High-Quality Images Inkjetted on Different Woven Cotton Fabrics

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Applications of Polymer, Composite, and Coating Materials

High Quality Images Ink-jeted on Different Woven Cotton Fabrics Cationized with P(St-BA-VBT) Copolymer Nanospheres Haizhen Yang, Kuanjun Fang, Xiuming Liu, and Fangfang An ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b07848 • Publication Date (Web): 19 Jul 2019 Downloaded from pubs.acs.org on July 25, 2019

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High Quality Images ink-jeted on Different Woven Cotton Fabrics Cationized with P(St-BA-VBT) Copolymer Nanospheres Haizhen Yang1, Kuanjun Fang1,2,*, Xiuming Liu1, Fangfang An1 School of Textiles Science and Engineering, Tianjin Polytechnic University, No. 399

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Binshui Xi Road, Xiqing District, Tianjin 300387, P. R. of China Collaborative Innovation Center for Eco-Textiles of Shandong Province, No. 308

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Ningxia Road, Qingdao 266071, P. R. of China *Corresponding author. Add.: School of Textiles, Tianjin Polytechnic University, No. 399 Binshui Xi Road, Xiqing District, Tianjin 300387, P. R. of China. Tel.: +86 138 0898 0221; fax.: +86 22 83955287. E-mail addresses: [email protected].

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Abstract: The porosity, roughness and thickness of woven fabrics limits inkjet printing quality, which is extremely important for obtaining high-quality inkjet printing images on fabrics. This study reveals the application of Poly[Styrene-Butyl acrylate-(P-vinylbenzyl trimethyl ammonium chloride)] nanospheres prepared via soap-free emulsion polymerization approach as a novel kind of cationization modifier for the inkjet printing of different woven cotton fabrics by pad-cure process. It was found that the nanospheres exhibited the average diameter of 65.5 nm, the Zeta potential of + 57.8 mV and glass transition temperature of 94.7 ℃. The nanospheres deposited on three cotton fabrics through the dip-rolling process, resulting in the increase of Zeta potential, hydrophobicity and thickness of the fabric, and the decrease of porosity and roughness. The high-quality inkjet printing images can be obtained on fabrics with different structures owing to the differences in Zeta potential, hydrophobicity, porosity, roughness and thickness of fabrics. The plain, twill and honeycomb weave fabrics obtained high quality inkjet printing images for portraits, oil paintings and landscape paintings, respectively. The nanospheres could strongly adsorb on the fiber by electrostatic attraction. The reactive dye molecules in the inks could react with the cationized fibers by electrostatic attractive force, resulting in the increase of the color strength, fixation rates and outline sharpness. The nanospheres cationization of different woven fabrics offers a new potential method for obtaining high-quality pattern without significantly affecting the fabric handle. Keywords: high-quality images, reactive inkjet printing, cellulose substrate, cationization, color strength, washability 1. Introduction Compared with traditional printing, inkjet printing on textiles is progressively common and important owing to its lower resource consumption, higher image

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quality and wastewater discharge.

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Nevertheless, the surface preparation of the

fabric must be done prior to inkjet printing to promote printing accuracy, color strength, fixation rate.

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Furthermore, inkjet printing is a technique for producing

liquid ink droplets, which are deposited on a substrate with a specific pattern. The image is generated when the fluid contains a colorant.

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However, the porosity,

roughness and thickness of fabrics greatly limit the quality of inkjet printing, which is especially essential for high-quality images ink-jeted on the fabric. 8-9 Conventional printing pretreatment agents, for example, acrylate copolymers, carboxymethyl cellulose and sodium alginate, are commonly applied in the pretreatment of fabrics.

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Nevertheless, after the steam treatment of the printed

fabric, the urea and thickener and chemicals filled on the fabric must be washed to ameliorate the color performance and handle, increasing water and energy consumption and the amount of pollutants in wastewater.

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In order to solve the

environmental problems result from pretreatment of printing fabrics with printing thickeners, cationic compounds have been applied in pretreatment of fabrics.

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The

surface pretreatment of cotton fabrics with cationic polymer microspheres proves that there is electrostatic attractive force between cationic polymer microspheres and dyes with negative charge, increasing handle and the fixation rate, and obtaining salt-free dyeing effects. The cotton fabrics modified with Poly[Styrene-Butyl acrylate-Acrylic acid-Glycidyl methacrylate] polymer microspheres displayed superior pigment dyeing effect than those modified with Poly[Styrene-Butyl acrylate-Acrylic acid] polymer microspheres.

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Cotton fabrics treated with cationic polymer microspheres show

excellent anti-bleeding performance and handle after dyeing with acid dyes. The fabrics treated with cationic polymer microspheres exhibited the high color strength and high dye utilization. 18,19

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Since the theoretical research on inkjet printing is mainly based on papers printing, and the fabric shows the rough surfaces and large pores than the paper, the interaction between fabric and ink droplets is a crucial factor affecting the inkjet printing performance.

