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Water repellent treatment for cotton fabrics with

long-chain fluoropolymer and its short-chain eco-
friendly alternative

Sondes Gargoubi, Ayda Baffoun, Omar Anis Harzallah, Mokhles Hamdi &
Chedly Boudokhane

To cite this article: Sondes Gargoubi, Ayda Baffoun, Omar Anis Harzallah, Mokhles Hamdi
& Chedly Boudokhane (2019): Water repellent treatment for cotton fabrics with long-chain
fluoropolymer and its short-chain eco-friendly alternative, The Journal of The Textile Institute, DOI:
10.1080/00405000.2019.1664796

To link to this article: https://doi.org/10.1080/00405000.2019.1664796

Published online: 14 Sep 2019.

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THE JOURNAL OF THE TEXTILE INSTITUTE
https://doi.org/10.1080/00405000.2019.1664796

ARTICLE

Water repellent treatment for cotton fabrics with long-chain fluoropolymer

and its short-chain eco-friendly alternative
Sondes Gargoubia,b, Ayda Baffounc, Omar Anis Harzallahd, Mokhles Hamdic and Chedly Boudokhaneb,e
a
Textile Engineering Laboratory - LGTex, University of Monastir, Monastir, Tunisia; bLaboratory of Dyeing Services and Textile Treatments,
Chimitex Plus, Sousse, Tunisia; cTextile Materials and Processes Research Unit (MPTEX), National Engineering School of Monastir, Av. Ibn
ElJazzar 5019, University of Monastir, Monastir, Tunisia; dLaboratory of Physics and Mechanics Textile (LPMT), ENSISA - University of Haute
Alsace, Mulhouse, France; eResearch Unity of Applied Chemistry and Environment, Faculty of Science of Monastir, University of Monastir,
Monastir, Tunisia

ABSTRACT ARTICLE HISTORY

As the long-chain fluorochemical molecules used to obtain water and stain repellent textiles persist in Received 11 July 2018
the environment, chemical suppliers are trying to develop new products in order to find ecological Accepted 3 September 2019
alternatives. The current most developed substituents are based on molecules with shorter fluorine-
KEYWORDS
carbon chains. In the current work, a long-chain fluoropolymer and its short-chain homologue were
Water repellency; cotton;
applied on cotton fabrics at different finishing conditions. Textile properties such as wettability, air per- long-chain fluoropolymers;
meability, mechanical properties and handle properties, for untreated and treated cotton samples short-chain fluoropolymers;
were investigated. Laundering test was also performed to predict the durability of the finishing. The performance; eco-friendly
obtained results demonstrated that cotton samples treated with short-chain fluoropolymer show good
water repellency and good washing durability. The use of short-chain fluoropolymers, as nontoxic and
eco-friendly finishing chemicals, has allowed obtaining comparable performances to those produced
with long chain fluoropolymer.

Introduction on almost all textiles (Slade, 1997). The use of fluorochemi-

In recent years, there has been a growing concern from con-
sumers in advanced textile materials which provide func-
tional properties while remain nontoxic and eco-friendly in
use (El-Shafei, ElShemy, & Abou-Okeil, 2015; Gargoubi
et al., 2016). Water repellent textiles are among the most
required advanced materials for protective clothes and prod-
ucts (Shateri-Khalilabad & Yazdanshenas, 2013). Water has
a high surface tension (72.8 mN/m). Therefore, water repel-
lency properties are conferred by reducing the surface
energy of textile substrate to prevent drops of water from
spreading on the surface and wetting the fabric (Ferrero &
Periolatto, 2015). The surface modification of textile mater-
ial energy can be carried out by physical or chemical treat-
ments or by the association of both (Ferrero & Periolatto,
2013; Ferrero, Periolatto, & Tempestini, 2017). The current
textile and fabric finish market is dominated by the use of
chemical treatments (Holme, 1993). Chemical method
allows the treatment of garments and large textile substrates
that would be difficult to treat by most physical techniques
such as plasma and corona discharge treatments (Shahidi,
Wiener, & Ghoranneviss, 2013). A variety of chemicals has
been used to produce water repellent textiles. However, very
few of these compounds were found effective on all fiber
types. Commercially, chemical substances that contain fluor-
ine have been favored and recognized for their effectiveness
cals to produce water repellent surfaces is well established in
the current textile market.
Recently, finishes having perfluoroalkyl long-chains with
eight or more fluorinated carbons have come under survey
because of their potentially hazardous residual chemicals.
These long-chain polymers generally contain long-chain per-
fluoroalkyl acids (PFAAs) as traces impurities. Long-chain
PFAAs were found to degrade in the environment resulting
in the release of perfluorooctanoic acid (PFOA) and per-
fluorooctanesulfonate (PFOS). A vast range of these com-
pounds having toxicological properties of concern have been
detected in the environment, wildlife and humans (Buck
et al., 2011). As a result, the European Union has prohibited
PFOS and has recently published measures to regulate
PFOA, its salts and related substances (Jiang et al., 2016).
The major challenge facing textile industries developing water
repellent garments and fabrics is to rapidly switch to safe
alternatives. To achieve this goal, chemical suppliers are
developing new products in order to substitute long-chain
PFASs (Mazzoni, Polesello, Rusconi, & Valsecchi, 2015).
Reports in the literature show that alternative water repellent
finishes are increasing in availability and they are classified
into three groups: fluorine free chemicals, nanotechnology
finishes and short-chain fluorochemicals (Åkerblom &
G€oranzon, 2014; Jiang et al., 2016; Zhang et al., 2003).

