Accepted Manuscript Title: Cationic Starch (Q-TAC) Pre-Treatment of Cotton Fabric: Influence on dyeing with reactive dye Author: Shamshad Ali Mohsin Ali Mughal Umair Shoukat Mansoor Ali Baloch Seong Hun Kim PII: DOI: Reference:
S0144-8617(14)00974-6 http://dx.doi.org/doi:10.1016/j.carbpol.2014.09.064 CARP 9322
To appear in: Received date: Revised date: Accepted date:
13-3-2014 28-8-2014 15-9-2014
Please cite this article as: Ali, S., Mughal, M. A., Shoukat, U., Baloch, M. A., and Kim, S. H.,Cationic Starch (Q-TAC) Pre-Treatment of Cotton Fabric: Influence on dyeing with reactive dye, Carbohydrate Polymers (2014), http://dx.doi.org/10.1016/j.carbpol.2014.09.064 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Research Highlights •
Cationic starch was successfully applied on cotton fabric prior to reactive dyeing.
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Enhancement in color yield (70%) and dye fixation (20%) was achieved.
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Equivalent color fastness properties were obtained for treated cotton fabric.
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Cationic Starch (Q-TAC) Pre-Treatment of Cotton Fabric: Influence on dyeing with
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reactive dye
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Shamshad Ali a,b, Mohsin Ali Mughal a, Umair Shoukat a, Mansoor Ali Baloch a, and Seong Hun Kim a,*
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a
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Pakistan.
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Department of Textile Engineering, Mehran University of Engineering and Technology, Jamshoro 76062,
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b
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133-791, Korea.
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Department of Organic and Nano Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul
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18 * Corresponding Author: Seong Hun Kim
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[email protected] Tel: 0082-2-2220-4496
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Address:
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Department of Organic and Nano Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791, KOREA.
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ABSTRACT
39 Reactive dyes require high concentrations of an electrolyte to improve dye-fiber interaction, leading to the
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discharge of harmful effluent. One approach to reduce this unsafe release is treatment of the cotton fabric with
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cationic chemical reagents. This paper reports on the treatment of cotton fabric with cationic starch (Q-TAC), a
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commercial product, by batchwise method and pad batch method for the first time prior to reactive dyeing process.
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Furthermore, a commercial reactive dye, based on mono-chloro triazine chemistry, was applied on the cotton
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fabrics by continuous (pad-dry-cure) method. The treated cotton fabric by batchwise method produced 70%
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higher color yield (K/S) and 20% enhanced dye fixation (%F) than untreated cotton fabric. X-ray photoelectron
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spectrometer (XPS) analysis revealed the presence of N1s peaks in the treated cotton fabrics. The crystallinity of
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treated cotton fabrics was reduced in comparison to untreated cotton fabric as revealed by Wide angle X-ray
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diffraction (WAXD) measurements. Field Emission Scanning Electron Microscopy (FE-SEM) showed that the
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surface of treated cotton fabrics was rougher than untreated cotton fabric due to the deposition of cationic starch.
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Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrum confirmed the existence of
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quaternary ammonium groups, N+(CH3)3, in the treated cotton fabrics. The analysis of color fastness tests
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demonstrated good to excellent ratings for treated cotton fabrics. In this way, cationic starch treatment of cotton
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fabric before reactive dyeing process has been proven potentially a more environmentally sustainable method
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than conventional dyeing method.
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KEYWORDS: Reactive dyes, cationic chemical reagents, cationic starch, color yield, dye fixation.
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1. Introduction
71 Cotton is a dominant textile fiber over the years due to its unique properties including hydrophilicity,
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biodegradability, durability, good dyeability and relatively inexpensive (Fu et al. 2013). For these reasons, the
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share of cotton in total fiber consumption is about 50% (Hashem et al. 2009). Reactive dyes are vastly used in
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dyeing of cotton fiber owing to their wide gamut of hues and good wet fastness properties (Öner and Sahinbaskan
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2011). These dyes have a distinctive reactive nature due to active groups which form covalent bonds with
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hydroxyl groups of cotton (Khatri et al. 2011). However, considerable quantities of an inorganic electrolyte (e.g.
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sodium chloride or sulfate) and an inorganic alkali (e.g. sodium bicarbonate or carbonate or hydroxide) are
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required (Khatri et al. 2012). Under alkaline fixation condition (pH > 10.5), reactive dyes can react not only with
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the hydroxyl groups in cotton but also with water to form hydrolyzed dyes (Hao et al. 2012b); resulting into a
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considerable amount of colored effluent arises during washing off. Furthermore, unfixed dyes in the effluent pose
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an environmental hazard (Xie et al. 2009). Therefore, efforts have been made to enhance dye fixation (%F)
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leading towards higher color yield during cotton dyeing with reactive dyes.
