidly than DR-167:1. The Blue dye showed higher diffusion co-
higher than the Red dye to r-PET nanofibers. efficient at 90 °C than the Red dye.

Fig. 3. (a) Effect of color yield on dyeing time; and (b) diffusion plots of DB-56 and DR-167:1.
 F.K. Mahar et al. / Journal of Molecular Liquids 248 (2017) 911–919 915

6
Blue Dyed NF Blue Dyed NF
a 5
Red Dyed NF
b 1.6 Red Dyed NF

1.4
4
1.2

Log Q e
3
K/S 1.0
2
0.8
1
0.6
0
0 1 2 3 4 5 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
Dye Concentration % Log Ce

Fig. 4. (a) Effect of color yield on dye concentration, (b) Freundlich Isotherm for both DB-56 and DR-167:1.

3.3. Effect of dyeing concentration
To investigate the color buildup of both dyes, the influence of dye
concentrations on color yield was examined as shown in Fig. 4(a). The
dye concentrations (0.5%, 1%, 2%, 3%, and 5% on weight of nanofibers)
were examined using optimized dyeing time and temperature.
Fig. 4(a) showed linear relationship between initial dye concentration
and K/S values. This demonstrates r-PET nanofibers exhibit a very
good ability to color build-up properties. It can be observed from the
Fig. 4(a) that higher concentrations of DR-167:1 gives slightly higher
color yield form the DB-56. The reason is quite clear: the molar extinc-
tion coefficient and affinity for each dye are different, resulting in differ-
ent color yield values [20]. For instance, DB-56 is based on Antraquinone
group and DR-167:1 is based on Azo group chemistry. The adsorption
capacity of both dyes on r-PET nanofibers and their binding affinities
were calculated through application of two well known isotherms, i.e.
Langmuir and Freundlich as follows:
Ce 1 Ce
¼ þ
qe qm K L qm
1 dyed r-PET nanofibers under optimized conditions through SEM analy-
logqe ¼ logC e þ logK f
n sis and Fig. 5(b, d and f) show the histogram of neat, blue and red dyed
where Ce is the equilibrium concentration of both dyes in the bulk solu-
tion, qe (mg/g) is the equilibrium adsorption capacity of r-PET nanofiber,
KL is (L/mg) is the Langmuir equilibrium constant, qm (mg/g) is the max-
imum adsorption capacity when adsorption achieves monolayer cover-
age. n is the adsorption index that determines degree of heterogeneity
of adsorbent surface. Kf (mg/(g (L/mg)1/n) is the Freundlich constant re-
lated to the adsorption capacity.
The application of both isotherms to experimental data suggested
that Freundlich isotherm is the best to explain adsorption mechanism.
Since higher temperature alters the geometry and crystallinity of r-
PET nanofibers. Therefore, the entire surface becomes energetically het-
erogeneous and the dyes may fix in different manner due to different
orientations (cis/trans conformations) of accessible sites. The isotherm
parameters are given in Table 3. The monolayer adsorption capacity of
Table 3
Langmuir and Freundlich isotherm parameters for dyeing of r-PET nanofibers.
Dyes Isotherm
Langmuir Freundlich
qm R2 KL n R2
DB-56 76.9 0.9785 0.01203 1.43
DR-167:1 370.73 0.7283 0.0043 1.998
DR-167:1 is greater than DB-56, most probably due to greater size and
increased mass transfer driving forces. But the affinity constant KL for
DB-56 dye is greater than DR-167:1 suggesting good affinity for the for-
mer than the later.
3.4. Color fastness test
Table 4 explains the washing fastness, hot pressing and light fastness
results of the dyed nanofibers webs (2% shed of both dyes at 90 C ֯
temperature & 30 min). Both dyes showed very good results in the
light fastness in dyed nanofibers webs and are being rated 7 on the
blue wool reference scale. The DR-167:1 showed slightly better results
in hot pressing than the nanofibers dyed with DB-56. The washing
test was done to check the color fastness properties of dyed nanofibers.
The nanofibers dyed with DB-56 and DR- 167:1 showed good to excel-
lent grade respectively using gray scale.
3.5. Nanofiber characterization
ð7Þ
3.5.1. Nanofiber Morphology
Fig. 5(a, c and e) show physical morphology of neat, blue and red
ð8Þ
nanofibers respectively. Images showed that the nanofibers possessed
smooth and bead free morphology. The average diameter of both dyed
nanofibers increased as compared to undyed nanofibers. The average
diameter of undyed r-PET nanofibers was 500 nm. After dyeing with
DB-56, average diameter increased to 1600 nm while with DR-167:1 in-
creased to 2300 nm. This may be explained on the basis of size as CI Red-
167:1 dye has more molecular weight than CI blue-56 and this changed
physical morphology showed that dyes were highly aggregated on r-
PET nanofibers. In addition to this, dyeing did not affect morphology
of nanofibers that suggested that r-PET can sustain their morphology
after dyeing.
3.5.2. FTIR Analysis
The FTIR spectrum of r-PET is shown in Fig. 6. The more prominent
absorption bands in neat r-PET nanofiber sample at 3100–2830 cm−1
are due to C\\H aromatic and aliphatic bond stretching, respectively.
The band at 3435 cm− 1 could be attributed to terminal OH group
of PET chain [33]. The band at 1743 cm − 1 is due to C_O bond
stretching whereas, peak at 1304 cm − 1 is associated with ester
group stretching. The band at 1150 cm− 1 may be attributed to the
methylene group from ethylene glycol moiety in PET polymeric seg-
ment. The other multiple and complex absorption bands from 1400
Kf
to 800 cm− 1 may be associated with either crystalline/amorphous
0.996 1.326 regions or geometrical isomerization (cis/trans conformation) of
0.9784 2.08
both ethylene glycol and phenylene carbonyl bonds [34]. After
916 F.K. Mahar et al. / Journal of Molecular Liquids 248 (2017) 911–919

Table 4
Color fastness to light (ISO 105-B02), hot pressing (ISO 105-X11) and washing (ISO 105-C10: 2006).