CONTACT Sondes Gargoubi gargoubisondes@yahoo.fr Textile Engineering Laboratory- LGTex, University of Monastir, Monastir, Tunisia
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/tjti.
ß 2019 The Textile Institute
2 S. GARGOUBI ET AL.
Table 1. Cotton fabric specifications.
Composition Yarn count (tex)
Weave Warp Weft Warp
Twill 100% Cotton 95% Cotton, 5% elastane 16  3
Potential substitute fluorine free chemicals for the long-chain
PFASs include paraffin waxes, silicones, polyurethane and
dendrimers (Holmquist et al., 2016). Numerous organic and
inorganic nanoparticles were applied as nanotechnology fin-
ishes providing water repellency on textile surfaces. These
chemicals were applied using advanced techniques such as
plasma deposition (Manepalli, 2016). Short-chain fluorochem-
icals were also used as safe alternatives. They are fluorinated
substances that consist of much smaller molecules than their
long-chain homologues. Their short chain length make them
less stable in the environment and thus less toxic (Barmentlo
et al., 2015). Even though different alternative finishes were
able to provide water repellency, none of them was found to
perform as well as long-chain fluorochemicals (Wang,
Cousins, Scheringer, & Hungerb€ uhler, 2013). As they are
fluorine based, short-chain substances are considered the best
repellent alternatives since they offer the advantage to provide
good water repellency and to extend the finishing effect life-
time by reducing the staining tendency and thus reducing the
washing cycles (Schellenberger et al., 2017).
The main objective of this study is to investigate the
effect of the application conditions on the efficiency, the
performance and the lifetime of currently available long-
chain and short-chain fluoropolymers applied on cotton fab-
ric as water repellent agents. This comparative study can
help textile industries to find alternatives for the long-chain
fluorinated chemicals which are effective but harmful to the
environment.
Experimental
Materials
Long-chain (Fluorotex FO) and short-chain (Fluorotex
ECO) fluorochemicals, crosslinking agent (PU/B) and non-
ionic detergent (WIDET MS/V) were kindly provided by
S2C chemical supplier. Desized, bleached and mercerized
cotton fabric was used as substrate. The fabric was further
purified by washing in warm water using a nonionic deter-
gent (1 g/L). After washing, the fabric was rinsed with water
three times and dried at 70
C for 10 min. Specifications of
the used fabric are shown in Table 1.
Textile treatment with water repellent agents
The water repellent agents were applied on cotton fabrics by
typical padding-curing process using a horizontal padder
(MESDAN). Cotton samples were impregnated in the finish-
ing bath at a padder moving speed of 7 m/min, ambient
temperature (25
C) and a padding pressure of 1 bar. The
pick-up percentage was about 80%. The padded samples
were dried at 90
C for 20 min and then cured in a labora-
tory oven (Memmert) for two different durations (1 and
Density
Weft Warp (ends/cm) Weft (picks/cm) Weight (g/m2)
22  2 20 14 212
5 min) and at two different temperatures (120 and 150
C).
Acetic acid (0.1 mL/L) was used to adjust the finishing bath
pH between 5 and 6.
Different finishing baths were applied to evaluate the
water repellent properties of treated samples. First investiga-
tions were performed using two concentrations of long-
chain fluorochemical (3 and 5% by weight). For investiga-
tions on eco-friendly treatment, short-chain fluorochemical
was applied at two different concentrations (10 and 30%
by weight).
The concentration ranges were selected according to the
supplier’s recommendations in order to establish suitable
levels of performance. For short-chain repellents, application
of more chemical was recommended to limit any drop in
performance. In addition, a crosslinking agent based on
blocked isocyanate was used to increase performance.
Schematic of the proposed mechanisms of crosslinking reac-
tion regarding each fluorinated agent is presented in Table 2
(Audenaert, Lens, Rolly, & Vander Elst, 1999; Gao, Gu,
Wang, Li, & Bai, 2005; Nasar & Kalaimani, 2016).
Characterizations
Attenuated total reflectance Fourier-transform infrared
(ATR-FTIR) spectroscopy was used to monitor the differ-
ence between chain lengths and to characterize textile surfa-
ces. FTIR spectra were recorded using a commercial ATR-
FTIR attachment (Spectrum TwoTM FTIR, Perkin Elmer).
Spectra were recorded between 4000 cm1 and 400 cm1.
All samples (Table 3) were conditioned at 20 ± 2
C and
65 ± 2% RH for 24 h before the wetting tests. Contact angle
measurements were performed using Digidrop tester (GBX
Digidrop). A volume of 5 mL distilled water was deposited
on the sample surface and the drop shape was recorded for
60 s by means of a video camera. The results shown for
each sample are average of three measurements.
The spray rating test was realized in accordance with the
AATCC test method 22-2005. During the test, each sample
(18 cm  18 cm) was maintained at an angle of 45
under a
spray nozzle. Then, 250 ml of distilled water was sprayed
onto the surface of sample over 30 s. Each tested sample is
assigned a rating corresponding to the nearest standard in
the standard spray test ratings. Intermediate ratings can be
used for ratings of 50 or higher.
Surface morphologies of untreated and treated cotton
surfaces were carried out by pressure-controlled scanning
electron microscope (SEM Hitachi S-2360N). Cotton sam-
ples were sputter coated with conductive gold and observed
in the SEM at an accelerating voltage of 22 kV. Imaging
parameters were regulated on the appropriate way to protect
the original state of analyzed textiles.
 THE JOURNAL OF THE TEXTILE INSTITUTE 3

