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Multi-objective optimization in the development of oil and water repellent cellulose fabric

based on response surface methodology and the desirability function

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2017 Mater. Res. Express 4 035302

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 Mater. Res. Express 4 (2017) 035302 https://doi.org/10.1088/2053-1591/aa5f6a

PAPER

Multi-objective optimization in the development of oil and water

repellent cellulose fabric based on response surface methodology
RECEIVED
21 October 2016

and the desirability function

RE VISED
6 January 2017
ACCEP TED FOR PUBLICATION
9 February 2017
PUBLISHED
NaseerAhmad1,2, ShahidKamal1, ZulfiqarAliRaza2 and TanveerHussain2
1
3 March 2017 College of Statistical and Actuarial Sciences, University of the Punjab, Lahore, Pakistan
2
National Textile University, Faisalabad-37610, Pakistan
E-mail: naseerahmadntu@gmail.com and zarazapk@yahoo.com.

Keywords: cellulose, desirability function, optimization, response surface methodology, water repellent

Abstract
The present study investigated multi-response optimization of certain input parameters viz.
concentrations of oil and water repellent finish (Oleophobol CP-C), dimethylol dihydroxy ethylene
urea based cross linking agent (Knittex FEL) and curing temperature on some mechanical, (i.e. tear
and tensile strengths), functional (i.e., water contact angle WCA, oil contact angle OCA) and
comfort (i.e. crease recovery angle CRA, air permeability AP, and stiffness) properties of an oleo-
hydrophobic finished fabric under response surface methodology and the desirability function. The
results have been examined using analysis of variance (ANOVA) and desirability function for the
identification of optimum levels of input variables. The ANOVA was employed also to identify the
percentage contribution of process factors. Under the optimized conditions, which were obtained
with a total desirability value of 0.7769, the experimental values of Oleophobol CP-C (O-CPC),
Knittex FEL (K-FEL) and curing temperature (C-Temp) agreed closely with the predicted values.
The optimized process parameters for maximum WCA (135), OCA (129), AP (290 m s1), CRA
(214), tear (1492 gf) and tensile (764N) strengths and minimum stiffness (3.2928cm) were found
to be: concentration of OCP-C as 44.44g l1, concentration of cross linker K-FEL as 32.07g l1 and
C-Temp as 161.81 C.

1.Introduction

Multifunctional effects are imperative to produce high value added textile products, necessary not only for the
application of new technologies but also to achieve and maximize impact for industrial transformation [1].
Functionalization of textile materials provides new properties to textile and clothing materials. In most of the
cases, the functional effects involve a surface modification, which can be attained by means of physical, chemical
and biological means [2]. The novel effects in textiles are secured by the application of specialty chemicals. The
emergence of the so-called nanotechnologies opens a wide range of new possibilities. In this study, the main
emphasis had been given to the optimum functionalization of textiles accomplished by means of the incorporation
of chemicals in fabric finishing processes.
Hydrophilic and hydrophobic are commonly used descriptors of surfaces. A surface is hydrophilic which
attracts water and exhibits low contact angle. A surface is hydrophobic that expels water. More specifically, the
terms describe the intermolecular interactions when the liquid and solid are brought together [3].
Water, oil and stain repellence or hydrophobicity effect is one of the most widely used textile surface modi-
fication effect and is inspired from self-cleaning properties exhibited by birds feathers and lotus leaves
super-hydrophobicity effect in textile surface modification has gained significant attention of industrial as well as
scientific research because of todays most preferred solution for the self-cleaning textile [4].
The hydrophobicity depends on various process parameters, including the surface orientation, surface energy
of substrate, heat of emersion, surface adhesion, surface topography, type of finish, concentration of finish, curing
temperature and so forth [5]. From the literature, it is observed that the one-factor-at-a-time approach, i.e. only
one factor varing at a time while taking other factors fixed, is inefficient, because of not considering all possible

2017 IOP Publishing Ltd

Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Table 1. Important process parameters and their levels for finished fabric.

Coded and actual factor levels

Design variables Symbols a (2) Low (1) Center (0) High (1) (+2) Units
Finish concentration (O.CPC) A 10 20 30 40 50 g l1
Cross linker concentration (K. FEL) B 10 20 30 40 50 g l1
Curing temperature (C.Temp) C 150 155 160 165 170 C