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One method to overcome this problem is chemical modification of cotton with cationic agents, which can alter the
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surface charge of cotton enabling salt free dyeing with anionic dyes (Fu et al. 2013). The ionic attraction existed
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between the reactive dye and the cationized cotton brings about dye fixation (Hao et al. 2012a). Numerous
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chemical reagents were studied to prepare cationic cotton including 3-chloro-2-hydroxypropyl trimethylammonium
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chloride (CHPTAC) for enhancing color strength (K/S) of reactive dyes (Patiño et al. 2011) and natural dyes using
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ultrasonic technique (Kamel et al. 2011). Similarly, poly-aminochlorohydrin quaternary ammonium polymer with
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epoxide functionality was successfully used as cationising agent for applying anionic pigments (Hao et al. 2012b)
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and natural dyes extracted from Cochineal insects (Kamel et al. 2009) and plant waste (Oktav Bulut & Akar 2012).
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Cationic starch is the modified starch, produced by etherifying reaction of starch with the tertiary amino and
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quaternary ammonium cationising reagents (Käki et al. 2007); and are extensively used commercially due to their
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low cost and biodegradability (Zhang 2001). It has a large molecular size and binds to cotton by means of ionic
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bonding, hydrogen bonding and van der Waals forces (Zhang et al. 2005). The presence of quaternary
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ammonium groups, N+(CH3)3, in cationic starch enables anionic reactive dye molecules to attach rapidly forming
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ionic bonds.
100 Previous studies showed that cationic starch having higher degree of substitution (DS) = 0.8 was applied on
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cotton fabric only by pad-bake method; in which high quantity of surfactant was used to achieve leveling. Later on,
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the duration of reactive dyeing step employed was considerably high. For instance, it was carried out in 19
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minutes using a continuous (PadÆDryÆSteam) method (Zhang et al. 2005); and in 70 minutes by batchwise
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method (Zhang et al. 2007) excluding washing off duration. To the best of our knowledge, no earlier attempts
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have been made for treatment of cotton fabric with cationic starch with low DS by batchwise method and pad
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batch method for enhancing K/S and increasing %F of reactive dyes. Moreover, keeping in view the significance
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of high production rate required by the dye houses, the duration of reactive dyeing step should be short.
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The aim of our study was to apply the cationic starch (Q-TAC) having low DS on cotton fabric by batchwise
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method and pad batch method. Furthermore, the treated fabrics were dyed with reactive dye by using a single-
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bath continuous (Pad Æ Dry Æ Cure) method. We performed the reactive dyeing step in just 4 minutes excluding
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washing-off duration.
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2. Experimental
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2.1 Materials
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In this work, a commercially bleached and mercerized ready-to-dye cotton fabric (weight 120 g/m2 produced from
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warp yarn count of Ne 30/1 and weft yarn count of Ne 30/1) was used. Three commercial reactive dyes were used
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for dyeing cotton fabrics, namely CI Reactive Red 120 (Monochlorotriazine), CI Reactive Blue 19 (Vinylsulfone)
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and CI Reactive Red 195 (Monochlorotriazine + Vinylsulfone), supplied by DKC corporation Korea. Sodium
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hydroxide (36oBe), acetic acid, urea, sodium carbonate and sodium chloride were of analytical grade. Q-TAC
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(Rafhan Maize Pakistan) having DS in the range of 0.036-0.042%, Thermacol MIN (Migration Inhibitor based on
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solution of an acrylic copolymer, Hunstman Pakistan), Ladipur RSK (Anionic Detergent based on polycarboxylic
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acid, Clariant Pakistan), and Drimagen E2R (Anionic Leveling Agent based on aromatic polyether sulphonate,
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Clariant Pakistan) were of commercial grade. Deionized water was used for all the experiments done in this work.
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2.2 Application of cationic starch
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Q-TAC was applied on cotton fabric without using surfactant by batchwise method and pad batch method. In
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batchwise method, the cotton fabric was treated with 2-6% o.w.f Q-TAC solution at 40oC for 30 minutes in Rapid
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laboratory dyeing machine (Rapid Color C Type, Taiwan). Furthermore, the treated cotton fabric was washed with
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cold water and then with boil water for 5 minutes. The pH of the treated cotton fabric was neutralized in acetic
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acid solution followed by rinsing in cold water for 5 minutes. Treatment conditions were optimized by varying
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temperature (40-80oC) and pH (8-12). 20:1 was the liquor-to-good ratio taken during experiments. In pad batch
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method, the cotton fabric was padded with 5-25 g/L Q-TAC solution at ambient temperature on Rapid horizontal
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padding mangle (Air-Pad P-B1, Taiwan). The pick-up% was set at 70. The padded fabric was immediately
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wrapped in a polyethylene bag to avoid any air exposure. Washing-off process was performed as stated
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previously. Dwell time (6-24 Hours) and pH (8-12) were optimized.