Table 2. Schematic of the mechanisms of crosslinking reaction regarding each fluorinated agent.
Fluorinated agent Mechanism of attachment
Long-chain
R'
O
H 2
h - C
OR NH
f
OR
CO CO C O
OH OH OH
+

Cotton

T R' OH

Long-chain
Cotton

O
OH OH
-O
H2
-C
OR
h
NH
f
OR
CO CO CO

Short chain
OR
h
OR
f
' O
CO CO R'
OH OH
+ R N C B +

H
Cotton
Blocked isocyanate

T B
Short chain

R' CO
OR
CO

'
OR

h
CONH
f

OH OH O

Cotton

Air permeability and mechanical properties

Air permeability was determined by the rate of flow of air
passing perpendicularly through the textiles at a given pres-
sure difference and over a given time period. The tests were
conducted using air permeability tester FX 3300 (Karl
Schr€
oder KG, Germany), as specified in ISO 9237 at pres-
sure drop of 200 Pa.
Tensile tests were carried out according to NF EN ISO
13934-2 standards using a Lloyd tensile testing machine
(Lloyd LR 5k, Lloyd Instruments Ltd.) with 5 kN load cell.
A gauge length of 75 mm and testing speed of 50 mm/min
were used. The samples were conditioned before testing.
Tests were conducted at the warp direction of the fabric
and ran in triplicate to reduce experimental error.
4 S. GARGOUBI ET AL.

Table 3. Treating conditions and spray test rating of different samples.

Spray test rating
Concentration (FA) a b c d
Long-chain
Sample 1 3% 70 70 80 70
Sample 2 5% 70 70 90 80
Short-chain Concentration
(FA) (CA)
Sample 3 10% 5% 70 70 70 70
Sample 4 15% 70 70 80 70
Sample 5 30% 5% 80 80–90 90 80
Sample 6 15% 70 70 80–90 70–80
Untreated 50
Curing conditions: a (120
C/1 min), b (120
C/5 min), c (150
C/1 min) and d (150
C/5 min)

Table 4. Evaluated properties and specifications of standard KES-FB system.
Tester Properties Parameters
KES-FB1 Shear G: Shear stiffness
2HG: Shear hysteresis at 0.5

2HG5: Shear hysteresis at 5

KES-FB3 Compression LC: Linearity of compression curve
WC: Compressional energy
RC: Compressional resilience
T0: Thickness at pressure 0.5 gf/cm2
Tm: Thickness at pressure 50 gf/cm2
KES-FB4 Surface MIU: Coefficient of friction
MMD: Mean deviation of MIU
SMD: Geometrical roughness
Objective evaluation of handle properties
The handle properties of cotton fabrics were evaluated by
the testers of KES-FB series (Kawabata’s Evaluation System
for Fabrics). This system consists of four test instruments
for conducting surface, bending, compression, tensile and
shear tests. It was used for the investigation of the cotton
fabrics before and after water repellent finishing. Table 4
gives some data on parameters, properties and the testers
used during this study. Tests were realized following cotton
samples preconditioning in a standard atmosphere
(20 ± 2
C, 65% ± 2% RH). Standard size samples of 200 mm
 200 mm were tested in warp direction. Three replicate
measurements were made for each sample. Tests were con-
ducted according to standard KES-FB specifications.
Evaluation of laundering durability
The permanence of water repellent treatment after washing
was investigated by subjecting each fabric sample to repeated 8
washing cycles. The treated cotton fabrics were washed in
Autowash, using ISO 105-C06 standard method
(Phattanarudee, Chakvattanatham, & Kiatkamjornwong, 2009).
Laundering involved a washing temperature of 40
C for
30 min with 150 mL of water containing 0.6 g of nonionic
detergent. Samples were then dried for 10 min at 70
C.
Results and discussion
ATR FTIR characterization
Using ATR-FTIR spectroscopy, fluorinated repellent agents
were identified as polyfluoro(meth)acrylates chemicals.
These copolymers, also known as perfluoroalkyl, are usually
Units obtained from copolymerization of fluorinated(meth)acry-
gf/cm.
(N/m.
) lates (Rf) with common hydrocarbon monomers (Rh)
gf/cm (N/m )
gf/cm (N/m )
(Ceretta, 2013; Yao, Li, & Huang, 2014).
– Part a) in Figure 1 shows the FTIR spectra of these
gf.cm/cm2 agents. The ester carbonyl (C ¼ O) group of the acrylate-
(N.m/m2)
%
copolymer was identified by the characteristic peak at
mm approximately 1730 cm1. The typical broad peak at
mm 1640 cm1 was designated as the characteristic of double
–
– bonds (C ¼ C) in acrylic and methacrylic monomers. The
mm characteristic absorption peaks of aliphatic C  H stretching
appear at 2850 and 2920 cm1. Overlapping peaks of
F  CF and C  OC stretching appear between 1100 and
1250 cm1 (Jiang et al., 2016; Yang, Shen, Zhang, & Li,
2015). The characteristic absorption peak of the symmetric
CF2 stretching vibration (ms CF2) band has recently been
revealed useful for the detection of the number of CF2 units
(the chain length) (Hasegawa, 2017). The results of
Shimoaka et al. (2017) show that the (ms CF2) band has an
apparent higher wavenumber shift with increasing the chain
length (n) (Shimoaka et al., 2017). Based on these results
and the ATR-FTIR data shown in Figure 1(a), we were able
to estimate the spread of chain lengths. The bands at
1145 cm1 and 1149 cm1 are assigned to the symmetric
CF2 stretching vibration of short chain and long chain fluo-
rochemicals, respectively.
The inset in Figure 1(a) shows the wavenumber shift of
(ms CF2) band. We found that for Fluorotex FO (n  9) and
for Fluorotex ECO (5 < n  7).
FTIR spectra of the cotton fabric before and after treat-
ment with fluoropolymers were presented in Figure 1(b).
Spectra of all samples showed characteristic peaks of cellu-
lose. The broad bands in the 3330 cm1 regions are attrib-
uted to hydroxyl groups (O-H) stretching vibrations, the
broad stretching vibration of C-H is centered at 2890 cm1,
while C-H bending vibrations are detected at 1416, 1360
and 1300 cm1, asymmetric stretching of C-O-C appeared at
1157 cm1 and the vibration involving the C-O stretching
appeared at 1055 cm1 and 1034 cm1 (Gargoubi et al.,
2016). The ATR spectrum of the polyfluorinated cotton
using short-chain fluoropolymer displayed a new peak at
approximately 1740 cm1. This absorption peak corresponds
to ester moieties in polyacrylate (Maity, Kothary, O’Rear, &
Jacob, 2010). The absorbance of this peak appears affected
by polymer chain length. Typical peaks due to C-F

