Accepted Manuscript

Effect of reverse micelle-encapsulated reactive dyes agglomeration in dyeing

properties of cotton

Cheng Hao Lee, Yiu Lun Tang, Yanming Wang, Chi Wai Kan

PII: S0143-7208(18)30641-7
DOI: 10.1016/j.dyepig.2018.09.037
Reference: DYPI 7019

To appear in: Dyes and Pigments

Received Date: 23 March 2018

Revised Date: 7 August 2018
Accepted Date: 16 September 2018

Please cite this article as: Lee CH, Tang YL, Wang Y, Kan CW, Effect of reverse micelle-encapsulated
reactive dyes agglomeration in dyeing properties of cotton, Dyes and Pigments (2018), doi: https://
doi.org/10.1016/j.dyepig.2018.09.037.

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 ACCEPTED MANUSCRIPT
Effect of reverse micelle-encapsulated reactive dyes agglomeration in
dyeing properties of cotton

Cheng Hao Lee1, Yiu Lun Tang 2, Yanming Wang2, Chi Wai Kan2*

1
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University,
Hung Hom, Kowloon, Hong Kong SAR, China

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2
Institute of Textile and Clothing, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong
SAR, China

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*

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Correspondence author: tccwk@polyu.edu.hk

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Abstract

Reverse micelles using nonionic poly(ethyleneglycol) (PEG)-based surfactant as building

block were introduced to encapsulate reactive dye for cotton dyeing. The morphological

transition of reactive dyes from well-dispersive spherical form into highly agglomerated

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form via various surfactant-to-co-surfactant molar ratios and surfactant-to-water molar ratios

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have been preliminary investigated. The dyeing properties of cotton has been analyzed in

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terms of dispersion of reverse micelle structure from transmission electron microscopy,

identification of chemical signatures of dye-cotton interaction from Raman spectroscopy,

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color strength and relative levelness. The reverse micellar structures under both highly

dispersed and agglomerated forms are in good agreement with color strength and levelness
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data. The optimization of surfactant conditions can be considered as major parameters for
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investigating the quality of cotton dyeing including color strength and levelling conditions.
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Keywords: Reverse micelle, Cotton, Surfactant, Co-surfactant, Reactive dye, Dye

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agglomeration
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1. Introduction

Reactive dyes are the most commonly used dyes for cellulosic materials and provide a

complete color range and are easily applied [1,2]. It is also applicable for organic cotton

due to the presence of strong dye-cotton fiber interaction. The parameters affecting reactive

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dyeing are dye chemistry, reactivity, diffusion coefficient and solubilization of dye

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component [1,3]. Another most important parameter affecting exhaustion and “fixation” of

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reactive dyes are temperature, salt concentration, alkali concentration, and liquid ratio.

Dyeing conditions especially the alkali requirement and temperature as well as the use of salt

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depend on the type of reactive group [2,4-7]. Reactive dyes are characterized by

undesirable hydrolysis in solution, which impedes effective dye fixation.

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Reactive dyes react with of the water molecule via hydrogen bond result in poor
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colorfastness of the cotton fiber. However, the hydrophilicity nature of both water and cotton
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fiber inevitably compromises the dyeing efficiency because water shares the similar reactive
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functionality with cotton cellulose. The size of agglomerated dye particles could also
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influence the surface free energy and diffusion of encapsulated dye into subsurface region of
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the cotton fiber matrix [8]. Control of dye dispersibility improves the fastness properties as

well as the productivity of dyeing process. The fastness improvement may be reflected as

better dye fixation with textile fiber via covalent bonding.

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The effective dyeing properties of cotton fabric has received a considerable attention

from the mechanism of dye–cotton interaction. As we known that native cotton fiber is a

highly crystalline fiber, in which linear macromolecules keep together via intra and

inter-molecular hydrogen bonds, and form a well-organized chain structure. Even its

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amorphous regions also consist of ordered stiffed chain structures. From the conventional

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pore model theory [9], dye molecules can only adsorb and diffuse or penetrate into the

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network of interconnecting pores in amorphous regions of cotton fabric under swelling in

water in conventional aqueous dyeing.

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As the diffusivity of dyes with controlled size into the cotton matrix and binding of

reactive dye to hydrophilic cellulosic fabric surface exert a significance influence on dye
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fixation, ultimate color yield and colorfastness of a dyed fiber [10-12].