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Farooq et al found that twill weave fabrics exhibited less porosity

and high color strength than those of satin fabrics with the identical density, indicating that the porosity was directly related to the color strength of the fabric.

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Bae et al

discussed the relationship between fabric textures and the color strength of inkjet printing fabrics, indicating that fabric textures displayed a measurable effect on inkjet printing.

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Furthermore, since the formation of the apparent color of the fabric is not

pre-mixed, fabric and various color ink droplets are selectively absorbed and reflected by the light irradiated on the fabric as needed, and then the inkjet printing pattern is presented on the fabric by mixing colors. Therefore, the printing pattern mainly was decided by the precise distribution of the ink droplets.

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Moreover, the cross-

sectional shape of the yarn or fiber in the fabric caused the deformation of the ink droplets and the spread, diffusion and penetration of ink droplets in the printing process, affecting the interaction between the light and the fabric, which affected the inkjet printing performance.

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Yang et al found that the honeycomb weave fabric

possessed the better apparent color strength and the worse outline sharpness than those of plain weave fabric after the same surface pretreatment, indicating that there was a close relationship between the apparent color strength and fabric structures. 9 Li et al revealed that the droplet diffusion area on the polyester knitted fabric was inversely proportional to the effective porosity of the fabric. 20,23 Fang et al found that the finer yarn and the larger tightness contributed to the higher color strength and the better anti-bleeding performance.

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An et al revealed that there was a close

relationship between the tightness of silk fabric, the spreading of ink droplets and the

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color strength.

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However, the yarn linear density, weaving process and the

pretreatment process of the fabric in the above studies were different, which could affect the inkjet printing performance, and there was few theoretical studies on the relationship between the fabric structure and the inkjet printing performance. The ink droplets become negatively charged owing to the ionized dye molecules in the ink droplets. Consequently, ink droplets can be immobilized on the surface of cationized fabrics. In this study, we aim to investigate the potential of the nanospheres as cationic modifier for textiles, focusing on obtaining high-quality printing images on different weave structures textiles. The effect of nanospheres concentrations and fabric structures on the fabric porosity, roughness, thickness, hydrophobicity, Zeta potential and inkjet printing images quality of fabrics are investigated. It was found that the nanospheres pretreatment strongly improved the color strength and outline sharpness of different fabrics. More importantly, the nanospheres can not only effectively increase Zeta potential, hydrophobicity and thickness of fabrics, but also decrease porosity and roughness of fabrics. The high quality inkjet printing images were obtained on fabrics with different structures. Furthermore, the nanospheres were adsorbed on cotton fibers. Since the cationization modification process without urea significantly reduced the amount of pollutant of the wastewater, this reported process was environmentally friendly. 2. Experimental Methods 2.1. Materials Three cotton fabrics (warp and weft density: 18 ends cm-1 and 15 picks cm-1) with plain, 3/1 twill weave and honeycomb weave, a basis weight of 231.59 g/m2, 248.32 g/m2 and 271.91 g/m2 were fabricated by the automatic rapier loom (ASL2300, China). The weave structures of three fabrics were displayed in Figure 1. P-

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vinylbenzyl trimethyl ammonium chloride (VBT) was kindly provided by Tianjin Heowns Biochem Technologies Co., Ltd. Butyl acrylate (BA) was obtained from Tianjin BASF Chemical Co., Ltd. Styrene (St) was kindly provided by Tianjin Ruijinte Chemical Reagent Co., Ltd. Sodium bicarbonate was obtained from Tianjin Kemiou

Chemical

Reagent

Co.,

Ltd.

2,2'-azobis[2-methylpropionamidine]

dihydrochloride (AIBA) was kindly provided by Qingdao Kexin New Material Technology Co., Ltd. The inks were kindly provided by Hangzhou Honghua Digital Technology Co., Ltd. 2.2. Preparation of nanospheres First, the 90mL of deionized water was added to a 250mL four-neck-flask. After nitrogen for 5 min, 5mL of VBT solution with the concentration of 0.4 mol/L was added to the four-neck flask and stirred at 300 r/min for 15 min. The solution was subsequently mixed with 9.2 g of St and 0.8 g of BA and stirred for 2 h. Then, the solutions temperature increased from 25 ℃ to 80 ℃, 5 mL of AIBA with the concentration of 20 g/L solution was put into it within 5 min, then reaction at 80 ℃ for 4 h. The nanospheres were finally obtained by cooling materials. The preparation and polymerization of nanospheres were displayed in Figure 2. 2.3. Nanosphere modification of fabrics The initial nanospheres solutions were diluted with deionized water, then 400 mL of modification liquids containing sodium bicarbonate (10 g/L) and nanospheres (0.5 ~ 2.5 g/L) was homogenized by an ultrasonic cleaner (Heidolph KQ-100DZ, China) at 25℃ for 30 min. Cationization modification of the fabric was conducted by a padder (PO-B, China) with a pick-up of (70 ± 1) % via the two-dip, two-nip technique. Subsequently, all samples were dried in the baking box at 80 ℃ for 5 min. Among