interactions between the factors [6]. However, when studying multi-factors at a time then design of experiment
(DOE) is more effective tool for statistical analysis and is employed to study the output variables with the simul-
taneous change in the input factors. Statistically designed experiment can greatly increase the efficiency of experi-
ments. The purpose of DOE is to find out the combination of conditions of the process variables that provides the
optimum response over a region of interest [7].
Response surface methodology (RSM) is an assembly of mathematical and statistical tools helpful for exper
imental planning, modeling, analyzing and optimizing of scientific, modern mechanical and engineering prob-
lems [8]. The RSM and its underlying philosophy was originated by Box and Wilson in 1951 [9] followed by Box
in 1954 [10]. Recently, the RSM has gained great significant in optimization of textile engineering problems by
using its main robustness and smoothness properties [11]. Using relatively smaller amount of data, the RSM has
the ability to develop and optimize the estimated model resulting in reduction of time and cost [12].
The objective of this study was to identify the relationships between the oil and water repellency process
parameters by using RSM with the desirability function approach, which is the next version of our previous study
in the formation of water and oil repellency cellulose fabric using Taguchi based grey relational analysis [13]. The
RSM has successfully been employed to optimize oleo-hydrophobic process in order to investigate the effects of
concentration of O-CPC finish (oil and water repellent finish), concentration of K-FEL (crosslinking agent), and
curing temperature (C-Temp). The conventional RSM approach focuses on a single response; however, in prod-
uct or process development, it is common to have several responses of interest. So it was desirable to find the best
comprise of the product characteristics, at a glance. The desirability function method is one of the most flexible
and popular multi-response optimization approaches. The present study undertook the desirability function
approach for the simultaneous optimization of a series of quadratic models [15].

2. Materials and methods

2.1.Materials
A plain weave (11) 100% greige cotton fabric of 129.40g m2 areal density, comprising 30/1 Ne counts yarn
(warp and weft), 86 ends and 76 picks per inch, was purchased from the local market. A fluoro-chemical oleo-
hydrophobic finish (Oleophobol CP-C), dimethylol dihydroxy ethylene urea based crosslinking agent (named
Knittex FEL) and a catalyst based on magnesium chloride (Knittex MO), were kindly arranged by SwissTex
Chemicals Office, Faisalabad-Pakistan. The pretreatment of the greige cotton fabric was reported in our earlier
study [13].

2.2. The choice of factors

To optimize the hydrophobicity of finished fabric, three factors were considered, i.e. concentration of the
O-CPC finish, concentration of the cross-linker (K-FEL) and the C-Temp (table 1). The relationship between
hydrophobicity of the finished fabric and the experimental factors was hypothesized to be non-linear.

2.3. Experimental design

DOE is a systematic, rigorous statistical approach for experimental planning, so that the data obtained could be
analyzed to yield valid scientific conclusions. The main advantage of DOE techniques is to identify important
factors that affect the process of interest resulting in an estimated model for the response based on ANOVA [14].

2.4. Response surface methodology

The RSM is an assembly of mathematical and statistical techniques that are beneficial for empirical modeling,
analyzing and optimizing of industrial problems. The main objective of RSM is to analyze and optimize the
response variable influenced by a number of continuous independent parameters with negligible errors. The
RSM has extensively been used in analytical applications, industrial sector and bioprocesses [15]. The RSM also
quantifies the functional relationship, usually a second-order model, between independent parameter and the
obtained response variable is represented as equation(1) [16].

2
Mater. Res. Express 4 (2017) 035302 N Ahmad etal

k k k k

y = o +
(1)
i=1
ix i +
i=1
2
ii xi +
i=1 j=1

ijx ix j +
i<j

Where, y is the desired response, s are regression coefficients, which are obtained by least square method, and
is the error term.
The RSM generates a graphical view of the system, since the response can be represented like a solid surface in
a three-dimensional (3D) space. When more than two factors are being optimized, the graphical representation is
made for two of them, maintaining the other ones at constant values; thus, a small fraction of the surface is shown.
Besides, contour maps may be plotted as another way of visualization. The contour plot is a topographical map
representing 3D relationship between three variables in two dimensions.
The model is considered satisfactory when the regression is significant and a non-significant lack-of-fit is
obtained for the selected confidence level. However, obtaining a significant model does not necessarily means
that it explains correctly the variation in data. Resultantly, it is necessary to calculate residual plots, the determina-
tion coefficient (R2) and the adjusted determination coefficient (R2 adj), representing the percentage of variance
explained by the model.

2.5. Analysis of variance

The ANOVA which is the extension of z and t tests, developed by Fisher in 1920s [17], is a series of statistical
techniques used to identify the significant terms in the developed model. The ANOVA technique also gives the
relative contribution that each input variable makes on the overall estimated response. Significance of model
terms are judged by determining the p-value is less than level of significance, usually 5%. The relative significance
of process parameters is often denoted in terms of percentage contributions or F-ratio.

2.6. Water and oil contact angles measurement

Usually, hydrophobicity is determined by finding the contact angle of a water droplet contacting a surface. The
contact angle is the angle where a liquid vapour-interface meets a solid surface. In the present study, water and oil
contact angles of the finished fabrics were evaluated by using an optical tensiometer (Theta Lite, Finland). For
complete wetting to occur, the contact angle of water droplet should be zero. A contact angle in degrees (90)
corresponds to high wettability, while large value of contact angles in degree (90) implies low wettability or
high hydrophobicity [18]. Superhydrophobic surfaces are those surfaces that are extremely repellent for water
having contact angle greater than 120. Theoretically, perfectly hydrophobic surfaces have a contact angle of 180.