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In textile processing, development of environmental-friendly reactive dyeing

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technology has been made to improve the cotton dyeability such as surface modification
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of cellulosic fibers with amide-terminated dendrimer [13] and amino-terminated

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hyperbranched polymer [14]. However, the preparation of highly branched polymeric

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structures via melt polymerization is tedious and additional purification steps are required,

In addition, the uneven distribution of cationic groups on cotton fabrics may potentially

lead to substantial unlevelness problem of dyed cotton fabrics. Other modification such as

introduction of clay as nano-adsorbent for better adsorption and fixation of basic dyes [15].

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The drawbacks include clay particles are required to reduce to appropriate size by

ultrasonic crashing process and particle size distribution are significantly broad, the clay

mineral particles have to be well dispersed via introduction of dispersing agent and long

pretreatment time prior to dyeing. Among all methods mentioned, chemical modification

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of cellulosic fabric surface may generate extra chemicals in the effluent. In order to

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effectively minimize the effluent pollution, various types of treatment processes have been

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developed for reduction of dye wastewater [16]. However, replacement of water with the

use of recyclable non-aqueous solvent as the dyeing medium can highly reduce the

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production of dye wastewater. Water-soluble reactive dyes can be well dispersed and

maintained in non-hydrolyzed form in non-aqueous solvent with the aid of reverse micelles
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[17-20]. At present, the reverse micelles have been concerned as dyeing media with
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minimized water consumption and high concentration dyeing. Reverse micelles are
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self-assembled nanosized structure formed by surfactants with amphiphilic nature in organic

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solvent [21,22], and a stable aqueous microenvironment, the so-called “water-pool” are
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formed by the solubilization of water in their polar or hydrophilic cores and hydrophobic
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segment molecules exposed to organic solvent [23]. The reverse micelles with spherical

shape are usually formed in ternary phase of surfactant-water-organic solvent mixtures

including surfactants (~10%), water (0-10%), and organic solvent (80%-90%), so the reverse

micelles are also called water-in-oil (W/O) emulsions. Moreover, reverse micellar systems

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are colloidal solutions and the characteristic properties of these systems are thermodynamic

stable (no phase separation with time), spontaneous formation, low interfacial tension (＜

10-2 mN·m-1), transparent nature (nanometer size range from 10 nm to 100 nm), large surface

area (102-103m2·cm-3), viscosity comparable with pure organic solvents [24].

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This work aimed to evaluate the effects of co-surfactant to surfactant molar ratio and

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waterpool-to-surfactant molar ratio on the agglomeration behavior of reverse micelle-based

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dye carrier and its morphological evolution. Various agglomeration behaviors are significant

for the evaluation of dyeing quality of cotton fabric.

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2. Materials and Methods
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2.1 Materials and reagents

Commercially scoured knitted fabric was first washed with commercial detergent in a
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thermal-control washing machine at temperature of 50oC. After treatment, the fabric was
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dried at an ambient temperature. The nonionic surfactant, poly(ethylene glycol) (12)

tridecylether (C13H27(OCH2CH2)nOH) (n~12) was of reagent grade. Heptane was used as

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major organic solvent and n-octanol was used as co-surfactant in dyeing procedure. Both

solvent and co-surfactant were of reagent grade. Before the adsorption experiments,
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Levafix CA-typed reactive red dye was directly used without further purification. Deionized
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water was used as dye dispersant throughout the dyeing process.

2.2 Preparation of reverse micelle encapsulated dye in heptane

A series of nonionic PEG-12 Tridecyl ether based reverse micelle was prepared by a

simple injection method at room temperature. The liquor ratio was 8:1 (1g of cotton in 8 ml

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of heptane). The non-ionic surfactant and co-surfactant (n-octanol) were first premixed

through agitation in a beaker. The sample preparation are divided into two parts: (i) The

surfactant/co-surfactant mixtures with co-surfactant to surfactant molar ratios (6:1, 8:1 and

9:1) when water to surfactant molar ratio was fixed as 25 : 1. (ii) The water to surfactant

molar ratio (20 : 1, 25 : 1 , 30 : 1 and 40 : 1) when co-surfactant to surfactant molar ratio was