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them, the fabric modified with a solution of sodium hydrogencarbonate without nanospheres was used as a control sample. 2.4. Reactive inkjet printing Printing on fabrics was performed using a digital inkjet printer (VEGA 5000, China), and the allowable printing resolution was 720 dpi. Lines of 1 mm and rectangle patterns color filled with 100% and 20% were inkjet printing on three fabrics. The fabrics were subsequently steamed in the steamer at (102 ± 1) ℃ for 6 min. Then the fabrics were washed successively with water until no color was peeled off on the fabric. Lastly, all samples were dried in the baking box at 80 °C for 5 min. 2.5. Characterizations The morphologies of nanospheres were conducted using transmission electron microscope (H7650, Hitachi). Crystallinity analysis of nanospheres was measured using the X-ray diffractometer (D/MAX-2500, Japan). The surface morphologies of the fabric were performed using a scanning electron microscope (S4800, Hitachi). The kinds and contents of elements in three fabrics were conducted using X-ray photoelectron spectroscopy (K-alpha, Thermofisher). The chemical structures of three fabrics were conducted using the fourier transform infrared (Nicolet 6700, USA). Hydrophobicity of three fabrics was conducted using the optical contact angle meter (DCAT11, Dataphysics, Germany). The roughness of three fabrics was measured using a fabric style instrument (KES-FB, China). The thickness of three fabrics was performed on a digital thickness instrument (YG 141 LA, China). The ink droplet shapes and outline sharpness of three fabrics were observed through the optical microscope (YYS-560E, China). The rubbing fastness properties of three fabrics were conducted by the rubbing machine (Y571, China) on the basis of ISO 105-X12: 2001. The washing fastness properties of three fabrics were performed on a washing

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colorfastness tester (SW-24, China) according to ISO 105-C10:2007. The details of basic characterization were listed in Supporting Information. The porosity (ε) of three fabrics was calculated according to the equation (1): 8



V pores V fabric

  100  1  fabric   fiber 

  M fabric  100  1    T fabric  1000   fiber  

  100  

(1)

where Vfabric and Vpores are the fabric volume and pores volume in fabrics (cm3), respectively. pfiber is physical densities of fibers (g/cm3). pfabric is physical densities of fabrics (g/cm3). Tfabric is the thickness of the fabric (mm). Mfabric is the mass per square metre of the fabric (g/m2). 3. Results and discussion 3.1. Preparation and morphology of nanospheres The sizes and distributions of nanospheres are exhibited in Figure 3a-b. It was apparent that the nanospheres showed a regular spherical shape with an average particle diameter of 65.5 nm and the dispersibility index of 0.147, indicating that the size distribution of nanospheres was narrow and the dispersion was better, providing the important conditions for obtaining high quality inkjet printing images on fabrics. 17

Figure 3c shows the Zeta potential of nanospheres, it was evident that the

nanospheres possessed the Zeta potential of + 57.8 mV, owing to the presence of cationic groups in initiators and emulsifiers for nanospheres preparation,

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indicating

the stable existence of nanoparticles in the dispersion solution. It was found that the nanospheres possessed the glass transition temperature of 94.7 ℃, as illustrated in Figure 3d, meaning that the nanosphere could be applied to the cation modification of textiles, avoiding the textile printing uneven phenomenon of textiles.

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Furthermore,

there was a crystallization peak at 2θ of 25.6°, indicating the existence of crystals in nanospheres, as illustrated in inset of Figure 3d.

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3.2. SEM morphologies observation and chemical analysis From Figure 4, it could be noticed that the geometric microstructures of plain, twill, and honeycomb cotton fabrics have been conducted by utilizing scanning electron microscopy (SEM), respectively. The untreated cotton fabrics displayed the smooth surface with little micropits and grooves (Figure 4d1). Whereas the regular weave structure of plain, twill, and honeycomb weave fabrics with bits of protruding fibers can be clearly observed (Figure 4a1-c1).

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In these magnified SEM images (Figure

4a2-c2), there was many nanospheres adhered to fiber surfaces of plain, twill and honeycomb weave fabrics randomly without the formation of the film structure, significantly roughening the cotton fiber surface, similar to the previous phenomenon. 27

The morphology differed greatly from the morphology of the film on cotton fabrics

modified with sodium alginate, as reported by Liu et al.