1145 cm
Transmittance (%)
1149 cm
1160
Short-chain
Long-chain
4000 3500 3000 2500 2000 1500
Wavenumbers (cm)-1
Figure 1. ATR-FTIR spectra of: (a) long-chain and short-chain fluorochemicals and (b) the treated and untreated cotton fabrics. (An offset is added between spectra
for clarity).
stretching between 1150 and 1210 cm1 are just barely
detectable. They are overlapped to cellulose peaks (Ferrero
et al., 2017). These peaks indicate that the fluoroalkyl chains
have been attached to the cotton surface.
Wetting properties and surface morphology analysis
Static contact angle measurements were used to evaluate
hydrophobic property of cotton fabrics before and after flu-
orinated finishes. Figure 2 shows the value of water contact
angle obtained at various conditions. It is seen from
Figure 2(a) that cotton fabrics treated with 3% of long-chain
fluoropolymer exhibit a higher contact angle of 127
. With
the increase in concentration from 3% to 5%, water contact
angle is increased from 127
to 133
.
The same behavior was observed with fabrics treated in
baths containing 10% to 30% of short-chain fluoropolymer.
Water contact angle was increased. With 30% short-chain
chemical, the droplet reaches a contact angle of 130–132
degrees. This result reveals that fluoropolymer concentration
has strong effect on the hydrophobic property of the treated
fabric. With more chemical, surface became polymer-satu-
rated and all porous are recovered.
Figure 2(b,c) show that the use of the crosslinking agent
at certain concentration has slightly increased contact angles
values. Crosslinking agent has a significant effect on creating
interactions between the short-chain fluoropolymer and the
cotton surface.
Static contact angle measurements were also used to
evaluate variations in hydrophobic property that result from
variation in curing conditions (temperature and time).
The conditions investigated in the study were chosen for
their common application in textiles coating finishes. The
data presented in Figure 2 indicate that heat treatment led
to a gradual increase in the water repellency of the treated
surface. Therefore, the greater is the curing temperature, the
greater is the contact angle value. Referring to the literature,
the result was explained by the fact that higher temperature
THE JOURNAL OF THE TEXTILE INSTITUTE 5
(a) (b)
-1
-1
1120
Short-chain
Long-chain
brut
Untreated
1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm)-1
helps better polymer chains crosslinking and surface attach-
ment leading to better water barrier performance (Pan,
Schaefer, & Ilavsky, 2006; Rabilloud, 1997).
Curing time was also found to be related to the change in
water repellency property of textile substrates. With a curing
temperature of 120
C, the longer the textiles were cured, the
greater was their hydrophobicity. However, fabrics cured for
several min (5 min) at 150
C showed a decrease in contact
angle values. High curing temperature for long treating time
was reported to develop coating microcracks which leads to
debonding of the coating and allows water accessing
the surface.
In addition to water contact angle, that shows the surface
wettability of treated fabrics, water repellency was evaluated
to show waterproof properties. The spray rating of all sam-
ples were shown in Table 3, respectively. It was found that
all treated samples showed increased resistance to water
penetration. Like contact angle results, the spray rating
increased continuously with increasing fluorochemicals con-
centration and the best could reach 90, indicating good
water repellency gained from water repellent treatment.
Crosslinking agent concentration and curing conditions
were also found to affect the spray rating in same manner
as for contact angle values.
SEM images were taken to investigate changes in the
fiber surface morphology after water repellent finishes as
well as the distribution of fluoropolymers on the surface.
Some representative pictures taken on different samples at a
magnification of 1000 are shown in Figure 2. The
untreated surface was found relatively smooth. Long chain-
treated surface using 3% of polymer was as smooth as the
untreated surface. Pictures do not reveal significant differen-
ces between them. It was extremely difficult to visualize
polymer entities on the fibers. Surface apparent smoothness
showing no evidence of polymer attachment does not
appear to negatively affect the effectiveness of the water
repellent treatment as indicated by the contact angle meas-
urements. With the increase in concentration from 3% to
6 S. GARGOUBI ET AL.
Figure 2. SEM images and static contact angle values of treated cotton fabrics. The inset is the image of untreated cotton.
5%, the surface of the cotton becomes a little rougher with
the presence of some dispersed polymer entities. It was
clearly visible that the fluoropolymer was successfully
imparted to cotton fabric.
In the case of the short-chain fluoropolymer, both rough
aspect and polymer traces were observed on the fiber surfa-
ces as shown in Figure 2(b,c). In addition, a trend of
increasing hydrophobicity with surface roughness was again
observed with increasing fluoropolymer concentration. This
result is in agreement with previous studies showing that an
increase in surface roughness will increase its contact angle
(Chau, Bruckard, Koh, & Nguyen, 2009; Extrand, 2004).
Increasing crosslinking agent concentration was unexpect-
edly inadequate to enhance water repellency when using
30% of short-chain fluoropolymer. SEM analysis suggests
that this behavior could be due to nonuniform coating of
the fabric, possibly caused by excess of chemicals (fluoro-
polymer and crosslinking agent).
Air permeability and mechanical properties
Air permeability is an important property in the perform-
ance of textile substrates. It is used to provide an indication
of the breathability of fabrics. Applying long-chain fluoro-
polymer to the fabric (Figure 3(a)) led to a decreased air
permeability compared to the untreated fabric (53 mm.s1).
Increasing the concentration of the long-chain fluoropoly-
mer also has the negative side effect on air-permeability,
which steadily decreased with increasing concentration. The
same behavior was noticed for samples treated with short-
chain fluorinated agent (Figure 3(b,c)).
When the crosslinking agent was added to the finishing
solution at a concentration of 5% (by weight), the coated
fabric exhibits an air permeability ranging between 29 and
42 mm.s1. Increasing the concentration of the crosslinking
agent to 15% led to a steady decrease in air permeability
which reached 24 mm.s1. MEB results have shown that
when the fluoropolymer coating was applied on cotton sub-
strates, the surface exhibited a more dense structure, which
correlates well with the air permeability measurements and
contact angle results. All treated cotton fabrics had increased
contact angle values and reduced air permeability, but to a
different degree depending on the treatment conditions
(temperature, time and chemicals concentration). The
coated fabrics with the lowest air permeability exhibited
superior water repellency. This result suggests that there are