2.7. Air permeability measurement

Air permeability is the comfort property of a woven fabric used to measure the flow of air through it. The air
permeability of both controlled and treated fabric samples were evaluated according to ASTM D737-04, using
an air permeability tester (SPLATLAS, M021A). Briefly, the fabric specimen is clamped into the air permeability
tester. Using vacuum, different air pressure on both sides of the fabric is created so that air from higher pressure
to lower pressure may pass. The air permeability is determined with 100 Pa rate of airflow from one side of the
fabric specimen.

2.8. Measurement of crease recovery angle

The ability of textiles to recover from creasing which is determined by measurement of its moving clamp angle
(creases). This angle quantifies the crease recovery of a fabric. A higher CRA indicates better crease recovery of the
fabric. The CRA of both controlled and treated fabric samples were evaluated according to the standard testing
method-AATCC 66, using a Shirley crease recovery tester. In this method, the fabric specimen is first placed
between two glass plates under a load of 500g for a 1min; after releasing, the creased fabric is clamped on the angle
measuring instrument and the fabric is allowed to recover from the crease under its own weight for a specific time
(usually 1min). The clamping end is rotated slowly to keep the free edge of the specimen vertical. The recovery
angle of the specimen is noted by using a graduated tester.

2.9. Measurement of stiffness

The stiffness, a comfort property of cotton fabric, was measured according to the standard test method ASTM
D1388. In short, a woven fabric specimen is slid at a constant speed on the even horizontal surface, until the front
edge of the specimen projects from the smooth horizontal surface. The length of the hanged specimen is measured
when the front tip of the fabric is depressed to the point- the bending angle (45) indicator. With this procedure,
the bending or falling length and flexural rigidity are measured.

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

2.10. Measurement of tear strength

The tear strength is an important property of the finished fabric and depends on the chemical finishing treatment
applied to the fabric. The tear strength of the treated and untreated both warp-way and weft-way specimens were
tested in accordance with the standard test method ASTM-D5587. A test sample with slit at the center was gripped
between fabric jaws of the tester. The specific force was applied and the maximum load (gf) was recorded when
the specimen was torn.

2.11. Measurement of tensile strength

Tensile stressstrain is one of the most important mechanical properties of woven fabrics. It is used to describe the
behaviour of the fabric under axial stretching load. The strength of finished fabric specimen was measured using
the strip method in accordance with standard test method ISO 13934-1 on a tensile strength tester. A test specimen
was gripped in two or more fabric jaws and extended until it broke. This method gives the breaking load (N) and
elongation at maximum force.

2.12. Desirability approach

When a large number of responses are required to be optimized, the desirability function is the most
popular mathematical tool to be employed. The desirability function is a mathematical method to analyze a
multi-response optimization problem [19]. Harrington [20] first proposed the desirability function and
it was later modified to be more flexible in practical application by Derringer and Suich [19]. This approach
is one of the most popular and extensively used for the simultaneous optimization in industrial quality
management [15].
The desirability function is based on an idea that a product or process can contain the simultaneous study of
several quality characteristics and it may be totally unacceptable for the customer if one of them is missing. Its
goal is to find working conditions to ensure compliance with all the relevant standards in response and, at the
same time, to provide the optimum compromise in the desirable joint response [8].
Desirability function approach transforms each estimated response ( yi ) into unit-free value called desirability
of ith response denoted by d i (yi ) that varies over the range 0 d i 1 and with the increase in the value of d i, the
estimated ith response yi becomes more desirable, d i (yi ) = 1 implies an ideal response, where d i (yi ) = 0 for an
unfavourable response.
In first step, an individual desirability function, d i (yi ), for each response yi must be evaluated using the fitted
models and establishing the optimization criteria.
Based on whether a particular response yi is to be minimized, maximized, or assigned to a target value, the
respective desirability function (d i (yi )) is used as given below:
The desirability function for the nominal-the-better is (equation (2)):
0 yi (x ) < yimin or yi (x ) > yimin

yi (x ) yimin i min
s

yi yi (x ) Ti, s 0
Ti Y imin
d i (yi ) =
yi Y imax i
(2) t

T yi (x ) yimax , t 0

i T y max

1
i

yi (x ) = Ti

Where, exponents si and ti are the shape parameters of the desirability function and yimin and yimax are lower and
upper specification limits, respectively. The shape constants, in general, are chosen in the range from 0.01 to 10
[21].
The desirability function for the smaller the better (equation (3)):
1 yi (x ) Timin

y (x ) yimax r
d (yi ) = i min
(3) yimin yi (x ) yimax r 0
yi yimax
0
yi (x ) > yimax

If the response y is anticipated to be larger-the- better, then the desirability function is (equation (4)):

4
Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Table 2. Central composite design and experimental responses.