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fixed as 8 : 1. The amount of surfactant and co-surfactant introduced in the reverse micellar

solution were listed in Table 1. All mixtures were respectively dispersed in n-heptane to

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obtain a designated PEG-12 Tridecyl ether reverse micelle solution. Reactive red dye

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aqueous solution (0.06g soluble in 0.5 mL water) was then applied into the reverse micelle

systems dropwise. After the injection, the mixtures were vigorously stirred for 2 min until the

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clear reverse micelle encapsulated Levafix CA-typed reactive dye was obtained.
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Table 1 The amount of surfactant and co-surfactant used in 8ml of heptane to 1 g of cotton
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fabric
Co-surfactant to H2O to surfactant Surfactant amount Co-surfactant amount
surfactant molar ratio molar ratio (g) (g)
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6:1 1.246 1.39

8 :1 25 :1 1.246 1.85
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9:1 1.246 2.08

20 : 1 1.56 2.32
8 :1 25 : 1 1.246 1.85
30 : 1 1.04 1.54
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40 : 1 0.779 1.16
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2.3 Cotton dyeing and fixation using aqueous solution (with salt)
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The schematic diagram of the whole cotton dyeing process in aqueous solution was

shown in Figure 1a. 4g of salt was dissolved in 50 mL of water. Then cotton fabric (1 gm)

was immersed into the salt solution and the container was placed in the water-shaking bath

for 10 min. The temperature and shaking rate were 60 oC and 110 shakes per minute. 0.06g

Levafix CA-type reactive red dye was dissolved in salt solution. The container with dye

solution was placed in the water-shaking bath for 40 min. dyeing process. The temperature

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and shaking rate were 60oC and 150 shakes per minute. After dyeing, 0.25g soda ash

(Na2CO3) were added into the container and further shaking for 1 hr fixation process under

the same condition as dyeing process. After fixation, the cotton fabric was then immersed

into 15 mL of detergent solution (2g/L) and subsequently placed in the water-shaking bath at

50oC for 15 min and 150 shakes per minute. The detergent-treated dyed cotton was then

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rinsed with water, air-dried and conditioned at a relative humidity of 65 ± 2% and 20 ± 2 °C

for at least 24 hours.

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2.4 Cotton dyeing and fixation using nonionic surfactant-based reverse micelle in heptane

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(without salt)

The schematic diagram of the whole reverse micelle dyeing process was shown in

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Figure 1b. A series of nonionic PEG-12 Tridecyl ether reverse micelle was prepared by a
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simple injection method at room temperature. Dye-encapsulated reverse micelle samples

with various surfactant parameters were first premixed respectively through agitation in a
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beaker. Then the surfactant/co-surfactant mixture was both dissolved in 8 mL of n-heptane to

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obtain organic surfactant solution with a designated PEG-12 Tridecyl ether reverse micelle
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solution. Levafix CA-typed reactive dye aqueous solution (0.06g soluble in 0.5 mL) and soda

ash (Na2CO3) aqueous solution (0.12 g soluble in 0.3 mL) mixture were then applied into the
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reverse micelle systems dropwise. After the injection, the mixtures were vigorously stirred

for 2 min until the clear reverse micelle encapsulated Levafix CA-typed reactive red dye was
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obtained. Then cotton fabric (1 gm) was immersed into the reverse micelle solution and the
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container was placed in the water-shaking bath with heating rate of 1oC/min. The
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temperature and shaking rate were 70 C and 150 shakes per minute. After dyeing and

fixation combined process for 90 min., the cotton fabric was then immersed into 15 mL of

detergent solution (2g/L) and subsequently placed in the water-shaking bath at 50oC for 15

min and 150 shakes per minute. The detergent-cleaned cotton fabric was then rinsed with

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water, air-dried and conditioned at a relative humidity of 65 ± 2% and 20 ± 2 °C for at least

24 hours before further characterization.

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Figure 1. The workflow of the dyeing, fixation and rinsing of cotton fabric (a) in aqueous
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solution (with salt) and (b) using reverse micelle approach in heptane without addition of
salt.
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2.5 The color strength (K/S sum value) measurement

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The color strength (K/S sum value) of the dyed fabric was calculated using the

Kubelka-Munk equation as follows:

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K/S = (1-R)2/2R

where R is the spectral reflectance of a colored fabric at a wavelength of maximum

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absorption (where the reflection is minimum). The wavelength measured ranged from 400 to
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700 nm, with an interval of 10 nm by SF650 Spectrophotometer (DataColor International,

USA). The greater the K/S sum value, the greater the color strength of the cotton fabric.