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2.3 Reactive Dyeing
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The cotton fabrics were dyed by padding (single dip-single nip, 70% liquor pick-up) through a dye bath solution on
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Rapid laboratory horizontal padding mangle (Air-Pad P-B1, Taiwan). Dye bath solution contains 10 g/L Reactive
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Dye, 2 g/L Drimagen E2R, 20 g/L Thermacol MIN, 15 g/L Sodium Carbonate and 100 g/L Urea. The padded
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fabric was immediately dried at 120oC for 90 seconds followed by curing at 160oC for 90 seconds on Rapid
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laboratory mini dryer (R-3, Taiwan). Furthermore, the washing-off process was carried out by batchwise method
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(cold wash Æ hot wash Æ soaping-off Æ hot wash Æ neutralization Æ cold wash). The soaping-off was done at
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boil for 15 minutes in the presence of 2 g/l Anionic detergent (Ladipur RSK, Clariant). The liquor-to-good ratio was
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taken as 50:1.
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2.4 Color measurement and testing
155 K/S was assessed for each dyed sample with Gretag Macbeth CE-7000A spectrophotometer using the following
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instrument settings (8.4 mm sample aperture, illuminant D65, UV included and specular component included).
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Each specimen was measured from five different locations and the average value was reported. The relative color
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strength was assessed by using the Kubelka-Munk equation (Equation 1) as described in a previous report (Ali et
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al. 2013).
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(1)
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where R = decimal fraction of the reflectance of the dyed fabric,
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K = absorption coefficient and S = scattering coefficient.
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The percentage of reactive dye fixed on cotton fabric was measured using equation 2.
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……………………………….…………… (2)
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(K/S) a = color strength after wash and (K/S) b = color strength before wash.
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Color fastness to washing test was performed in Gyrowash (James H. Heal Co., UK) by following ISO-105-
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C10:2006; Color fastness to light test was carried out in Apollo (James H. Heal Co., UK) according to ISO-105-
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BO2:2013 (20 Hours) and Color fastness to rubbing was done on Crockmeter (James H. Heal Co., UK) by
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following ISO-105-X12:2001. The evaluation of color fastness properties of dyed fabrics were performed in
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accordance with ISO-105-AO2:1993 (Grey scale for assessing change in color) and ISO-105-AO3:1993 (Grey
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scale for assessing staining).
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2.5 Characterization
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Water absorbency of mercerized cotton fabric was monitored in accordance with AATCC Test Method 39 (Water
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Drop Disappearance). Degree of whiteness expressed as CIE Whiteness of cotton fabric was determined on
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reflectance spectrophotometer (Gretag Macbeth CE-7000A). pH of cotton fabric was measured by following
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AATCC Test Method 81-2012. The chemical composition of the cotton fabric surfaces was examined by X-ray
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photoelectron spectrometry (XPS; Theta Probe Base System, Thermo Fisher Scientific Co.) with Al Kα radiation.
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Survey spectrum was recorded at a detector pass energy of 100 eV and the high resolution spectra for N 1s
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regions were also obtained at a pass energy of 50 eV. The crystallinity of cotton fabrics were measured using
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wide angle X-ray diffraction (WAXD; Rigaku Denki Co. Japan), with Cu Kα radiation (λ = 1.5402 °A) at a scanning
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speed of 2ϴ = 2o/min. The data were taken in the range of 5o to 40o in steps of 0.02o at 40 kV and 60 mA. The
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morphology of untreated and treated cotton fabrics were examined under field emission scanning electron
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microscopy (FE-SEM; JSM 6701F, JEOL Japan) at two magnifications, namely 1000x and 4000x, using 15 kV
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accelerating voltage. The fabrics were coated with Platinum under vacuum by sputtering method. The attenuated
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total reflectance-Fourier transform spectroscopy (ATR-FTIR) spectra of cotton fabrics were recorded on Nicolet
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6700 FTIR spectrometer equipped with the ATR accessory (ThermoElectron Corporation, USA) in the range of
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4000-800 cm-1.
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3. Results and discussion
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3.1 Analysis of untreated cotton fabric
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Before Q-TAC treatment, some important fabric properties were measured of the mercerized cotton fabric used in
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this study. The fabric had an absorbency of one second, CIE whiteness index of 60.44 and pH extract of 8.5.
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Furthermore, the untreated cotton fabric was dyed with three different commercial reactive dyes by continuous
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(PadÆDryÆ Cure) method. The K/S value obtained was: CI Reactive Red 120 - 4.30, CI Reactive Blue 19 – 2.01
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and CI Reactive Red 195 – 5.20.