Factors Responses

AP Stiffness Tear Tensile

Coded Actual WCA OCA (mm s1) CRA (cm) strength (gf) strength (Nf)

Std. O.CPC K.FEL C.Temp

order A B C (g l1) (g l1) (C) Warp+weft Warp+weft Warp+weft Warp+weft

1 1 1 1 20 20 155 115 100 233 195 3.9255 1540 745

2 1 1 1 40 20 155 123 121 268 194 3.8797 1580 849
3 1 1 1 20 40 155 122 116 218 218 3.9351 1490 767
4 1 1 1 40 40 155 135 130 216 211 3.7234 1470 802
5 1 1 1 20 20 165 118 100 218 194 3.8182 1498 735
6 1 1 1 40 20 165 129 126 280 195 3.7985 1520 858
7 1 1 1 20 40 165 128 121 220 220 3.8959 1400 630
8 1 1 1 40 40 165 136 124 285 218 3.0011 1498 716
9 2 0 0 10 30 160 110 98 210 218 4.1864 1430 677
10 2 0 0 50 30 160 133 125 288 218 3.4269 1460 787
11 0 2 0 30 10 160 127 122 247 201 4.1863 1520 859
12 0 2 0 30 50 160 135 130 218 218 3.8171 1440 741
13 0 0 2 30 30 150 119 95 239 186 3.8835 1580 798
14 0 0 2 30 30 170 133 128 290 211 3.0469 1490 676
15 0 0 0 30 30 160 133 129 273 212 3.9324 1480 698
16 0 0 0 30 30 160 130 124 283 207 3.5727 1580 684
17 0 0 0 30 30 160 131 130 269 204 3.4635 1570 727
18 0 0 0 30 30 160 128 125 258 201 3.9014 1550 751
19 0 0 0 30 30 160 130 127 269 209 3.4904 1510 726
20 0 0 0 30 30 160 132 129 260 207 3.5635 1498 723

Note: O.CPC=OLEOPHOBOL CP-C; K. FEL=KNITTEX FEL; C.Temp=curing temperature; WCA=water contact angle;
OCA=oil contact angle; AP=air permeability; CRA=crease recovery angle.

0 yi (x ) < yimin
y (x ) L r
i
yimin yi (x ) yimax , r 0
i
( )

d
(4) 
y =

i i
U i L i
1 yi (x ) > yimax


The overall desirability is named as global desirability (D) that varies from 0 to 1. Harrinton [22] proposed
geometric mean to estimate the overall desirability as (equation (5)):

m m
1

D = (d1 (yi ) d2 (y2)  dm (ym )) m = d i(yi )

1
(5)
i=1
Where, di is the individual desirability of the ith response and m is number of responses in the measure [15].
The optimized results of response variables suggested by the desirability function were rechecked by perform-
ing the experiments.

2.13. Scanning electron microscopy

The surface morphologies of the O-CPC treated cotton fabrics were observed under an FEI Quanta 250 scanning
electron microscope (SEM) equipped with EDX detectors at an accelerating voltage of 20kV.

2.14. Fourier transform infrared spectroscopy

In order to verify the application of O-CPC finish on the cotton fabric, the Attenuated Total Reflectance-Fourier
transform infrared spectroscopy (ATR-FTIR, Bruker Tensor 27) was performed at a wave number range of 4000
500cm1.

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Table 3. Estimated coefficients and p-values of significant model terms for different response variables.

Tensile
WCA OCA CRA AP Stiffness Tear strength strength

Model terms Coeff. p Coeff. p Coeff. p Coeff. p Coeff. p Coeff. p Coeff. p

Model 0.0001 0.0001 0.0003 0.0001 0.0015 0.0013 0.0001

A-O.CPC 5.38 0.0001 7.38 0.0001 0.56 0.6922 19.75 0.0001 0.17 0.0039 12.50 0.1305 35.50 0.0001
B-K.FEL 3.25 0.0001 3.75 0.0165 7.69 0.0001 7.38 0.0219 0.10 0.0591 27.50 0.0033 31.75 0.0001
C-C.Temp 2.75 0.0002 4.375 0.0069 3.69 0.0191 10.63 0.0026 0.16 0.0047 21.50 0.0153 29.25 0.0003
A2 2.42 0.0001 4.02 0.0023 2.50 0.0370 5.51 0.0268 21.66 0.0031
B2 9.63 0.0008 0.09 0.0315 12.91 0.0515 19.96 0.0008
C2 1.29 0.0108 4.02 0.0023 2.38 0.0460
AB 3.75 0.0738 0.13 0.0803
AC 11.75 0.0118
BC 9.25 0.0378 27.75 0.0066
Lack of fit 0.2243 0.0194 0.1404 0.2501 0.6297 0.9239 0.4752

Table 4. Quadratic models for predicting the responses.