2.6 Relative levelness of dyed cotton

The reflectance values of four randomly selected spots on the dyed cotton (water-based

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and heptane-based) were measured over the visible spectrum (λ = 400-700 nm) at interval of

10 nm. All measurements were taken on the Macbeth ColorEye 7000A spectrometer using

illuminant D65 as light source and an aperture of 30 mm diameter.

The data obtained were the correlation between visual and instrument assessment of

levelness, expressed as the relative unlevelness index (RUI) [25]:

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RUI = ( / )

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The standard deviation, S, of reflectance values measured at a specific wavelength, is the

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mean reflectance value of the n measurements for each wavelength. V is the photonic relative

luminous efficient function [25].

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2.7 Micro-Raman spectroscopy

FT-Raman spectra were recorded ranged from 1800 to 300 cm-1 with a Bayview Raman
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spectrometer equipped with an optical microscope. All samples were irradiated with the
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1064 nm line of a Nd:YAG laser and collecting 20 scans for each sample. The spectra of
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dyed fibers under various parameters were acquired in the micro-sampling mode with a 10 X

objective lens and an output laser power of 150 mW. The scattered radiation was collected at
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180o and the spectral resolution was set to 4 cm-1.

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2.8 Transmission electron microscopy

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The dye-encapsulated reverse micelles were first deposited on carbon-coated Cu grids

via drop-casting following by staining with an aqueous solution of 1.0 wt. % uranyl acetate

for 10 minutes. The wet TEM samples were subsequently freeze-dried before TEM

observation. Uranyl acetate selectively stained the carbonyl and sulfonate group present in

dye molecules and appeared darker contrast than the shell (surfactant layet) in the TEM

micrographs. TEM bright field imaging was performed on a JEOL 100 CX II transmission
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electron microscope operating at 80 kV accelerating voltage.

3. Results and discussion

Raman spectra of pure cotton, water-dyed and reverse micelle dyed fibers could be

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analyzed in the region between 1750-800 cm-1 and 610-300 cm-1 as illustrated in Figure 2.

The literature study indicated that the bands from 1750 to 800 cm-1 were related mainly to

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skeletal, symmetric, and asymmetric vibration of glycosidic ring linkages of cellulose (1096

and 1121 cm-1), methylene (-CH2-) bending, rocking and wagging (at 1460, 1375, 1336, and

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996 cm-1) [26].

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The general features of spectra between water-dyed and heptane-dyed cotton using
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reverse micelles are very similar. The high intensity of the vibrational modes of the

chromophore apparently swamps changes that might occur to parts of the molecule not
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coupled to the chromophore, namely, the reactive group. Since it is difficult to distinguish
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visually the spectra of the dye states in water and heptane, minor differences from the spectra

may be detected, such as the overlapping bands at ~1275 cm-1, which exhibit changes in
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peak width and resolution; similarly, the group of weak, poorly resolved bands at ~1204 cm-1
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changes in peak shape.

In order to discriminate the undyed fiber, water-dyed fiber and heptane-based using
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reverse micellar approach and further investigate the effect of co-surfactant in the
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surfactant/co-surfactant mixture on the dye-cotton interaction, Raman spectroscopy has been

used to investigate how well the reactive dyes chemically adsorbed on cellulosic fiber in

terms of the concentrations of dye in the fiber under various co-surfactant-to-surfactant

molar ratios (Fig. S1 in Supporting Information) and water-to-surfactant mole ratios (Fig. S2

in Supporting Information). The analysis of asynchronous spectra as illustrated in Figure 2

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provides information on the occurrence of cross peaks at 1204 cm-1, 1275 cm-1, 1416 cm-1

attributed to -COH deformation, -C-O-C vibration and aromatic -N=N- vibration of reactive

dyes and 1309 cm-1 was attributed to the chemical signature of fixed dye state on cellulose,

respectively [26]. The intense signal at 1568 cm-1, attributed to the stretching vibrations of

the cross conjugated system of C=C, and aliphatic N=N groups [26]. The relative Raman

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peak intensity of functional group signals detected on dyed cotton is assumed to be

proportional to the surface concentration of the reactive dye.