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In his study, sodium

alginate formed a film structure coating on cotton fibers. However, in the current study, the nanospheres coating is deposited on the cotton fabrics formed a separate layer composed of spherical particles, indicating that cationic nanospheres can not form a coating structure on a fabric substrate. It was expected that the differences in the individual layer structure would have a different influence on the shape of the ink droplets and the final distribution of ink droplets on fibers. This was because the cellulose hydroxyl groups were ionized into cellulose hydroxyl anion in an alkaline medium, causing the surface of cotton fiber to exhibit a negative charge, while cationic nanospheres possessed a strong positive charge. Therefore, the cationic nanospheres could strongly adsorb on the surface of the fibers by means of electrostatic attractive force. Moreover, the viscosity of the nanosphere solution was small, and the wetting and spreading ability of the nanosphere on cotton fibers was strong. During the padding and drying process, the nanosphere could spread rapidly

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on the surface of the fiber and less remains between the fibers. After inkjet printing (Figure 4f1), there were some larger particles on the inkjet printed cotton fibers, mainly because the ink droplets become negatively charged because of the ionized dye molecules in ink droplets, and reactive dyes could react with the cationized fibers by means of electrostatic attractive force. After steaming and fixing (Figure 4g1), the spherical shape of the nanosphere changed, forming a continuous thin film coating on the fibers, implying that nanospheres possess self-curing effect.

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Furthermore, this

phenomenon also changed the hygroscopic properties of the fabric, affecting the dye fixing effect and the shape of the formed droplets. After washing (Figure 4h1), the surface of the fiber developed into smooth mainly due to the excess of unreacted reactive dye on the cotton fiber being washed away, indicating that the modification of the nanosphere displayed less effect on the fabric handle, which was also confirmed by the later fastness performance. The energy dispersive X-ray spectroscopy (EDS) analysis of cotton fabrics at different stages of inkjet printing is represented in Figure 4d2-h2.

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The major

elemental content of untreated cotton fabrics was carbon (C) and nitrogen (O) (Figure 4d2). After cationization of the nanospheres (Figure 4e2), the nitrogen (N) elemental content of cotton fibers increased significantly, which confirmed the existence of nanospheres on the fibers.

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After inkjet printing (Figure 4f2), the elemental content

of S was remarkably increased because the reactive dye inks were mainly composed of a choro triazine reactive dye, a polyol solvent, an acetylenic surfactant, a pH buffering agent and so on, resulting in an increase in the elemental content of S in the fiber. After steaming and fixing (Figure 4g2), the major elemental content of cotton fabrics was C, N, O, S, and no new elements appeared. However, the element content of S was slightly reduced, mainly because more dyes could quickly seep into the fiber,

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leading to a slight decrease of S element content on the fiber surface. After washing (Figure 4h2), the element content of S in the fiber was further reduced, mainly due to the excess of unreacted reactive dye on the cotton fiber being washed away. FTIR and XPS survey spectra were applied to confirm the successful adsorption of nanospheres on cotton fabrics. The chemical structures of nanospheres are confirmed by FTIR as exhibited in Figure 4i. It was apparent that the spectrum of all fabrics displayed some peaks at 3332 cm-1, 2898 cm-1, 1028 cm-1, correlated to the stretching vibrations of O-H, C-H, C-O, respectively. Compared with three untreated fabrics, it appeared some new absorption peaks for three treated fabrics. The new peak at 1454 cm-1 was corresponding to the stretching vibrations of C-N in -N+(CH3)3, indicating that nanospheres were successfully deposited on three cotton fabric surfaces. 31,32 The kinds and contents of elements in three fabrics are confirmed using XPS as seen in Figure S1. It was found that all the spectra consist of at least two principal peaks: carbon and oxygen, according to their binding energy. Notably, in comparison with the untreated plain, twill and honeycomb weave fabrics, the new nitrogen (N) atoms appeared on the treated plain, twill and honeycomb weave fabrics, indicating that nitrogen (N) atoms were in the form of quaternary ammonium group (-N+(CH3)3), which are originated from nanospheres,

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and atomic percent of N reached up to

1.92%, 2.04%, 3.07% for plain, twill and honeycomb weave fabrics, respectively, as seen in Figure S1. In addition, XPS survey spectra also confirmed the changes in the cotton fiber at various stages of inkjet printing, as seen in Figure 4j. Figure 5 exhibited SEM images of non-coated and coated fabrics with different amounts of nanospheres. Compared with the uncoated fabric, it was found that at 0.22 g/m2, most of the pores of the fabric were not covered by the nanosphere coating. When the coating amount was increased to 0.75 g/m2, most of the pores in the fabric