R2 Adjusted Predicted
Response Equation (%) R2 (%) R2 (%)

WCA 1331.04 + 1.99X1 + 0.33X2 + 17.12X3 0.02X12 0.05X 32 15.33 92.84 90.28 80.61
OCA 4231.14 + 4.27X1 + 1.50X2 + 52.30X3 0.04X1X2 0.04X12 0.16X 32 29.33 85.26 85.26 29.79
AP 1766.80 32.32X1 24.56X2 10.48X3 + 0.24X1X3 + 0.19X2X3 0.06X12 0.10X 22 413.33 89.98 84.13 63.65
CRA 2342.13 1.556X1 + 0.77X2 + 31.14X3 + 0.03X12 0.10X 32 73.33 78.11 70.30 35.44
Stiffness 9.34 + 0.02X1 0.03X2 0.03X3 0.001X1X2 + 0.0009X 22 0.22 72.35 62.48 48.14
Tear 1954.71 + 14.246X1 + 5.00X2 4.30X3 0.22X12 0.33X 22 8413.33 72.96 63.31 50.75
strength
Tensile 828.16 + 3.55X1 + 73.65X2 + 10.80X3 0.56X2X3 + 0.20X 22 2814.83 88.74 84.72 76.34
strength

Note: X1, X2, and X3 are the actual values of the concentration of O-CPC finish, concentration of cross linker K-FEL and the C-Temp,
respectively.

3. Results and discussion

The surface modification through finishing processes is used to convert the grieg woven fabric into value added
textiles. Recently, oil and water repellent finishing processes in textiles are getting more and more importance
towards the improvement of value added textile effects. Great efforts are being made in the development of
products and processes for attaining super-hydrophobicity. In the present study, a plain woven cotton fabric
specimen was processed with oil and water repellent finish, optimum conditions of the process were identified
and the characterization of the optimized surface fabric was done in detail.

3.1. Regression model and ANOVA

The ANOVA is an effective statistical technique to identify the effect of categorical factors on an output variable.
The quality of fitted model is evaluated with the mean square value, coefficient of determination (R2), adjusted
R2, predicted R2 and lack-of-fit values. Statistical significance of each term in the model is checked by the Fischer
variation value [F-value=(the mean square of factors)/(the mean square of errors)] and the significant
probability value (p-value). The associated p-values less than (level of significance) for the model indicate that
the model terms are statistically significant. A total of 20 sets of experimental runs obtained from central composite
design (CCD) and the corresponding experimental responses are shown in table2. Statistical significant model
terms (linear and quadratic) of each response along with their respective estimated coefficients and p-values are
shown in table3. Any term in the fitted model having small p-value has significant effect on the response variable.
The fitted quadratic models of the response variables are shown in table4, with R2, adjusted R2 and predicted R2
values which indicate the adequacy of the fitted models to describe the significant effect of independent variables
on the respective responses.
Based on the ANOVA results presented in table3, the variable with the largest effect on water contact angle
(WCA) was the linear term of concentration of O-CPC finish (1), the linear terms of K-FEL and C-Temp

6
Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 1. (ac) 3D Response surface plots, (d) predicted versus actual plot (e) normal probability plot, and of the response water
contact angle.

(p-value<0.05), the quadratic terms of O-CPC and C-Temp (p-value<0.05)(11, 22) have significant effect
on WCA, The lack-of-fit F-value of 2.04 implies the lack-of-fit is not significant relative to the pure error, which
implies there is a 22.43% chance that a lack-of-fit F-value; this large F-value could occur due to noise. An insig-
nificant lack-of-fit is good, which is required for the adequecy of fitted model. Concentration of O-CPC finsh had
the largest effect on OCA (F-value=29.25, p-value=0.0001), AP (F-value=49.64, p-value=0.0001), stiffness
(F-value=11.87, p-value=0.0039), whereas concentration of cross linker (K-FEL) had the largest effect on
the responses including WCA (F-value=33.07, p-value=0.0001), CRA (F-value=30.51, p-value=0.0001),
and on tesnsile setrength (F-value=26.58, p-value=0.0001). Lack-of-fit of all the responses including
WCA (F-value=2.04, p-value=0.2243), AP (F-value=1.89, p-value=0.2501), CRA (F-value=2.73,
p-value=0.1404), stiffness (F-value=0.81, p-value=0.6297), tear strength (F-value=0.34, p-value=0.9239),
and tensile strength (F-value=1.12, p-value=0.4752), was noted insignificant except OCA (F-value=7.62,
p-value=0.0194). It was found that, the WCA varied due to a variation in the level of concentration of the finish,
and K-FEL, and the C-Temp in between 110136 oC.
Finally, 3D graphical representation was used to visualize the interaction effects of process parameters on the
output variables. The plots of predicted versus actual values ensure the adequacy of the fitted models. The prob-
ability plots show that the data are normally distributed within acceptable range of deviation, (figures 1(a)(c)
through 6(a)(c)). Table 5 gives the percentage contribution of significant factors to the respective responses.