Figure 3. Air permeability and mechanical properties of treated cotton fabrics.
very few connected pores through the coated fibers and that
a film was formed on the surface. This film will constitute
an obstacle for the transport of penetrates such as water
and air.
Mechanical properties were also evaluated since they are
essential for the fabric overall function. Tensile strength is
one of the most relevant textile mechanical properties. For
this reason, this performance should be checked after finish-
ing processes. Figure 3 shows the force–elongation curves of
untreated and some treated samples. All fabrics failed within
the middle of the sample, away from the grips. It can be
seen from the curves that fluoropolymer treated samples
were stiffer. The behavior of the fabric treated with short-
chain fluoropolymer using 15% of the crosslinking agent
differs significantly from the rest of the fabric samples. This
fabric resists more than the others. The water repellent
treatment has enhanced the mechanical properties of the
treated fabrics. This could be mainly attributed to the strong
adhesion and bonding affinity of fluoropolymers towards
cotton fibers. Based on these results, it suffices to confirm
that as a result of water repellent treatment, no deterioration
in the mechanical properties (breaking load and maximum
elongation at break) of the original fabric occurs.
Objective evaluation of handle properties
Handle properties of textile fabrics are important parameters
for quality and hence it is important to achieve water repel-
lency without altering the fabric’s characteristics to a
THE JOURNAL OF THE TEXTILE INSTITUTE 7
significant extent. The handle properties were studied, using
only the samples cured at 150
C for 1 min since they have
shown good water repellency.
Shear behavior
The shear behavior of different samples was characterized
by two shear parameters: shear stiffness (G) and shear hys-
teresis values at 0.5
(2HG) and at 5
(2HG5). In
Figure 4(a) an example of shear curves of untreated and
treated fabrics is presented. A change in the shearing prop-
erties is observed for the treated fabrics. The same tendency
is observed for both long-chain (Figure 4(a1)) and short-
chain fluoropolymers (Figure 4(a2)). Moreover, Figure 4(a2)
shows that the change of shearing properties is affected by
the amount of the crosslinking agent.
The data reported in Table 5 indicate that the values of
shear stiffness (G) and shear hysteresis at 0.5
(2HG) and 5

(2HG5) of the control sample are the lowest. For the treated
fabrics, there is an important increase in values compared
with the control fabric. This result could be attributed to
the fact that, during padding-curing process, only the outer
surface of the fibers is treated. This method is often accom-
panied by excessive weight add on, loss of drape and
reduced comfort (Gulrajani & Gupta, 2011). In addition, the
finishing bath pH was between 5 and 6. This condition may
have led to increased stiffness (Lam, Kan, Yuen, & Au,
2011). In the case of treated fabric using 3% of the long-
chain agent, the shear stiffness has increased by 63%.
Furthermore, 50% increase in the hysteresis of shear force at
8 S. GARGOUBI ET AL.

Figure 4. Kawabata shear (a) and compression (b) test curves of treated fabrics.

Table 5. Parameters obtained by shear, compression and surface tests of untreated and treated fabrics.
Shear parameters Compression parameters Surface parameters
G 2HG 2HG5 LC WC RC T0 Tm MIU MMD SMD
Long-chain
Sample 1-c 1.88 4.89 9.205 0.35 0.21 39.96 0.65 0.41 1.89 0.76 1.30
Sample 2-c 2.545 6.565 10.54 0.39 0.23 40.10 0.64 0.47 2.14 1.81 1.51
Short-chain
Sample 3-c 2.33 5.44 9.98 0.42 0.22 38.41 0.68 0.46 1.71 1.26 1.47
Sample 4-c 3.38 7.925 16.575 0.36 0.17 45.56 0.65 0.46 1.74 1.05 1.17
Sample 5-c 2.58 4.89 10.805 0.37 0.20 43.81 0.683 0.481 1.67 0.80 1.33
Sample 6-c 3.865 9.06 14.605 0.38 0.18 44.60 0.79 0.59 2.05 1.11 1.71
Untreated 1.153 3.257 5.54 0.34 5.543 40 0.57 0.34 1.55 0.55 1.04
c (150
C/1 min): curing conditions giving best wetting properties.