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3.2 Analysis of treated cotton fabric
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3.2.1 Batchwise method
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Table 1 summarizes the effect of different process parameters including temperature, pH and Q-TAC
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concentration on CIE whiteness and absorbency. It can be seen that by increasing process liquor temperature
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from 40oC to 80oC, CIE whiteness of treated cotton fabrics were enhanced. The optimum CIE whiteness was
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obtained at 80oC. Comparing with the untreated cotton fabric, CIE whiteness of treated cotton fabrics remained
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inferior. It was earlier reported that treatment of cotton fabric with cationic agents reduced CIE whiteness (Kanik &
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Hauser 2002). It was also revealed that fabric absorbency of treated cotton fabrics remained same at different
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process liquor temperatures. The observed water drop test rating of all specimens was one second. Hence, the
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amorphous content of cotton fiber polymer system was retained. Moreover, change of fiber surface polarity, from
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negative to positive, did not bring any adverse effect to moisture absorption characteristic of treated cotton fabrics.
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The optimized temperature considered for further experiments was 80oC.
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Additionally, the CIE whiteness of treated cotton fabrics were gradually enhanced as the alkalinity of Q-TAC
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solution increased. However, CIE whiteness was sharply declined at pH 12 possibly due to the yellowing effect of
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cotton fabric. The optimum CIE whiteness was achieved at pH 11. It was also observed that increasing alkaline
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pH of process liquor has not affected the fabric absorbency. The water droplet wet the surface of all specimens in
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one second. The optimized pH selected for further experiments was 11.
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It was also revealed that increasing Q-TAC concentration enhanced CIE whiteness of treated cotton fabrics. At
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6% Q-TAC concentration, optimum CIE whiteness of treated cotton fabric was achieved. Hence, it can be
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assumed that Q-TAC has been deposited well on the cotton fiber surface at optimized conditions. Fabric
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absorbency remained unchanged at different Q-TAC concentrations suggesting that amorphous region of treated
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cotton fabrics is retained which contributes towards wettability. Also, the duration of Q-TAC treatment by
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batchwise method before reactive dyeing step was found higher than the previous reports (Zhang et al. 2005;
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Zhang et al. 2007).
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3.2.2 Pad batch method
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Table 2 demonstrates the effect of different process parameters including batching time, pH and Q-TAC
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concentration on CIE whiteness and absorbency. It is evident that a gradual decline in CIE whiteness, that is,
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dullness was observed with increasing batching time possibly due to the yellowing effect on cotton fabrics. Fabric
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absorbency remained identical, that is, water droplet wet the treated cotton fabric surface in one second. The
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optimized batching time considered for further experiments was 6 hours.
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Referring Table 2, a steady enhancement in CIE whiteness was achieved with increasing alkalinity of process
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liquor. Water droplet wet the treated cotton fabric surface in one second for all the samples. The optimized pH
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chosen for further experiments was 12.
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Furthermore, a gradual decrease in CIE whiteness was achieved with a simultaneous increase in the Q-TAC
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concentration. Similar results were also reported previously (Kanik & Hauser 2002). At 5 g/L Q-TAC concentration,
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optimum CIE whiteness of treated cotton fabric was obtained. The treated cotton fabrics showed identical
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absorbency which suggest that their amorphous content is retained. Additionally, the duration of Q-TAC treatment
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by pad batch method before reactive dyeing step was found higher than the previous reports (Zhang et al. 2005;
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Zhang et al. 2007).
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We have successfully applied Q-TAC as a cationic agent on the cotton fabric by batchwise method and pad batch
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method for the first time. However, it was accompanied with some loss of CIE whiteness. In general, cotton
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fabrics treated with Q-TAC by batchwise method exhibited higher CIE whiteness in comparison to pad batch
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method. The probable reason could be the combined effect of temperature and agitation given in the earlier
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method.
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3.3 Surface chemical composition of cotton fabrics
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Table 3 shows the atomic composition of cotton fiber surface at a 10 nm depth and the binding energy of
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electrons associated with those atoms. The measurements were recorded on XPS. The cotton fabrics showed
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C1s and O1s peaks at 285 eV and 532 eV respectively. However, the untreated cotton fabric has no N1s peak at
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399 eV, which is consistent with its chemical structure and reported previously (Patiño et al. 2011). The treated
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cotton fabrics showed N1s peak indicating the presence of Q-TAC on the surface of cotton fiber (Scheme 1a).
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The treated cotton fabric by batchwise method produced higher nitrogen content (1.27%) in comparison to the
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treated cotton fabric by pad batch method (0.53%) suggesting greater attachment of Q-TAC by earlier method.
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Comparing with untreated cotton fabric, the application of Q-TAC by batchwise method was resulted into a
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decrease in the carbon content by 3.46% as well as an increase in the oxygen content by 2.2% (Patiño et al.
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2011).
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decreased the oxygen content by 4.92% in comparison to the untreated cotton fabric. This may possibly be due to
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the lack of temperature and agitation present in pad batch method resulting into an inadequate deposition of Q-
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TAC on the cotton surface.
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On contrary, Q-TAC treatment by pad batch method increased the carbon content by 4.39% and
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3.4 Crystallinity of cotton fabrics
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Cationic agent treatment of cotton fabrics can change the crystal form and crystallinity of fibers (Wang et al. 2009).