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Figure 2. FT-Raman spectra of (a) Undyed cotton fabric; (b) Reactive red dye (Levafix
Red-CA dye); (c) Water-dyed cotton fabric and (d) Heptane-dyed cotton fabric using reverse
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micelle approach.

3.1 Effect of co-surfactant to surfactant molar ratio

Surfactant and co-surfactant are mainly located at the interfacial region separating the

water pool and the surrounding organic medium to stabilize their mutual dispersion. A

nonionic surfactant adsorbs strongly to an interface toward the air or toward an organic phase

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because of its dual structure with a nonpolar hydrocarbon segment chain with limited

interaction with water (the hydrophobic part) and a polar group with strong interaction with

water (the hydrophilic part).

The co-surfactant can act by interchelating between surfactant molecules at the interface

between organic phase and aqueous phase as a well-defined partition. This partition reveals a

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reduction of the interfacial free energy and hence the interface becomes rigid. A change in

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the fluidity of the interface should also have an effect on aggregated size and possibly

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morphology of the individual reverse micelle; an increase in micellar clustering could lead to

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an increase in the average size of the solubilized dyes, and an increase in rigidity should
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make morphological fluctuations less favorable. In a stepwise process, it is significant in
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which the surfactant and alcohol (co-surfactant) with appropriate carbon chain length are

combined in use in order to stabilize the waterpool structure with confined size in
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non-aqueous solvent.

The chain length-dependent effect of alcohol as a role of co-surfactant can be explained

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by R value [27]. R is the ratio of the net interaction energy of surfactant with organic phase
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to the net interaction energy of surfactant with water phase both in the presence of
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co-surfactant (n-octanol).

−( − )
=
−( − )

Where Xa is the mole fraction of alcohol in the interfacial region of reverse micelles. The
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interaction energies of alcohol and surfactant with organic phase (heptane) are and ,

respectively. Similarly, and are the interaction energies of alcohol and surfactant

with water phase, respectively. The R ratio measures the tendency for the surfactant to

disperse in organic phase with respect to its tendency to disperse in water phase and further

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provide a way to determine the convexity of the surfactant layer, which is phase behavior of

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organic, surfactant and aqueous regions. For R<1, the interfacial layer of surfactant has more

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interaction with the water which exhibit well dispersion in aqueous phase and normal

micelles are formed [27]. With the surfactant in our study, and are fixed. For

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PEG-12-Tridecylether surfactant used in our study, > because the carbon atoms of

surfactant chain (hydrocarbon chain length with 13 carbon atoms) is larger than those of the
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n-octanol (hydrocarbon chain length with 8 carbon atoms) and » due to the
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interaction formed between surfactant and water is much stronger than interaction between
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co-surfactant (n-octanol) and water in terms of hydrogen bonding. However, can be

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considered as a constant value because all alcohol-type co-surfactants have only a single OH
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group in contact with water and their hydrocarbon chains tend to be exposed in organic
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phase. On the other hand, will increase with the number of carbon atoms of the

hydrocarbon chain of alcohol. Thus, the lesser amount of the alcohol is necessary to satisfy R

> 1 condition for the formation of stable reverse micelle including ( − ) is larger than

( − ) and the hydrocarbon chain of alcohol-type co-surfactant is sufficiently long

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compared to carbon number of alkane chain. [27].

Closer inspection of the micellar morphology from TEM micrographs in Figure 3a

reveals that the dye aggregates at co-surfactant-to-surfactant molar ratio (6: 1) exhibited

ill-defined structure and size can be agglomerated into several microns, i.e., rougher

interfaces than micellar structures in other two surfactant-to-co-surfactant molar ratios. It

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appears that reverse micelles with less co-surfactant-to-surfactant molar ratio have exhibited

larger aggregates, the higher molar ratio of co-surfactant relative to the surfactant (9:1)

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results in the increase in the w/o interfacial tension to higher micellar curvature at which the

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interfacial surface area would further expand to form ultra-small reactive dye particles with

average size ranged from 10 to 40 nm in diameter as illustrated in Figure 3c.