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were filled, leading to the decrease of the porosity and roughness of the fabric. These results are in the agreement with the following test results (Figure 6b-d), showing the smoothening effect of nanospheres coatings on cotton fabrics. 3.3. Fabric properties analysis The roughness, porosity, thickness, the contact angle of water, Zeta potential, K/S values, fixation rates, pattern sharpness and apparent color of the woven fabrics are displayed in Figure 6. Compared with the control sample (the nanospheres concentration was 0 g/L), the warp and weft roughness and porosity of the three fabrics decreased with the increase of the nanospheres concentrations, and gradually tended to stabilization when the nanospheres concentrations was greater than 1.0 g/L (Figure 6a-d). Compared with the control sample, whereas the thickness, the contact angle of water, Zeta potential and color strength, fixation rates and outline sharpness of three fabrics gradually increased with the increase of the concentration of nanospheres, and gradually tended to stabilization when the nanospheres concentrations was greater than 1.0 g/L (Figure 6e-k). Mainly because the cellulose hydroxyl groups were ionized into cellulose hydroxyl anion in an alkaline medium, causing the surface of cotton fiber to exhibit a negative charge, that is, the nanospheres concentrations was 0 g/L, the cotton fiber exhibited a negative charge. The Zeta potential of three fabrics gradually changed from a negative charge to a positive charge with the nanospheres concentrations increased from 0 g/L to 2.5 g/L (Figure 6g), mainly due to the strong positive charge of the cationic nanospheres, which could strongly adsorb on the surface of the fibers by means of electrostatic attractive force, resulting in the increase of the cationization degree of cotton fabric. Meanwhile the ink droplets become negatively charged because of the ionized dye molecules of ink droplets, and reactive dyes could react with cotton fibers modified

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by nanospheres by means of electrostatic attractive force, resulting in the increase of the color strength and fixation rates. In addition, with the improvement of cationization degree and hydrophobicity of cotton fabric, ink droplets were more easily fixed on cationized fabrics, preventing the penetration and diffusion of ink on cotton fabrics, resulting in the improvement of outline sharpness of the fabric. Therefore, among these properties, the Zeta potential was the most important factor, which was the strongest correlations that demonstrate the impact of the presence of the nanospheres on the color strength, fixation rates and pattern sharpness, and the hydrophobicity, porosity and roughness were the secondary factors, and the combination of these influencing factors enhanced the color depth, fixation rates and pattern sharpness of the fabric. Besides, the apparent color of the woven cotton fabrics in Figure 6l can be presented more clearly. Surface energy of solid (  S ) consists of polar component (  Lp， Sp ) and dispersive component (  Ld， Sd ), as well as surface tension of liquid (  L ), as implied by Fowkes. 10,11

The dispersion contribution stems from the interactivity of fluctuation electronic

dipoles and induced dipoles of adjacent species as well as perturbations of electronic orbitals. The polar component included hydrogen bonding as well as various dipole interactions. Consequently, the wettability of cotton fabrics was generally described using the dispersion component as well as polar component of the surface energy. Contact angles and surface energy of fabrics are seen in Table 1. Obviously, the polar component and the dispersion component of surface energy of untreated plain, twill and honeycomb weave fabrics were almost the same. The dispersion component of the surface energy of the plain, twill and honeycomb weave fabrics was sharply reduced by 24.47、 25.09 and 25.59 mJ/m2, and the polar component was increased by 2.59 、0.60 and 0.57 mJ/m2 than those of the untreated fabrics, which indicating 13


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that the wetting properties of the modified plain, twill and honeycomb weave fabrics were reduced. Owing to the electrostatic attractive force between the negative charge of cotton fibers and the quaternary ammonium salt groups carried on the nanospheres, the hydrophilic portion of the nanospheres moved toward the cotton fiber surface, besides, the hydrophobic portion gradually moved away from the cotton fibers

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and was aligned toward the air, reducing the inter-molecular force. 3.4. Outline sharpness test The influence of fabric structure on the outline sharpness was evaluated by ink jet printing. Some rectangular patterns filled with 100% color and lines of 1 mm with magenta, cyan, black and yellow inks were printed on the fabrics, as seen in Figure 7. The outline sharpness of the fabric was tested via optical analysis software from the warp and weft directions. Obviously, the printing patterns in the warp direction of three fabrics were broader than those in the weft direction for magenta, cyan, black and yellow inks, which was attributed to the different wicking effects resulted from the warp and weft yarns(Figure 7 and Figure S2).