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In addition to this, WAXD patterns of undyed cotton fabrics were measured and presented in Fig. 1a-c. The cotton
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fabrics showed a sharp peak at 2ϴ = 22.9o along with other small peaks at 2ϴ = 15o, 16.7o and 34.7o,
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corresponding to (3.94Å), (6.01Å), (5.35Å), and (2.58Å) d-spacing, which is the characteristic of cellulose I
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structure (Ford et al. 2010). The results revealed that Q-TAC treatment does not change the crystalline form of
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treated cotton fabrics. However, the peak intensities of the treated cotton fabrics were reduced compared to
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untreated cotton fabric (Shateri Khalil-Abad et al. 2009), possibly due to the hydroxyl groups being substituted by
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grafting of the Q-TAC (Scheme 1a). Furthermore, the crystallinity of treated cotton fabrics were reduced as the
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density of hydrogen bonds lowered because of the hydroxyl group substitution. The cotton fabric treated by pad
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batch method showed the least crystalline form (Fig. 1c). This may possibly be attributed to the prolonged
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reaction time (6 hours) given to the cotton fabric at high alkaline pH.
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3.5 Morphology of cotton fabrics
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Fig. 2a-f shows the surface morphology of undyed cotton fabrics using FE-SEM. It can be observed that the
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untreated cotton fibers are relatively parallel with smooth surface. But they are bent due to the two reasons; firstly
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the effect of twist in the yarn and secondly is the interlacing of the yarns in the fabric structure (Fig. 2a-b). In
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contrast, the treated cotton fibers showed rough surface (Fig. 2c-f); which is in agreement with earlier reports
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(Shateri Khalil-Abad et al. 2009; Wang et al. 2009). This is due to the attachment of cationic agent on the cotton
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fiber surface (Ristić & Ristić 2012). The deposition of Q-TAC by batchwise method (Fig. 2c-d) is higher than pad
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batch method (Fig. 2e-f) probably due to the combined effect of temperature and agitation used in the latter
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method. This result also supports the XPS findings in which the cotton fabric treated by batchwise method
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exhibited higher nitrogen content than the cotton fabric treated by pad batch method.
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3.6 Analysis of color strength (K/S) and dye fixation (%F)
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Fig. 3 shows the effect of processing method employed for Q-TAC treatment on K/S and %F of cotton fabrics with
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three different reactive dyes. In general, the results revealed that higher K/S and %F values were obtained for
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treated cotton fabrics than the untreated cotton fabric. This may possibly be due to the two reasons. Firstly, higher
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ionic attraction existed between the dye anion and the quaternary ammonium groups of Q-TAC leading to higher
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dye absorption (Scheme 1b). Secondly, the crystallinity of cotton fabrics was reduced after Q-TAC treatment
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resulting into the greater diffusion of dye molecules into the treated cotton fabrics. It was also found that the
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cotton fabric treated by batchwise method exhibited maximum K/S and %F (Fig. 3) possibly due to the greater
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deposition of Q-TAC on its surface as shown in Fig. 2c-d.For CI Reactive Red 120,the results indicated that the
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Q-TAC treatment of cotton fabrics significantly enhanced the K/S to 10% and 70% for pad batch method and
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batchwise method respectively, and the treated cotton fabric yielded higher %F than the untreated cotton fabric
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showing an increase of 6% and 20% for pad batch method and batchwise method respectively.
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We have achieved %F of 90, which is 18% higher than a previous study (Zhang et al. 2005) for
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Monochlorotriazine (MCT) dye. Furthermore, 17% and 15 % higher %F were obtained for Monochlorotriazine +
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Vinylsulfone (MCT/VS) dye and Vinylsulfone (VS) dye respectively (Zhang et al. 2007). More significantly, the
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duration of reactive dyeing step used was considerably shorter than the previous reports (Zhang et al. 2005;
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Zhang et al. 2007). Additionally, the combined duration of Q-TAC treatment by batchwise method and reactive
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dyeing steps was shorter by 65 minutes (Wang et al. 2009), 39 minutes (Zhang et al. 2007) and higher by 17
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minutes (Zhang et al. 2005).
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3.7 Analysis of color fastness tests 12 Page 12 of 26
326 Table 4 outlines the results of color fastness to washing, rubbing and light. By comparing with untreated dyed
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fabric, the color fastness properties of the treated dyed fabric were similar demonstrating that the dye fixation was
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equally good on them. In the color fastness to rubbing test, the dry and wet rubbing fastness was found good with
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no significant color change for all the samples. The light fastness rating was good to excellent for both samples.
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The results for color fastness to washing (change in color) was good, and the color fastness to washing (staining
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on multifiber) ratings were good to excellent except CO, PA and PES which were good probably due to the
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greater affinity of reactive dyes towards these three types of fibers. The better results for the color fastness to
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washing (staining on multifiber) for CT, PAC and WO was ascribed to their anionic nature resulting into the
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repulsion of reactive dyes under the testing condition (Hao et al. 2012b). We have successfully applied reactive
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dye using a continuous (PadÆDryÆCure) method in just 4 minutes without compromising color yield as well as
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fastness properties.