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Figure 3. TEM image of reverse-micelle encapsulated red reactive dye with co-surfactant to
surfactant molar ratio of (a) 6:1; (b) 8:1 and (c) 9:1, respectively.
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Based on effect of the co-surfactant in the solvent properties, the incorporation of

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co-surfactant may eventually adjust Hydrophilic-Lipophilic Balance (HLB) value and

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interfacial curvature for effective waterpool partition. It indicates that the HLB value of the

reverse micellar system significantly decreased with the addition of octanol, because the

HLB value of octanol (=5.1) is about 2.7 times lower than that of poly(ethylene glycol) (12)

tridecylether (HLB = 14). The solubility of octanol in water is extremely low but preferably

miscible in heptane, therefore most of octanol would fully distribute in heptane. The TEM

micrographs in Figure 3b shows the co-surfactant to-surfactant molar ratio (8: 1) reduced the
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degree of reverse micelle agglomeration and the reverse micelles can be well maintained in

both spherical-like structure and narrow size distribution, owing to the optimal dispersion of

reactive dye encapsulants.

The solubilized co-surfactant in the organic phase distributed at the micellar interface as

well as in the bulk organic phase (heptane) and the waterpool of the reverse micelles. In

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other words, the micellar interfacial layers were made up of nonionic surfactant (PEG (12)

tridecylether), co-surfactant (octanol) having their hydrophilic group in contact with the

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waterpool and their alkyl chains in the heptane solvent. The optimization of surfactant to

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co-surfactant weight ratio becomes significant in the stabilization and solubilizing of reverse

micelle. The co-surfactant to surfactant weight ratio (9: 1) in Table1 revealed the highest K/S

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value and better levelness in terms of reverse micelle confined in much smaller size (< 100
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nm) with highly dispersed state. As shown in Figure 3, at the constant surfactant molar

concentration, the average size of dye-encapsulated reverse micelle increased from 80 nm to

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approximately 1.5 µm when the mole ratio of co-surfactant to surfactant decreased from 8：1
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to 6：1. The results indicated that the role of octanol as co-surfactant was to reinforce the
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tension at the interface between inner and outer sides of the micellar structure and prevent

further aggregation of encapsulated dyes. The reduction of octanol amount results in the
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decrease in the rigidity of the hydrophobic chains of surfactant, leading to morphological

distortion and favors micellar clustering [28].

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3.2 Effect of water to surfactant molar ratio

Previous reports have shown that excess amount of water or other solubilizing agents

induce a change in the geometry of the host reverse micelles and the size is much bigger than

the empty micelles [29-32]. Generally speaking, the parameter Wo, defined as molar ratio of

waterpool to surfactant (S) (Wo = [H2O]/[S]). Wo can only affect the morphology of the

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resultant reverse micellar structure synthesized by routine chemical methods via various

microemulsion parameters (the rigidity of the interface, the size of the water pool, etc.) [33].

As indicated from Table 2, the relative K/S value and unlevelness index was shown to

be considered from good to poor levelness as the water to surfactant molar ratio (Wo)

increased from 25 to 40. To investigate the dye aggregate mechanism of reverse micelle

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structure in our case, the morphological transition for Wo ranged from 20 to 40 was

investigated by transmission electron microscopy (TEM). The morphological changes with

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the addition of water were preserved through freeze-drying process and then visualized by

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TEM, as presented in Figure 4. In this study, the value of Wo was increased from 20 to 40 at

fixed surfactant concentration and precursor concentration. The TEM micrographs (Figure 4)

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exhibited agglomerated dye in micron-size (1-2 µm) with ill-defined morphology in higher
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Wo compared to the well-defined dye carrier in spherical-like morphology with an average

micellar size (diameter) of 125 nm under lower Wo value (Wo = 20).

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Water exists in reversed micelle is categorized into two forms: water bonded to the
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surfactant and free water. In nonionic surfactant system, when Wo value is small, the water is
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strongly hydrogen-bonded to the hydrophilic segment of the surfactant and the structure is

rigid and less mobile, viscosity is increased and the interface between oil phase and aqueous
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phase is highly rigid and the spherical morphology is maintained. This microscopically

trapped waterpool region can be compared to confined water region in biological membrane
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water with regard to its physicochemical properties [34]. According to an accepted model for
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waterpool region in reversed micelles using a two-state model [35]. A highly confined water

structure close to the interface would be in equilibrium with that at the center of the waterpool

which exhibits properties similar to those of bulk water.