3.2. Effect of experimental factors on various responses

3.2.1. Water contact angles.
WCA measurement is a very common technique to measure of the wettability of fabric surfaces.The normal
probability plots of the residual for WCA in figure1(d) are distributed normally and all the above consideration
fulfill the requirements of an excellent adequacy of the fitted model. It is evident from figure1(a) that the WCA
of the finished fabric increased with increase in concentrations both O-CPC concentration and K-FEL. However,

7
Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 2. (ac) 3D Response surface plots, (d) predicted versus actual plot, (e) normal probability plot, and of the response oil
contact angle.

the effect of O-CPC concentration was greater (coefficient 5.38) (table 3) than that of the K-FEL concentration
(coefficient 3.25) (table 3). The effect of C-Temp on WCA is also statistically significant (p=0.0002). The WCA
increased gradually, with the increase in concentrations of O-CPC and K-FEL, and the C-Temp (figures 1(a)(c)).
The square terms A2 (p=0.0001) and C2 (p=0.0108) as given in table3, which shows the significant results. The
experimental results showed that O-CPC concentration was the most significant factor (64%) in improving the
hydrophobicity (table 5). Increase in WCA due to increase in finish, cross linker and curing temperature implies
that the said three factors were important in increasing the hydrophobicity effect of the cotton fabric. Moreover,
figure1(c) shows the satisfactory results of comparison of the observed values with the predicted values form the
fitted model.

3.2.2. Oil contact angle.

It is observed from figure2(a) that the OCA of finished fabric increased rapidly (from 98 to 130) with increasing
both O-CPC (from 25 to 35g l1) and K-FEL (from 20 to 40g l1) concentrations. However, the effect O-CPC
concentration was greater (coefficient 7.375) (table 3) than that of the K-FEL concentration (coefficient 3.75)
and that of C-Temp (coefficient 4.38) (table 3). Furthermore, from table3 it can be seen that the main effect of the
both O-CPC concentration and K-FEL concentration was insignificant whereas the curvature effect of O-CPC
concentration A2 (p=0.0023) and cure temperature C2 (p=0.0023), given in table3, was statistically significant.
Table 5 shows that O-CPC concentration has the most significant (54%) effect on oil contact angle followed by
C.Temp (31%) and then K.FEL (9%). The increasing effect of contact angle could be attributed to the increased
amount of oil repellent hydrophobic finish as well as the increased concentration of resin (K-FEL). The degree of
crosslinking network increased as resin amount was increased from 20 to 40g l1, which reduced the accessibility
and availability of hydroxyl groups of cotton responsible for hydrophilic nature [23].

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 3. (ac) 3D Response surface plots, (d) predicted versus actual plot, and (e) normal probability plot, of the response air
permeability.

3.2.3. Air permeability.

It is clear from figure3 that AP increased with the increase in concentration of O-CPC and decreased with the
increase in concentration of K-FEL. The C-Temp had also significant effect on AP. This might be due to crosslinking
of the finish with the cellulose surface and on penetration of finish and resin through the cellulosic matrix caused
inter-chain crosslinking hence blocking the AP. However, the O-CPC concentration was much effective (coefficient
19.75) than that of the K-FEL concentration (coefficient7.38); with the increase in K-FEL, the porosity decreased
as mentioned above (table 3). Furthermore, it had been observed that both interaction terms of AC (coefficient
11.75) and BC (coefficient 9.25) were significant which gave the curvature effect in the behavior of AP. It might
be inferred that concentration of finish and curing temperature have important role in increasing comfort level
after the finishing process. Due to the crosslinking effect of resin, a layer of network forms on fabric which not only
imparts hydrophobicity but also the poor AP rating. The effect of resin has been reported previously for reduced
AP rating on cellulosic fabrics [24].

3.2.4. Crease recovery angle.

It can be seen from figure4 that increase in the concentration of K-FEL taking O-CPC and temperature C-Temp
constant, there observed a rapid increase in CRA of the finished fabric. The effect of K-FEL concentration
was much greater (coefficient 7.69) than that of the O-CPC concentration (coefficient 0.56) and C-Temp
(coefficient 3.69) (table 3). The R2 value is 0.78 and the adj. R2 value is 0.70. The lack-of-fit F-value of 2.73
and the corresponding p-value 0.6297 implied that the lack-of-fit was insignificant as good for fitted model
statistically.

3.2.5.Stiffness.
It can be seen from figure5 that the factors O-CPC, K-FEL and C-Temp all the three have negative effect, higher
the concentration of O-CPC, concentration of K-FEL and higher the curing temperature, lesser the stiffness which
implied that the fall of fabric was better with higher the level of the said three factors. Easy care or resin finishing

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 4. (ac) 3D Response surface plots, (d) predicted versus actual plot, and, (e) normal probability plot of the response crease
recovery angle.

increases the stiffness of fabric due to crosslinking. Generally, 8% increase in stiffness value has been reported after
the application of resin finish on cotton fabrics.