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3.8 Chemical structure of cotton fabrics
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Fig. 4a-b shows the ATR-FTIR spectra of undyed and dyed cotton fabrics previously treated with Q-TAC. The
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treated cotton fabrics showed characteristic cellulose peaks at around 1000-1200 cm-1 (Khatri et al. 2013a) in
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which the peaks present at 1160 cm-1 and 1028 cm-1 are ascribed for C-N stretching vibration and primary C-O-H
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stretching deformation respectively (Kamel et al. 2009; Oktav Bulut & Akar 2012). Other characteristic bands
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related to the chemical structure of cellulose were the hydrogen-bonded O-H stretching around 3500-3200 cm-1,
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the C-H stretching at 2900 cm-1, and the C-H wagging at 1316 cm-1 (Chung et al. 2004; Jonoobi 2011). ATR-FTIR
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spectra of dyed fabrics (Fig. 4b) have retained their chemical structure after being dyed with Procion Dark Blue
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HEXL. The interaction in between the reactive dye molecule and the treated cotton fabrics is difficult to identify
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probably due to the small amount of dyestuff used in the experiments (Khatri et al. 2013b).
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4. Conclusion
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We investigated that after Q-TAC treatment by batchwise method; K/S and %F have increased to 70 % and 20%
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respectively in comparison to the conventional method. Excellent color fastness properties were achieved for both
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untreated dyed cotton and treated dyed cotton fabrics. The existence of N1s peaks was found by XPS
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measurements showing the presence of Q-TAC on the surface of treated cotton fabrics. The crystallinity of
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treated cotton fabrics was reduced in comparison to untreated cotton fabric as demonstrated by WAXD analysis.
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The existence of Q-TAC deposits on the cotton fiber surface was revealed by FE-SEM micrographs. The cotton
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fabrics showed characteristic cellulose peaks, and they retained their chemical structure after being dyed as
360
demonstrated by ATR-FTIR analysis.
us
cr
ip t
353
361 362
Acknowledgements
an
363
This research was supported by the National Research Foundation of Korea (Project No. 2013-055716) and
365
Mehran University of Engineering and Technology Jamshoro Pakistan. Mr Shamshad Ali is grateful for the
366
financial support received from Higher Education Commission Pakistan under the HRDI-UESTPs/UETs
367
scholarship. Mr Abdul Khalique Jhatial and Mr Aijaz Ahmed are also acknowledged for their assistance during
368
experimental work.
te
369
d
M
364
Abbreviations
371
o.w.f–on the weight of fabric; CT-cellulose triacetate; CO-cotton; PA-polyamide; PES-polyester; PAC-
372
polyacrylonitrile; WO-wool.
373 374 375
Ac ce p
370
REFERENCES
376
Ali, S., Khatri, Z., Khatri, A., & Tanwari, A. (2013). Integrated desizing–bleaching–reactive dyeing process for
377
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380
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Hao, L., Wang, R., Liu, J., & Liu, R. (2012a). The adsorptive and hydrolytic performance of cellulase on cationised
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Hao, L., Wang, R., Liu, J., & Liu, R. (2012b). Ultrasound-assisted adsorption of anionic nanoscale pigment on
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Jonoobi, M., Khazaeian, A., Tahir, P., Azry, S., & Oksman, K. (2011). Characteristics of cellulose nanofibers
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Käki, J., Hendrik, L., Kari, N., Gösta, B., Hanna, G., Anneli, H., Aki, L., & Jari, Y-K. (2007). Type of cationic starch
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Kamel, MM., El Zawahry, MM., Ahmed, NSE., & Abdelghaffar, F. (2009). Ultrasonic dyeing of cationized cotton
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fabric with natural dye. Part 1: Cationization of cotton using Solfix E. Ultrasonics Sonochemistry, 16 (2), 243-249.
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408
fabric with natural dye. Part 2: Cationization of cotton using Quat 188. Industrial Crops and Products, 34 (3),
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1410-1417.
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Kanik, M., & Hauser, PJ. (2002). Printing of cationised cotton with reactive dyes. Coloration Technology, 118 (6),
411
300-306.
412
Khatri, A., Padhye, R., & White, M. (2012). The use of trisodium nitrilo triacetate in the pad–steam dyeing of
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cotton with reactive dyes. Coloration Technology, 129 (1), 76-81.
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Khatri, Z., Arain, R., Jatoi, A., Mayakrishnan, G., Wei, K., & Kim, I.-S. (2013a). Dyeing and characterization of
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cellulose nanofibers to improve color yields by dual padding method. Cellulose, 20 (3), 1469-1476.