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The patterns of twill weave

fabrics were wider than those of plain weave fabrics for the warp and weft directions, as well as the patterns of honeycomb weave fabrics were wider than those of twill weave fabrics for the warp and weft directions. It was mainly because of the larger fabric roughness, porosity and thickness that led to the increase of ink diffusion, i.e. the capillary pores between the yarn, the fiber and the fibril made it easier for the inks to spread on the surface of the fabric by means of hydrogen bonding and capillary pressure, 11,35 indicating that fabric structures could affect the outline sharpness of the fabric. Figure 8 represents the diffusion shape of the ink droplets on the cotton fabric of different woven structures. Obviously, the ink dots on fabrics with different weave

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structures displayed an irregular strip-like shape. It can be attributed to the differences in fabric structures, resulting in the different diffusion of ink droplets. Obviously, the droplets on twill and honeycomb fabrics became larger than those of plain fabrics, as shown in Figures 8a-c, indicating that the ink droplet spreading speeds on twill and honeycomb fabrics were larger than those on plain fabrics. This was because twill and honeycomb fabrics had greater porosity, roughness and thickness, and the capillary pores between fibrils, fibers and yarns let it easier for inks to diffuse into the interior of the fabric, even into the amorphous areas of the fibers by means of hydrogen bonding and capillary pressure, which may contribute to the diffusion and penetration of droplets on the fabric. 8,9 3.5. Colorimetric values test According to the Kubelka-Munk theory,

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the color strength (K/S) values at a

certain wavelength which is considered to the printed fabric color strength. The larger the color strength values, the darker the fabric color. The K/S curve and the reflectance curve of fabrics with different woven structures are displayed in Figure 9. Obviously, for the cyan, magenta, yellow and black block with a filling rate of 100%, at the maximum absorption wavelength (λ = 670 nm, 550 nm, 430 nm, 590 nm), the honeycomb weave fabrics possessed the greatest K/S values, whereas plain fabrics exhibited the smallest K/S values due to the honeycomb fabric having the least interlacing points of warp and weft, maximum roughness, porosity and thickness. The capillary pores between fiber and fibril let inks diffuse into the interior of the fabric, and even permeated into the amorphous areas of the fiber by means of hydrogen bonding as well as capillary pressure, resulting in most dyes being immobilized on the front of the fabric.

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The color of printing fabric is

defined by by the light source, light reflection, absorption, scattering, transmission,

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fabric and observer.

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The distribution of dyes immobilized on the fabric greatly

affected the absorption and reflection of light. Consequently, more dyes being immobilized on fabrics contributed to the absorption of light and the reduction of light reflection, which corresponded to the reflectance curve of fabrics after inkjet printing, as illustrated in Figure 9. According to color depth equation, the color depth of the fabric increased as the reflectivity decreased, which also explained why the color strength of honeycomb weave fabric was larger than those of twill weave fabric after the same treatment. Color parameters of the printed cotton fabric with different organizational structures are seen in Table 2. Obviously, the twill fabric possessed lower L* values than those of plain fabric, and L* values of honeycomb weave fabric was lower than those of twill weave fabric for magenta, cyan, black and yellow inks, implying that the color of honeycomb weave fabric was deeper, while that of plain weave fabric was lighter. a* refers to the redness (+) and greenness (–), b* to the yellowness (+) and blueness (–). Furthermore, C* expresses color saturation, h° is hue.

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For a* and

b* parameters, taking cyan as an example, the a* and b* values of the three fabrics was all negative, indicating that the apparent color of three fabric was inclined to both green and blue. C* values of plain weave fabric were lower than those of twill weave fabric, and C* values of twill weave fabric were lower than those of honeycomb weave fabric, indicating that the honeycomb weave fabric displayed brighter color. For black and cyan inks, the h° values of three fabrics were very close, meaning that fabric structures had little effect on color hues. For yellow and magenta inks, the h° values of three fabrics changed slightly, close to 90° and 360°, respectively, indicating that the yellow and magenta color of three fabrics were purer, owing to the different molecular structure of dyes in inks.

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Table 3 illustrates the washing and rubbing color fastness of fabrics with different weave structures. Obviously, three fabrics exhibited outstanding washing as well as rubbing fastness, meaning that cationization modification had little influence on the color fastness of fabrics. However, the dry and wet rubbing fastness of twill and honeycomb weave fabrics was nearly 0.5 grade higher than those of plain weave fabrics, indicating that the fastness properties of fabrics possessed a certain relationship with the surface roughness of fabrics. The larger the roughness of fabrics contributed to the higher the fastness performance of fabrics. 8,9 3.6. Analysis of high quality inkjet printing imaging mechanism The high quality inkjet printing imaging mechanism was exhibited in Figure 10. It was found that part of the hydrogen bonds between the cellulose macromolecular chains was replaced by hydrogen bonds between the water and cellulose hydroxyl groups by the action of water molecules when three cotton fabrics were treated with NaHCO3 liquids, resulting in the swelling of cellulose fibers. The cellulose hydroxyl groups (Cell-OH) were ionized into cellulose hydroxyl anion (Cell-O-) in an alkaline medium, so that the surface of cotton fiber exhibited electronegativity, as illustrated in Figure 10a. The ammonium salt groups (-N+(CH3)3) of the nanospheres with large specific surface area were adsorbed on the fibers by means of electrostatic attractive force,