0.5
shear angle and 66% increase in the hysteresis of shear
force at 5
shear angle were observed. In the case of treated
fabric, using 5% of the same agent (long-chain), about 200%
increase in the shear stiffness and its hysteresis value has
been registered.
The shear stiffness of the treated fabric using short-chain
agent has increased remarkably with a very high impact on
the hysteresis of shear force, both at 0.5 shear angle and 5
shear angle.
The finished fabric with maximum combination between
the short-chain fluorinated agent (30%) and the crosslinking
agent (15%) shows 235% increase in shear stiffness, 178%
increase in hysteresis of shear force at 0.5 shear angle and
163% increase in the hysteresis of shear force at 5 shear
angle. The excessive amount of fluorinated agents as well as
that of the crosslinking agent can lead to formation of glue-
like film on the textile surface. This film will result in poor
fabric recovering ability and then deterioration of handling
and drape properties of the treated fabrics.
Compression
Compressibility of woven fabrics is considered as one of the
major factors affecting handle properties. This property is
evaluated as a relationship between pressure and thickness
of the substrate. Compressional behavior of untreated fabric
 THE JOURNAL OF THE TEXTILE INSTITUTE 9

0 ,4 0 ,4

U n tre a te d S a m p le 2 -c
0 ,2 0 ,2
M IU

M IU
0 ,0 0 ,0

-0 ,2 -0 ,2

-0 ,4 -0 ,4
0 5 10 15 20 25 30 0 5 10 15 2 0 2 5 30
0 ,0 4 0 ,0 6
LF
eFnF
g tFhF(FmFm
F)
0 ,0 4
0 ,0 2

0 ,0 2

0 ,0 0
SMD

0 ,0 0

SM D
-0 ,0 2 - 0 ,0 2

- 0 ,0 4
-0 ,0 4

- 0 ,0 6

-0 ,0 6
0 5 10 15 20 25 30 - 0 ,0 8
L e n g th (m m ) 0 5 10 15 20 25 30
L e n g th (m m )

0 ,4 0 ,4

S am ple 5-c S a m p le 6 -c
0 ,2 0 ,2

M IU
M IU

0 ,0 0 ,0

-0 ,2
-0 ,2

-0 ,4
0 5 10 15 20 25 30 -0 ,4
0 ,0 6 0 ,0 6 0 5 1 0 15 20 2 5 30

0 ,0 4 0 ,0 4

0 ,0 2
0 ,0 2
SMD
SMD

0 ,0 0

0 ,0 0
- 0 ,0 2

- 0 ,0 2
- 0 ,0 4

- 0 ,0 4 - 0 ,0 6

0 5 10 15 20 25 30 0 5 10 15 20 25 30
L e n g th (m m ) L e n g th (m m )

Figure 5. Some representative graphs showing the variation of the values of MIU and SMD.