3.2.6. Tear and tensile strength.

The factors K-FEL and C-Temp both had statistically significant effect on the tear strength, as increasing the
K-FEL concentration and increasing the curing temperature, the tear strength decreased (figure 6, table3). While
in the case of tensile strength, it can be clearly seen from the figure7 that the factors K-FEL and C-Temp both had
statistically significant effect on the tear strength, as increasing the K-FEL concentration and increasing the curing
temperature, the tear strength decreased (table 3). One of the major drawbacks of resin finishing is the negative
effect on textile fabrics. The resin finish is known to significantly (up to 50 %) decrease in tear and tensile strength
of cellulosic fabrics has been reported previously [24, 25].

3.3. Quadratic models for response prediction

The experimental data were analyzed and second-order polynomial models were fitted. The regression
equationsdeveloped from the ANOVA in terms of actual factors for all the responses are given in table4.

3.4. Optimization through Derringers desirability function

We employed the Derringers desirability function approach to evaluate the effect of the optimized responses,
simultaneously. The least acceptable value of di was set as zero (totally undesirable), and the maximum value
as was set as one (totally desirable value). Oleo-hydrophobicity process optimization for maximizing the WCA,
OCA, AP, CRA, tear strength and tensile strength responses while minimizing the stiffness, simultaneously, under
desirability function approach (equation (3)(4)). Figure8 shows the individual desirability values and figure9
shows the 3D surface plot for the best result of the optimization process with 0.7769 overall desirability value (table
6). The best optimum settings were found to be O-CPC concentration of 44.44g l1, K-FEL concentration of 32.07
and C-Temp of 161.81 that optimized 134.53 WCA, 129.42 OCA, 290mm s1 AP, 213.76 CRA, 3.2928cm
stiffness, 1491.72 gf tear strength and 764.33 Nf tensile strength (table 7).

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 5. (ac) 3D Response surface plots, (d) predicted versus actual plot, and (e) normal probability plot of the response stiffness.

For the confirmation of the estimated optimized levels of each process parameter, a confirmation study was
also conducted. It was interesting to note that the WCA, OCA, AP, CRA, stiffness, tear strength and tensile strength
values obtained from confirmation study were almost matched with the values predicted by the desirability optim
ization approach (table 8). Yu etal [26] reported that WCA as 133 and OCA as 125 in their study without using
silica sol coating. Geun etal [27] used silica based nanoparticles synthesized via a solgel process and water repel-
lent agent to produce superhydrophobic of cotton fabric and reported 130 WCA as treated with combined silica
nanoparticles and water-repellent agent. Zhang etal [28] observed the WCA of 137 for the Scotchgard-protector-
coated cotton. Yinglei etal [29] applied the advanced statistical analysis techniques, of DOE and RSM for the
development of optimized design of compression sportswear which was a great contribution in the enhancement
of athletic performance and reduction of injury. Lee and Cho [30] employed RSM to investigate the effect of water-
repellent coating condition, concentration of polyurethane and curing temperature on vapor-permeable, water
resistance and fabric frictional sound. They suggested optimum surface coating conditions for the reduced fabric
friction sound and improved vapour-permeability.
In a fiber spinning process, Chung-Feng [31] employed the RSM for the development of statistical model
for the quality characteristics of filament to get more durable composite fiber by optimizing process parameters
including spinneret rotation speed, take-up roller speed and the spinning temperature. Hatice [32] studied optim
ization of elastane draw ratio, load and relaxation type for the best stretch and recovery properties of woven stretch
fabrics using RSM and the desirability function.

3.5. Scanning electron microscopy (SEM)

The SEM analysis of both control and treated cotton samples (figure 10) shows that surface of treated fabric was
impregnated with the finish particulates making it somehow roughened and glossy, whereas the control surface
was quite uniform and plane. These findings are in coherent with the reported literature [13] that the application
of a hydrophobic finish imparts roughness to the treated fabric.

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 6. (ac) 3D Response surface plots, (d) predicted versus actual plot, and (e) normal probability plot of the response tear
strength.

3.6. FTIR spectroscopy

The FTIR spectrum of control fabric (figure 11(a)) exhibited absorption values at 3271cm1and 2902cm1 due
to the presence of OH group and CH stretching, respectively, in the cellulose matrix. Again the absorption
peak at 1160cm1 was due to COC stretching in the cellulose chains. The spectrum of treated fabric (figure
11(b)) exhibited a peak at 1326cm1 due to CF bonds presence in the form of O-CPC finish. The peaks at
28003000cm1 were due to (CH3, CH2, CH and NH), again for the treated fabric.