14

and the surface of the cotton fiber changed from electronegativity to positive

charge, as illustrated in Figure 10b. After inkjet printing of the modified cotton fabrics, more dye molecules were forced to adsorb on the surface of the fibers under the action of static electricity. In addition, the vapor process can accelerate the ionic bonding between the ammonium salt groups of the cationic nanospheres and the reactive dye anions, as illustrated in Figure 10c. After the cationic modification of cotton fabrics, the positive charges carried on the fiber weakened the electrostatic

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repulsion between the reactive dyes and the fibers, and more reactive dye molecules were fixed on the fiber surface, resulting in the high color strength, good sharpness and low alkali consumption. Since the plain fabrics displayed the smallest porosity and roughness and the largest thickness, and honeycomb fabrics exhibited the greatest porosity, roughness and the smallest thickness, the nanospheres adsorbed on the surface of the plain fabric was the most, and the nanospheres adsorbed inside the fabric was the least after the nanospheres modification. Whereas the nanospheres adsorbed on the surface of the honeycomb fabric was the least, and the nanospheres adsorbed inside the fabric was the most, as illustrated in Figure 10b. It was obvious that the spreading areas of the ink droplets on the plain fabrics were the smallest and the anti-bleeding performance was the best, and honeycomb fabrics exhibited the greatest the spreading areas of the ink droplets and the worse the anti-bleeding performance after the same inkjet printing, which was attributed to the fact that the nanosphere modification led to the improvement of cationization degree and hydrophobicity of cotton fabric, as illustrated in Figure 10c. As a result, the plain fabrics displayed the lowest color strength and the optimal pattern sharpness, and honeycomb fabrics exhibited the highest color strength and the worst pattern sharpness. Because honeycomb fabrics had the maximum roughness, porosity and thickness, the capillary pores between the fibrils, fibers, and yarns made it easy for inks to diffuse into the fabric under the action of hydrogen bonding and capillary pressure, and even penetrate into amorphous regions of fibers, leading to more reactive dyes being immobilized on the front side of the fabric. 38,39 Since the formation of the apparent color of the inkjet printing fabric is not pre-mixed, the fabric and various color ink droplets are selectively absorbed and reflected by the light irradiated on the fabric as needed, the inkjet printed pattern is

18



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presented by mixing colors on the fabric. Therefore, the inkjet printed patterns mainly were decided by the precise distribution of ink droplets on fabrics.

37

The dye

distribution on the fabric exerted a tremendous effect on the light absorption and light reflection. The improvement on the color performance was because of the limitation of the fabric structure on the diffusion and penetration of inks on fabrics, resulting in most dyes immobilized on the surface of the fabric. Obviously, the fabric color depth increased with the decrease of reflectivity from color strength equation. The scanning images of fabrics with different weave structures are displayed in Figure 11. Combining the characteristics of landscape paintings, oil paintings and portraits, as described above, it was found that the honeycomb weave fabrics presented the excellent inkjet printing performance for landscape paintings. The twill weave fabrics exhibited the excellent inkjet printing performance for oil paintings. The plain weave fabrics displayed the excellent inkjet printing performance for portraits. 4. Conclusion In summary, the nanospheres were successfully synthesized and used for cationization modification of different weave fabrics by dip-rolling method. The results indicated that the average diameter, zeta potential and glass transition temperature of the nanospheres were 65.5 nm, + 57.8 mV and 94.7 ℃, respectively. The nanospheres deposited on three cotton fabrics through the dip-rolling process, resulting in the decrease of porosity and roughness of fabrics and the increase of Zeta potential, hydrophilicity and thickness of fabrics. On the contrary, it was precisely because of the differences in Zeta potential, porosity, roughness, thickness, and hydrophobicity of fabrics that the high quality inkjet printing images can be obtained on fabrics with different weave structures. The honeycomb weave fabrics presented