and some treated fabrics during loading and unloading are
presented in Figure 4(b).
The fabric compression/decompression leads to a hyster-
esis effect. It is clearly visible that compressibility is influ-
enced by finishing chemicals and conditions.
To aid a comparison between the different fabrics, we
have presented the KES-F compression parameters in
Table 4. The parameters are the average of three tests. As it
can be deduced, all samples undergo increase in thickness
T0 and Tm after water repellent treatment. It is obvious that
add-on of the fluoropolymer on cotton fiber surface caused
increases in fabric weight and thickness. The linearity of
compression curve can reflect the rigidity of the textile. The
noticed high LC values indicate more compression rigidity
of the water repellent fabrics.
The compression energy increased for all the treated
samples, except the short-chain treated fabric using 10%
and 30% fluoropolymer and 15% crosslinking agent. Surface
resin treatment imparted supplementary weight to the cot-
ton fabric and made it thicker and more resistant during
compression. For the fabric treated with 10% and 30%
fluoropolymer and 15% crosslinking agent, possibly the
reduction in compression energy is due to the nonuniform-
ity of the treatment as previously proved.
The compression resilience increased only for fabrics
treated with the crosslinking agent. This might be due to
the prevention of the movement of the fibers and yarns
after the crosslinking agent has filled in the gaps between
the threads. Fabrics with high RC value have better reten-
tion ability during decompression.
Surface
Surface properties of untreated and various treated fabrics
are shown in Table 5. The coefficient of friction MIU was
found to be highest for all treated fabrics. Samples treated
with long-chain fluoropolymer, as well as sample treated
with short-chain fluoropolymer baths having an excess of
crosslinking agent show higher values of MIU and hence
are less smooth (Figure 6). MMD reveals the similar ten-
dency in the values, as it is mean deviation of coefficient of
friction. Higher values of MIU and MMD correspond to
higher friction and larger variation of friction.
10 S. GARGOUBI ET AL.
Figure 6. Wetting times of treated cotton fabrics before and after wash-
ing cycles.
Comparing the surface roughness properties, it was con-
cluded that SMD values of treated fabrics tend to be higher
than that of untreated fabric. Highest SMD values were
found in the case of fabrics treated with an excess of chemi-
cals (fluoropolymer and crosslinking agent). Higher values
correspond to geometrically rough surface of treated fabrics
(Figure 5).
Laundering durability
The effect of laundering on the sustainability of water repel-
lency treatment was studied, using only the samples 2-c, 5-c
and 6-c. After each laundering cycle, the wetting time of a
droplet deposited on the treated support was determined.
The longer is the wetting time, the better is the fabric
water repellency.
Wetting times shown in Figure 6 revealed that the treat-
ment of cotton samples with long-chain fluoropolymer is
resistant to laundering. Water droplets fully spread on the
surface within few seconds after the eighth laundering cycle.
The same trend was noticed for the fabric treated with
short-chain fluoropolymer using 15% of the crosslinking
agent. Short-chain treated cotton using 5% of the crosslink-
ing agent indicated that the water droplets disappear within
few seconds after the fifth laundering cycle. The contact
angle of the different fabrics was found to be lower after
each laundering cycle. The loss of water repellency by wash-
ing is commonly attributed to leaching of the fluoropoly-
mer. It might also be due to the presence of residual
detergent on the fabric and distortions of the fab-
ric structure.
Conclusion
The aim of the present investigation was to evaluate the per-
formance of water repellent treatments conducted using
long-chain fluoropolymers and their short-chain homo-
logues. Towards this goal, different finishing conditions
were thoroughly investigated. Surface sensitive analyses such
as ATR FTIR, SEM and contact angle studies were carried
out to evaluate the effectiveness of different treatments. Air
permeability, mechanical properties and handle properties of
treated cotton were also tested. Finally, the permanence of
treatment after washing cycles was evaluated. It was found
that water repellent finishing using short-chain fluoropoly-
mer is a competitive alternative since this chemical provides
good repellency and good washing durability comparable to
those achieved using long-chain fluoropolymer. In addition,
this finishing gives comfort properties similar to those
obtained when using long-chain fluoropolymer. Short-chain
fluoropolymer, recognized as an eco-friendly alternative for
toxic long-chain fluoropolymers, was found to be very
promising as an effective chemical for developing water
repellent property on cotton fabrics. A study devoted to the
oil resistance of the realized samples is in progress. The
results will be reported separately.
Disclosure statement
No potential conflict of interest was reported by the authors.
References
Åkerblom, D., & G€ oranzon, E. (2014). Greener water repellency?
Feasible alternatives to fluoro chemicals for DWOR treatments on
textiles. Sweden: University of Borås/Swedish School of Textiles.
Audenaert, F., Lens, H., Rolly, D., & Vander Elst, P. (1999).
Fluorochemical textile repellents—synthesis and applications: A 3M
perspective. Journal of the Textile Institute, 90, 76–94. doi:10.1080/
00405009908659480
Barmentlo, S. H., Stel, J. M., van Doorn, M., Eschauzier, C., de Voogt,
P., & Kraak, M. H. (2015). Acute and chronic toxicity of short
chained perfluoroalkyl substances to Daphnia magna. Environmental
Pollution, 198, 47–53. doi:10.1016/j.envpol.2014.12.025
Buck, R. C., Franklin, J., Berger, U., Conder, J. M., Cousins, I. T., de
Voogt, P., … van Leeuwen, S. P. (2011). Perfluoroalkyl and poly-
fluoroalkyl substances in the environment: Terminology, classifica-
tion, and origins. Integrated Environmental Assessment and
Management, 7, 513–541. doi:10.1002/ieam.258
Ceretta, F. (2013). Synthesis and characterization of fluorinated com-
pounds for industrial applications (Doctoral dissertation). Padua,
Italy: University of Padova.
Chau, T., Bruckard, W., Koh, P., & Nguyen, A. (2009). A review of
factors that affect contact angle and implications for flotation prac-
tice. Advances in Colloid and Interface Science, 150, 106–115. doi:10.
1016/j.cis.2009.07.003
El-Shafei, A., ElShemy, M., & Abou-Okeil, A. (2015). Eco-friendly fin-
ishing agent for cotton fabrics to improve flame retardant and anti-
bacterial properties. Carbohydrate Polymers, 118, 83–90. doi:10.
1016/j.carbpol.2014.11.007
Extrand, C. (2004). Criteria for ultralyophobic surfaces. Langmuir, 20,
5013–5018.
Ferrero, F., & Periolatto, M. (2013). Application of fluorinated com-
pounds to cotton fabrics via sol–gel. Applied Surface Science, 275,
201–207. doi:10.1016/j.apsusc.2013.01.001
Ferrero, F., & Periolatto, M. (2015). Modification of surface energy and
wetting of textile fibers wetting and wettability (pp. 139–168). Rijeka,
Croatia: InTech.
Ferrero, F., Periolatto, M., & Tempestini, L. (2017). Water and oil
repellent finishing of textiles by UV curing: Evaluation of the influ-
ence of scaled-up process parameters. Coatings, 7, 60. doi:10.3390/
coatings7050060
Gao, Z., Gu, J., Wang, X., Li, Z., & Bai, X. (2005). FTIR and XPS study
of the reaction of phenyl isocyanate and cellulose with different
moisture contents. Pigment & Resin Technology, 34, 282–289. doi:10.
1108/03699420510620300