As Wo increases from 20 to 40, critical micelle concentration (cmc) values decrease. It

seems that in the presence of water, the hydrophilic segment of poly(ethylene glycol) (12)

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tridecylether surfactant chain becomes more hydrated, facilitating the aggregation of the

reactive dyes in organic medium. The relative tendencies to aggregate depend on the

solubilizing group of the reactive dyes. The dye aggregates more because it has more

solubilizing groups and these are arranged in such a way that the planar central region of the

molecule is subject stacked with less steric. Reactive dyes have disulphonated disazo dyes, but

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presumably the two phenolic groups and the hydrogen in Levafix CA-red provide much

greater scope for intermolecular hydrogen bonding with water. In particular, it is important to

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understand the morphological factors that determine the nature of dye–dye intermolecular

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interactions, and how they may be affected by interactions with the molecular surfaces of

cellulose. Cellulose provides a submicron-sized porous medium consisting of polysaccharide

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chains arranged into crystalline and amorphous regions with pores of approx. 1–3 nm
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dimension where binding occurs [36]. Thus, the properties of this water structure become

similar to those of bulk water and phase separation was observed as illustrated from the inset
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of Figure 4d. The nature of the water inside the reversed micelle is very important because it
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depends on the stability of reactive dyes in the micellar core as confined waterpool with
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minimal hydrolysis. Such changes in dye aggregate size are due to the interaction between

water molecules and the hydrophilic segment of surfactant at the micellar core region. Besides,
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water may form hydrogen bonding with both the solubilizing group of the reactive dye and the

hydrophilic segment of the surfactant so that the overall micellar size increases as the domain
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size of waterpool increases in microemulsion.

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The average micellar size in diameter increases from 90 nm to 1.2 µm as Wo increases

from 20 to 40. At lower Wo value ranged from 20 to 25, the reverse micellar morphology

was mainly in more stable spherical-like structures and well-dispersed in heptane as

illustrated from the inset of Figure 4b. As Wo increases up to 30, the dye aggregate

morphology was still maintained in spherical shape but based on the size distribution and the

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existence of the shell, the reverse micellar structures are speculated to be large compound

micellar structures as described by Zhang et al.[37] However, when increasing Wo, the

reactive dye encapsulated in reverse micelle began to lose their spherical shape uniformity.

As such, beyond Wo > 30, insufficient amount of surfactant was able to form stable reverse

micelles, and instead a separated two-phase was generated [37], as illustrated from the inset

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of Figure 4d. Therefore, the hydrophilic reactive dye distributed in a separated water phase,

thereby contributing to the irregular morphology of the large dye aggregates. The

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aggregation behavior and subsequent growth of the encapsulated materials are controlled by

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interaction between surfactant building block of reverse micelles, and they can also be

affected by phase behavior and solubility, average occupancy of reacting species in the

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aqueous medium and interfacial dynamic behavior of the reverse micellar solution [38].
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At higher water-to-surfactant mole ratio, ethylene glycol is speculated to interact with

both solubilized dye molecules and waterpool. This phenomenon suggests that one ethylene
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glycol segment may interact with even more hydrated dye molecules, leading to the
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formation of these highly swollen aggregates.

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When the water content increased up to the critical value for the occurrence of

microphase separation between the hydrophilic ethylene glycol segment and the hydrophobic
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tridecylether groups, resulting in the association of adjacent ethylene glycol segment with

dye molecules. The spherical morphology is stabilized by a reverse micelle with surfactant
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chains at the interface between aqueous and organic phase. These spherical-like reverse
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micelles would merge into larger dye aggregates and be kinetically “frozen” at high water

content as shown in Figure 4c and 4d. However, ethylene glycol segment interact with water

molecules via hydrogen bonding would eventually restrict the mobility of hydrophilic

portion of the surfactant chains. Moreover, the extraction of heptane or the phase separation

of ethylene glycol segment would further decrease the mobility of hydrophilic chains inside

the spheres. Since heptane was extracted more rapidly from the surface region than the core,
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the low chain mobility at the interfacial region caused the formation of a rigid surface would

prevent the homogeneous shrinkage of the whole micelle structure during water addition.