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Khatri, Z., Memon, MH., Khatri, A., & Tanwari, A. (2011). Cold Pad-Batch dyeing method for cotton fabric dyeing
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Oktav Bulut, M., & Akar, E. (2012). Ecological dyeing with some plant pulps on woolen yarn and cationized cotton
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Öner, E., & Sahinbaskan, BY. (2011). A new process of combined pretreatment and dyeing: REST. Journal of
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Patiño, A., Canal, C., Rodríguez, C., Caballero, G., Navarro, A., & Canal, J. (2011). Surface and bulk cotton fibre
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modifications: plasma and cationization. Influence on dyeing with reactive dye. Cellulose, 18 (4), 1073-1083.
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Ristić, N., & Ristić, I. (2012). Cationic Modification of Cotton Fabrics and Reactive Dyeing Characteristics. Journal
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Shateri Khalil-Abad, M., Yazdanshenas, M., Nateghi, M. (2009). Effect of cationization on adsorption of silver
436
nanoparticles on cotton surfaces and its antibacterial activity. Cellulose, 16 (6), 1147-1157.
437 Wang, L., Ma, W., Zhang, S., Teng, X., & Yang, J. (2009). Preparation of cationic cotton with two-bath pad-bake
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440
Xie, K., Liu, H., & Wang, X. (2009). Surface modification of cellulose with triazine derivative to improve printability
441
with reactive dyes. Carbohydrate Polymers, 78 (3), 538-542.
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438
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442
Zhang, L.-M. (2001). A Review of Starches and Their Derivatives for Oilfield Applications in China. Starch –
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Zhang, M., Ju, B-Z., Zhang, S-F., Ma, W., & Yang, J-Z. (2007). Synthesis of cationic hydrolyzed starch with high
447
DS by dry process and use in salt-free dyeing. Carbohydrate Polymers, 69 (1), 123-129.
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446
448
Zhang, S., Ma, W., Ju, B., Dang, N., Zhang, M., Wu, S., & Yang, J. (2005). Continuous dyeing of cationised cotton
450
with reactive dyes. Coloration Technology, 121 (4), 183-186.
te
d
449
452 453 454 455 456
Ac ce p
451
457
Table 1
458
Summary of experimental results of treated cotton fabric by batchwise method o
S. No:
Temperature ( C)
1
40
2 3
pH
Concentration (%)
Liquor-to-good ratio
Time (Min.)
CIE whiteness
Absorbency (Sec.)
10
2
20:1
30
40.43
1
50
10
2
20:1
30
42.16
1
60
10
2
20:1
30
44.01
1
17 Page 17 of 26
70
10
2
20:1
30
46.52
1
5
80
10
2
20:1
30
50.87
1
6
80
8
2
20:1
30
48.20
1
7
80
9
2
20:1
30
49.02
1
8
80
10
2
20:1
30
50.87
1
9
80
11
2
20:1
30
53.02
1
10
80
12
2
20:1
30
50.04
1
11
80
11
2
20:1
30
53.02
1
12
80
11
3
20:1
30
53.91
1
13
80
11
4
20:1
30
54.31
1
14
80
11
5
20:1
30
55.10
1
15
80
11
6
20:1
30
56.30
1
an
us
cr
ip t
4
459
M
460 461 462
d
463
te
464 465 467 468 469 470 471 472 473
Ac ce p
466
474
Table 2
475
Summary of experimental results of treated cotton fabric by pad batch method S. No:
Batching Time (Hrs.)
1
06
2 3
pH
o
Concentration (g/L)
Pick-up (%)
Temperature ( C)
CIE whiteness
Absorbency (Sec.)