Gargoubi, S., Tolouei, R., Chevallier, P., Levesque, L., Ladhari, N.,
Boudokhane, C., & Mantovani, D. (2016). Enhancing the functional-
ity of cotton fabric by physical and chemical pre-treatments: A com-
parative study. Carbohydrate Polymers, 147, 28–36. doi:10.1016/j.
carbpol.2016.03.084
Gulrajani, M., & Gupta, D. (2011). Emerging techniques for functional
finishing of textiles. Indian Journal of Fibre and Textile Research, 36,
388.
Hasegawa, T. (2017). Physicochemical nature of perfluoroalkyl com-
pounds induced by fluorine. The Chemical Record, 17, 903–917. doi:
10.1002/tcr.201700018
Holme, I. (1993). New developments in the chemical finishing of tex-
tiles. Journal of the Textile Institute, 84, 520–533. doi:10.1080/
00405009308658985
Holmquist, H., Schellenberger, S., van der Veen, I., Peters, G.,
Leonards, P., & Cousins, I. T. (2016). Properties, performance and
associated hazards of state-of-the-art durable water repellent (DWR)
chemistry for textile finishing. Environment International, 91,
251–264. doi:10.1016/j.envint.2016.02.035
Jiang, J., Zhang, G., Wang, Q., Zhang, Q., Zhan, X., & Chen, F. (2016).
Novel fluorinated polymers containing short perfluorobutyl side
chains and their super wetting performance on diverse substrates.
ACS Applied Materials & Interfaces, 8, 10513–10523. doi:10.1021/
acsami.6b01102
Lam, Y., Kan, C., Yuen, C., & Au, C. (2011). Fabric objective measure-
ment of the plasma-treated cotton fabric subjected to wrinkle-resist-
ant finishing with BTCA and TiO2 system. Fibers and Polymers, 12,
626. doi:10.1007/s12221-011-0626-y
Maity, J., Kothary, P., O’Rear, E. A., & Jacob, C. (2010). Preparation
and comparison of hydrophobic cotton fabric obtained by direct
fluorination and admicellar polymerization of fluoromonomers.
Industrial & Engineering Chemistry Research, 49, 6075–6079. doi:10.
1021/ie100564y
Manepalli, A. (2016). Fabrication of repellent fabrics using plasma
grafted siloxanes (Doctoral dissertation). Carolina, USA: Graduate
Faculty of North Carolina State University.
Materne, T., de Buyl, F., & Witucki, G. L. (2012). Organosilane technol-
ogy in coating applications: Review and perspectives. Dow Corning
Corporation, AGP11933, Form No.
Mazzoni, M., Polesello, S., Rusconi, M., & Valsecchi, S. (2015, March).
Investigating the occurrence of C8-based perfluorinated substitutes
in Italian waters. Norman Bulletin, Issue 4, Water Research
Institute, Italy.
Nasar, A. S., & Kalaimani, S. (2016). Synthesis and studies on forward
and reverse reactions of phenol-blocked polyisocyanates: An insight
into blocked isocyanates. RSC Advances, 6, 76802–76812. doi:10.
1039/C6RA15643F
THE JOURNAL OF THE TEXTILE INSTITUTE 11
Pan, G., Schaefer, D. W., & Ilavsky, J. (2006). Morphology and water
barrier properties of organosilane films: The effect of curing tem-
perature. Journal of Colloid and Interface Science, 302(1), 287–293.
doi:10.1016/j.jcis.2006.06.031
Phattanarudee, S., Chakvattanatham, K., & Kiatkamjornwong, S.
(2009). Pretreatment of silk fabric surface with amino compounds
for ink jet printing. Progress in Organic Coatings, 64, 405–418. doi:
10.1016/j.porgcoat.2008.08.002
Rabilloud, G. (1997). High-performance polymers: Chemistry and appli-
cations. Paris: Institut français du petrole, Editions Technip.
Schellenberger, S., Gillgard, P., Stare, A., Hanning, A., Levenstam, O.,
Roos, S., & Cousins, I. (2017). Facing the rain after the phase out:
Performance evaluation of alternative fluorinated and non-fluori-
nated durable water repellents for outdoor fabrics. Chemosphere,
193, 675–684. doi:10.1016/j.chemosphere.2017.11.027
Shahidi, S., Wiener, J., & Ghoranneviss, M. (2013). Surface modifica-
tion methods for improving the dyeability of textile fabrics (pp.
33–52). Rijeka, Croatia: INTECH Open Access Publisher.
Shateri-Khalilabad, M., & Yazdanshenas, M. E. (2013). Fabrication of
superhydrophobic, antibacterial, and ultraviolet-blocking cotton fab-
ric. Journal of the Textile Institute, 104, 861–869. doi:10.1080/
00405000.2012.761330
Shimoaka, T., Sonoyama, M., Amii, H., Takagi, T., Kanamori, T., &
Hasegawa, T. (2017). Study of perfluoroalkyl chain-specific band
shift in infrared spectra on the chain length. The Journal of Physical
Chemistry A, 121, 8425–8431. doi:10.1021/acs.jpca.7b08940
Slade, P. E. (1997). Handbook of fiber finish technology. New York:
CRC Press.
Wang, Z., Cousins, I. T., Scheringer, M., & Hungerb€ uhler, K. (2013).
Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids
(PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential
precursors. Environment International, 60, 242–248. doi:10.1016/j.
envint.2013.08.021
Yang, Y., Shen, J., Zhang, L., & Li, X. (2015). Preparation of a novel
water and oil-repellent fabric finishing agent containing a short per-
fluoroalkyl chain and its application in textiles. Materials Research
Innovations, 19, S8–401–S408-404. doi:10.1179/1432891715Z.
0000000001708
Yao, W., Li, Y., & Huang, X. (2014). Fluorinated poly (meth) acrylate:
Synthesis and properties. Polymer, 55, 6197–6211. doi:10.1016/j.poly-
mer.2014.09.036
Zhang, J., France, P., Radomyselskiy, A., Datta, S., Zhao, J., & van
Ooij, W. (2003). Hydrophobic cotton fabric coated by a thin nano-
particulate plasma film. Journal of Applied Polymer Science, 88,
1473–1481. doi:10.1002/app.11831