The formation of reverse micelles with optimal encapsulated waterpool volume requires

sufficient critical micelle concentrations and shows an intensive solvent dependence [39,40].

Excess waterpool volume may induce significant hydrolysis of reactive dyes rather than

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effective fixation reaction of the reactive dye, resulting in the generation of unfixed reactive

dye molecules and the aggregated size is too large for dye diffusion into cotton matrix.

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Figure 4. TEM image of reverse-micelle encapsulated red reactive dye with water to
surfactant molar ratio (Wo) of (a) 20; (b) 25; (c) 30 and (d) 40, respectively.

Table 2 illustrates the K/S sum values and relative unlevelness indices (RUI) of dyed
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fabrics with various co-surfactant/surfactant and water/surfactant molar ratios, respectively.

Values of RUI of dyed fabrics decreased with increasing co-surfactant to surfactant molar

ratio from 6:1 to 9:1, indicated the levelness is improved. The levelness is excellent based on

measured RUI value when Wo is 25. As the molar ratio of water to surfactant (Wo) increased

from 20 to 40, the RUI values changed from excellent to poor. This means the role of both

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Co-surfactant to surfactant molar K/S max (K/S) sum Visual
ratio appearance

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(water/surfactant = 25 : 1) of levelness
(RUI)
6:1 34.35 410.25 0.241

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8:1 33.89 411.05 0.174
9:1 33.90 414.53 0.137

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Water to surfactant molar ratio K/S max (K/S) sum Visual
(Co-surfactant/surfactant = 8 : 1) appearance
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of levelness
(RUI)
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co-surfactant and water in reverse micelle-encapsulated dye is significant for dye dispersion

in solvent and evaluation of levelness of dyed cotton samples.

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Table 2 K/S and RUI values for dyed cotton samples under various
surfactant-to-co-surfactant and surfactant-to-waterpool molar ratios.
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20 : 1 35.27 435.25 0.322
25 : 1 33.89 411.05 0.174
30 : 1 34.03 413.56 0.319
40 : 1 32.92 393.37 0.679

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4. Conclusions

The dispersibility of dye encapsulated in reverse micelle under various surfactant to

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co-surfactant molar ratios were investigated. Increasing of co-surfactant to surfactant molar

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ratio leads to the formation of well-dispersed dye nanoparticles. Higher water to surfactant
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molar ratio results in micro phase separation and the increasing waterpool volume behaves like
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bulk water which increase size of reverse micelle with dye aggregation. Raman spectra results
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can be considered as the effective estimation of dye fixation. The size of dye aggregates under
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various surfactant parameters suggesting that the morphology of dye aggregate plays a

significant role in dye distribution on cotton fabric with a better balance between color

strength and relative levelness.

Acknowledgement

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All authors would like to thank the financial support from the Hong Kong Polytechnic

University for this work.

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Supporting Information

Effect of reverse micelle-encapsulated reactive dyes agglomeration in

dyeing properties of cotton

Cheng Hao Lee1, Yiu Lun Tang 2, Yanming Wang2, Chi Wai Kan2*

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1
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University,
Hung Hom, Kowloon, Hong Kong SAR, China

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2
Institute of Textile and Clothing, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong

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SAR, China

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*
Correspondence author: tccwk@polyu.edu.hk
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(a)

6: 1
Intensity (a.u.)

(b)

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8: 1

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(c)
9: 1

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1800 1600 1400 1200 1000 800 600 400
-1
Raman shift (cm )
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Fig. S1. FT-Raman spectra of dyed cotton in heptane with co-surfactant to surfactant molar
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ratio of (a) 6:1, (b) 8:1 and (c) 9:1, respectively. (The water to surfactant molar ratio (Wo) is
25)
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Fig. S2. FT-Raman spectra of dyed cotton in heptane with water to surfactant molar ratio
(Wo) of (a) 20 and (b) 40, respectively. (The co-surfactant to surfactant molar ratio is 8:1)
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Highlights

Reverse micelle was introduced to encapsulate reactive dye for cotton dyeing.

Reverse micellar structures are highly dispersed and agglomerated forms.

Good color strength and levelness data were obtained.

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