10
5
70
25
43.51
1
12
10
5
70
25
41.50
1
18
10
5
70
25
40.17
1
18 Page 18 of 26
24
10
5
70
25
39
1
5
06
8
5
70
25
41.69
1
6
06
9
5
70
25
42.60
1
7
06
10
5
70
25
43.51
1
8
06
11
5
70
25
44.76
1
9
06
12
5
70
25
47.37
1
10
06
12
5
70
25
47.37
1
11
06
12
10
70
25
44.80
1
12
06
12
15
70
25
43.90
1
13
06
12
20
70
25
43.04
1
14
06
12
25
70
25
42.10
1
477
cr
M
478 Table 3
d
Atomic concentrations generated through XPS
Binding energy (eV)
te
Cotton fabric C1s
Ac ce p
Untreated Treated with batchwise method
285
O1s
532
N1s
399
Treated with pad batch method
481 482 483 484 485 486 487 488
us
an
476
479 480
ip t
4
Atomic concentration (%) C1s
O1s
N1s
67.02
32.98
---
63.56
35.18
1.27
71.41
28.06
0.53
Table 4 Color fastness to washing test ISO 105 C10:2006, Color fastness to rubbing test ISO 105 X12:2001 and color fastness to light test ISO 105 BO2:2013 of cotton fabric dyed with Procion Dark Blue HEXL
Dyed fabric
Rubbing
Light
fastness
fastness
Washing fastness
19 Page 19 of 26
Staining on multifiber
Untreated Cationic Starch
reference
Change in color CT
CO
PA
PES
PAC
WO
3.5
3.5
6
4
4.5
4
4
4
4.5
4.5
3.5
3.5
6
4
4.5
4
4
4
4.5
4.5
cr
treated
Wet
wool
ip t
Dry
Blue
489
us
490 491 492
an
493 494
M
495 496
te
d
497 498
Ac ce p
499 500 501 502 503 504 505 507
A H 2C
CH
CH2
N +(CH3)3Cl- + NaOH
H2C
OH
509
H 2C
CH O
CH
CH 2
N+(CH3)3 + NaCl + H 2O
O
CH 2
+
N (CH3)3 + Cell OH
OH -
20 Cell
O
H2C
CH
CH 2
N +(CH3)3
Page 20 of 26
510 511 512
516 518 520
B Cell
O
H2C
CH
CH 2
N+(CH 3)3 + : D-
Cell
an
526 Cl
N+(CH3)3D-
N
530 D NH
O
N N
D
NHR
S
CH
CH2
O
536 N +(CH 3 )3
te
d
534
SO-3
M
528
540
CH 2
VS dye
MCT dye
SO-3
CH
us
524
538
H2C
(D- =anionic reactive dye)
522
532
O
cr
514
ip t
513
N+(CH3 )3
543 544 545 546 547
Ac ce p
Q-TAC treated cotton f abric
542
Scheme 1. (A) Reaction of cationic starch with cotton fabric. (B) Reactive dye fixation on Q-TAC treated cotton fabric by ionic bonding.
548 549
Figure Captions
550 551 552 553
Fig. 1. XRD patterns of cotton fabric (A) untreated, (B) treated with Q-TAC by batchwise method, and (C) treated with Q-TAC by pad batch method.
21 Page 21 of 26
554 555 556 557 558 559
Fig. 2. FE-SEM images of cotton fabric (a,b) untreated, (c,d) treated with Q-TAC by batchwise method, and (e,f) treated with Q-TAC by pad batch method. Fig. 3. Effect of processing method on K/S and %F of dyed cotton fabrics with three dyes. (Dyeing conditions: Dye-10 g/L, sodium carbonate-15 g/l, urea-100g/L, pick-up 70%)
561
ip t
560
Fig. 4. ATR-FTIR spectra of cotton fabric (A)Untreated, (B)treated with Q-TAC / Reactive dyed.
Ac ce p
te
d
M
an
us
cr
562
22 Page 22 of 26
563
3590
4000 A
565
10
15
20
25
30
2 Theta (degree) 4000 2778 1150 1003
2000
0 5
te 10
15
20
349
d
1000
M
3000
40
an
B
35
us
5
cr
358
1000
0
Intensity, cps
ip t
1607 1345
2000
Ac ce p
25
30
35
40
2 Theta (degree)
4000
2615
C
3000
2000
1005 899
1000
322
571
Intensity, cps
569
Intensity, cps
3000
567
0 5
10
15
20
25
30
35
40
2 Theta (degree)
23 Page 23 of 26
573 575 577
ip t
579
Ac ce p
te
d
M
an
us
cr
581
24 Page 24 of 26
582
[SA1]
583 584
ip t
585 586
100
10 CI Reactive Red 120
60 %F
K/S
80
6
594 596
40
4
598
590
CI Reactive Red 120
us
8
592
cr
[SA2]
an
588
600
M
20
2
0
Un-treated
602
Pad Batch
Batchwise
Un-treated
Pad Batch Processing Method
d
Processing Method
te
CI Reactive Blue 19
4
612 2
614
Un-treated
616 10
618
610
40 20 0 Un-treated 100
CI Reactive Red 195
Pad Batch
Batchwise
Processing Method CI Reactive Red 195
80 60
6
%F
K/S
608
60
Batchwise
Processing Method
8
620
Pad Batch
CI Reactive Blue 19
80
%F
Ac ce p
K/S
8 6
604
100
10
606
Batchwise
40
4
20
2
0 Un-treated
Pad Batch Processing Method
Batchwise
25
Un-treated
Pad Batch
Batchwise
Processing Method
Page 25 of 26
621
[SA3]
622 623
[SA4]
-1.95
1028 1316 1160
3330
M
-1.95
-1.90
an
2900
-1.90
-1.85 1316 1160
-1.85
us
-1.80
1028
-1.80
Absorbance
-1.75 B
3330
-2.00
-2.00
3500
3000
2500
2000
1500 4000 1000 3500
d
4000
-1
Wavenumbers, cm
te
Absorbance
631
-1.75 A
3000
2500
2000
1500
1000
-1
Wavenumbers, cm
Ac ce p
629
cr
627
2900
625
ip t
624
26 Page 26 of 26