Dye conc.a (2%) Light fastnessb (20 h) Hot pressingc Washing fastnessc (shade change) Washing fastness (staining on multifibers strip)d

Change shade Staining CTA CT PA PET AC Wo

Blue disperse 7 4 3/4 4 4 4 4 4/5 4/5 3/4

Red disperse 7 4/5 4/5 4/5 4 4/5 4 4/5 4/5 4/5
a
Dyeing conditions: dyeing temperature 90 °C and time 30 min.
b
Blue wool scale 1–9 rating, 1 is poor and 9 is excellent.
c
Gray scale 1–5 rating, 1 is poor and 5 is excellent.
d
CTA cellulose triacetate, CT cotton, PA polyamide, PET polyester, PA polyacrylic, Wo wool.

dyeing with both dyes, the intensities as well as the positions of
all bands changed significantly. The band in r-PET nanofiber at
1743 cm − 1 shifted with band broadening to 1745 in both dyed
samples due to possible interactions of dyes functional groups
(most probably \\NH2 groups) with carbonyl carbon. The band at
1579 cm− 1 due to C_C aromatic stretching in r-PET nanofibers
also shifted to 1573 and 1575 cm− 1 due to weak Vander Waal forces
(π-π stacking between aromatic dye rings with PET aromatic rings).
All the regions from 1400 to 1000 cm− 1 due to crystalline and amor-
phous domains have also been changed in terms of their positions
and intensities that imply geometric changes due to participation
of hydrogen bonding and weak Vander Waal forces between dyes

Fig. 5. (a–b) SEM image and histogram of neat PET nanofibers; (c–d) SEM image and histogram of blue dyed r-PET nanofibers; (e–f) SEM image and histogram of red dyed r-PET nanofibers.
 F.K. Mahar et al. / Journal of Molecular Liquids 248 (2017) 911–919 917

Fig. 6. FTIR of Neat r-PET (a); blue dyed r-PET (b) and red dyed r-PET nanofibers (c); mechanism of interaction of DB-56 (d) and DR-167:1 with r-PET (e). (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

and PET functional groups [35]. Based on FTIR results, the proposed
mechanism of interactions of both dyes with r-PET may be illustrated
in Fig. 6(d and e).
3.5.3. XRD Analysis
The Fig. 7(a, b and c) shows the effects on diffraction patterns of
neat r-PET, blue dyed PET and red dyed PET nanofibers respective-
ly. There were two main peaks observed in neat r-PET nanofibers at
16.4° and 46.7°. The results show that diffraction angle shifts from
16.4° to18.4° and 46.7° to 44.7° when dyed with DB-56 PET nano-
fibers; while in case of red dyed PET nanofibers the diffraction
angle shifts from 16.4° to 25.6° and 47° to 46.5°. It clearly indicated
that crystallinity of dyed nanofibers increased after dyeing process
[36,37].
3.5.4. Mechanical behavior
Mechanical properties of dyed and undyed r-PET nanofibers are
shown in Fig. 8. The values showed that strength of dyed PET nano-
fibers increased. It can be due to more crystalline behavior achieved
during dyeing of r-PET nanofibers as compared to undyed nanofi-
bers. This result is in agreement with XRD results as well (Fig. 7).
This indicates that the dyed nanofibers become stiffer than the un-
dyed nanofibers and this was due to heat provided during dyeing
process. Exhaust dyeing was carried out on “blank sample” (i.e.
Just water or without water) with same parameters which
confirmed that major influence of strength on nanofibers was due
to heat during dyeing.
The Table 5 indicates that comparatively dyeing of r-PET nanofibers
have better results of color yield in less time, and concentration. This
confirmed that dyeing of r-PET nanofibers saves time, material
918 F.K. Mahar et al. / Journal of Molecular Liquids 248 (2017) 911–919

4. Conclusion

r-PET based waste bottles were electrospun to achieve highly cheap

and efficient nanofiber mat for apparel applications. The dyeing
properties of both dyes indicated that DB-56 had greater affinity towards
r-PET based nanofibers than DR-67:1. The partition coefficient of both
dyes gradually increased with increasing dyeing temperature and the
optimum temperature and time was found to be 90 °C and 30 min
respectively. The enthalpy and diffusion coefficient of DB-56 were
found greater DR-167:1 suggesting greater affinity of former than the
later. The nanofibers dyed with DB-56 and DR-167:1 showed good to ex-
cellent washing fastness. SEM analysis depicted that the average diameter
of both dyed nanofibers increased significantly compared to undyed
nanofibers. The dyeing process provided the r-PET nanofibers with higher
tensile strength and crystallinity. The mechanism of dye-PET was found to
be physical interactions through hydrogen bonds and weak Vander Waal
forces. Freudlich isotherm was found to fit well to experimental data. The
proposed r-PET nanofibers may be recommended for advanced apparel
applications due to their low energy consumption, less processing time,
low material cost, good color yield and higher mechanical strength com-
pared to other nanofiber materials previously reported.

Fig. 7. XRD patterns of neat, blue and red dyed r-PET nanofibers. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this
article.)
Acknowledgment
The work was supported by Mehran University of Engineering and
Technology, Jamshoro Pakistan and Shinshu University Japan.

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Fig. 8. Mechanical strength of undyed, blank and dyed PET nanofibers.
consumption and energy compared to previously reported materials
under exhaust dyeing method. Furthermore, this PET dyeing was uti-
lized from waste drinking bottles, through which waste disposal issue
can be resolved.
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