3.7.Validation
The optimum results obtained from the desirability function with a desirability of 0.7769, given in table6,
were tested by preparing a test specimen with the optimum recipe of O-CPC concentration 44.44g l1, K-FEL
concentration 32.07g l1 and C-Temp of 161.81 and the results of each response were repeated and found to
be close to the optimum as well as the model predicted results. The validation test results are given in table7.
The Derringers desirability function based optimum responses were 134.53 WCA, 129.42 OCA, 290mm
s1 AP, 213.76 CRA, 3.2928cm stiffness, 1491.72 gf tear strength and 764.33 Nf tensile strength (table 7). For
validation, these obtained results were further studied by conducting one more confirmation experiment on
the optimized conditions of the process parameter suggested by the Derringers desirability function, it was
interesting that the confirmation results were found satisfactory of hydrophobicity resulting 140 WCA, 130
OCA, 318mm s1 AP, 204 CRA, 3.8996cm stiffness, 1598 gf tear strength and 900 Nf. (table 8). The graphical
images of oil and water contact angles of both the treated and untreated fabrics are shown in figure12 which
shows that the optimized recipe of the process parameters gave excellent hydrophobicity and oleophobicity
properties.

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 7. (ac) 3D Response surface plots, (d) predicted versus actual plot, and (e) normal probability plot of the response tensile
strength.

Figure 8. 3D desirability plot.

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

Figure 9. Individual desirability values of response variables.

Table 5. Contribution (%) of significant factors on various responses.

WCA OCA AP CRA Stiffness Tear Strength Tensile Strength

A 64 54 49 11 28 31 29
B 17 9 23 61 24 35 39
C 17 31 13 23 27 16 19
Interaction 0 5 12 0 8 0 9
Error 2 1 3 5 13 18 4

Table 6. Optimal solution proposed by Derringers desirability approach for the responses.

Factors Response variables

A B C y1 y2 y3 y4 y5 y6 y7

Solution O.CPC K.FEL C.Temp Tear Tensile

no. (g l1) (g l1) (C) WCA OCA AP CRA Stiffness strength strength Desirability

1 44.44 32.07 161.81 134.54 129.42 290.00 213.76 3.2928 1491.72 764.33 0.776857
2 44.43 32.06 161.81 134.54 129.42 290.00 213.76 3.2931 1491.76 764.35 0.776856
3 44.44 32.07 161.81 134.54 129.41 290.00 213.76 3.2929 1491.72 764.37 0.776856
4 44.45 32.04 161.81 134.53 129.41 290.00 213.75 3.2935 1491.79 764.49 0.776856
5 44.46 32.05 161.81 134.53 129.41 290.00 213.76 3.2930 1491.70 764.49 0.776856

Table 7. Prediction performance of RSM model.

Response Prediction SE mean 95% CI low 95% CI high SE pred 95% PI low 95% PI high

WCA 130.32 0.74 128.73 131.91 2.38 125.22 135.42

OCA 126.43 1.79 122.57 130.29 5.74 114.03 138.83
AP 264.21 3.67 256.22 272.21 11.80 238.51 289.92
CRA 206.75 1.82 202.84 210.66 5.86 194.19 219.31
Stiffness 3.65 0.05 3.54 3.76 0.20 3.22 4.08
Tear strength 1532.86 10.19 1511.01 1554.71 32.75 1462.61 1603.10
Tensile strength 731.49 6.68 717.16 745.81 25.52 676.75 786.22

Table 8. Confirmatory test results at optimum conditions.

WCA OCA AP CRA Stiffness Tear strength Tensile strength

140 130 318 204 3.8996 1598 900

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

(a) (b)

Figure 10. Representative SEM images of (a) unfinished and (b) finished cotton fabrics.

Figure 11. FTIR spectra of (a) unfinished and (b) finished cotton fabrics.

Figure 12. Static contact angle (SCA) of (a) untreated fabric, (b) water drop on treated fabric, (c) n-hexadecane oil on treated fabric.

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Mater. Res. Express 4 (2017) 035302 N Ahmad etal

4.Conclusions

In the present study, it was interesting to note that the desirability function based on RSM study had demonstrated
the statistically reliable results for the production of oleo-hydrophobic cotton fabric with optimized process
parameters. The concentrations of finish, and of cross-linker and curing temperature were important parameters
for the development of desired cotton fabric with optimum technical features. However, handling the process
parameters, simultaneously, was a quite difficult job. Hence an efficient and more reliable RSM based central
composite design was employed to study the wider levels of obtained parameters and their optimum levels for
maximum responses (WCA, OCA, AP, CRA, stiffness, tear strength and tensile strength) and seven respective
statistical models were developed. Finally, based on these models of several responses, Derringers desirability
function was successfully employed for simultaneous optimization of these multi-responses.

Acknowledgment

The authors acknowledge the Higher Education Commission of Pakistan for funding this study.

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