19


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the excellent inkjet printing performance for landscape paintings. The twill weave fabrics displayed the excellent inkjet printing performance for oil paintings. The plain weave fabrics presented the excellent inkjet printing performance for portraits. Furthermore, EDS, FTIR and XPS results confirmed the presence of quaternary ammonium groups on cotton fibers derived from nanospheres. The nanospheres could strongly adsorb on the fiber by electrostatic attractive force. The reactive dye molecules in the inks could react with the cationized fibers by electrostatic attractive force, resulting in the increase of the color depth, fixation rates and pattern sharpness. The nanospheres cationization of different woven cotton fabrics could be potentially used in high-quality pattern without affecting the fabric handle significantly. Acknowledgments This research was supported by the National Key research and development program of China [Grant Number: 2017YFB0309800 and 2016YFC0400503]. References (1) Wang, C.; Wang, L.; Huang, Y.; Meng, Y.; Sun, G.; Fan, Q.; Shao, J. Fabrication of Reactive Pigment Composite Particles for Blue-light Curable Inkjet Printing of Textiles. Rsc Advances. 2017, 7, 36175-36184. (2) Shahariar, H.; Kim, I.; Soewardiman, H.; Jur, J. S. Inkjet Printing of Reactive Silver Ink on Textiles. ACS Appl. Mater. Interfaces. 2019, 11, 6208–6216. (3) Alam, M.; Christopher, L. A Novel, Cost-effective and Eco-friendly Method for Preparation of Textile Fibers from Cellulosic Pulps. Carbohydr. Polym. 2017, 173, 253-258. (4) Li, J.; Fan, J.; Cao, R.; Zhang, Z.; Du, J.; Peng, X. Encapsulated Dye/Polymer Nanoparticles Prepared via Miniemulsion Polymerization for Inkjet Printing. ACS Omega. 2018, 3, 7380–7387. 20



(5) Zhou, Y.; Yu, J.; Biswas, T. T.; Tang, R.; Nierstrasz, V. Inkjet Printing of Curcumin-Based Ink for Coloration and Bioactivation of Polyamide, Silk, and Wool Fabrics. ACS Sustain Chem. Eng. 2019, 7, 2073–2082. (6) Nechyporchuk, O.; Yu, J.; Nierstrasz, V. A.; Bordes, R. Cellulose NanofibrilBased Coatings of Woven Cotton Fabrics for Improved Inkjet Printing with a Potential in E-Textile Manufacturing. ACS Sustain Chem. Eng. 2017, 5, 4793–4801 (7) Wang, L.; Hu, C.; Yan, K. A One-Step Inkjet Printing Technology with Reactive Dye Ink and Cationic Compound Ink for Cotton Fabrics. Carbohydr. Polym. 2018, 197, 490–496. (8) Yang, H.; Fang, K.; Liu, X.; Cai, Y.; An, F.; Han, S. Effect of Ink-jet Printing Pretreatment on Fabric Structures. J Text Res, 2019, 40, 88-94. (9) Yang, H.; Fang, K.; Liu, X.; Cai, Y.; An, F. Effect of Cotton Cationization using Copolymer Nanospheres on Ink-jet Printing of Different Fabrics. Polymers. 2018, 10, 1219-1234. (10) Liu, Z.; Fang, K.; Gao, H.; Liu, X.; Zhang, J. Effect of Cotton Fabric Pretreatment on Drop Spreading and Colour Performance of Reactive Dye Inks. Color. Technol. 2016, 132, 407-413. (11) Kan, C.W.; Yuen, C.W.M.; Tsoi, W.Y. Using Atmospheric Pressure Plasma for Enhancing the Deposition of Printing Paste on Cotton Fabric for Digital Ink-jet Printing. Cellulose. 2011, 18, 827-839. (12) Soleimani-Gorgani, A.; Najafi, F.; Karami, Z. Modification of Cotton Fabric with a Dendrimer to Improve Ink-jet Printing Process. Carbohydr. Polym. 2015, 131, 168-176.

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(13) Shu, D.; Fang, K.; Liu, X.; Cai, Y.; Zhang, X.; Zhang, J. Cleaner Coloration of Cotton Fabric Dyed with Reactive Dyes using a Pad-batch-steam Dyeing Process. J. Clean. Prod. 2018, 196, 935-942. (14) Fang, K.; Zhao, H.; Li, J.; Chen, W.; Cai, Y.; Hao, L. Salt-free Dyeing of Cotton Fabrics Modified with Cationic Copolymer Nanospheres Using an Acid Dye. Fibers Polym. 2017, 18, 400-406. (15) Kaimouz, A.W.; Wardman, R.H.; Christie, R.M. The Inkjet Printing Process for Lyocell and Cotton Fibres. Part 1: the Significance of Pre-treatment Chemicals and Their Relationship with Colour Strength, Absorbed Dye Fixation and Ink Penetration. Dyes Pigm. 2010, 84, 79-87. (16) Fang, K.; Shu, D.; Liu, X.; Cai, Y.; An, F.; Zhang, X. Reactive Pad-steam Dyeing of Cotton Fabric Modified with Cationic P(St-BA-VBT) Nanospheres. Polymers. 2018, 10, 564-574. (17) Fang, K.; Song, T.; Zhang, K.; Chen, W.; Cai, Y.; Hao, L. Fixation of Cationic P (st-BA-AA-GMA) Emulsion on Pigment Particles in Dyeing of Cotton Fabrics. J. Appl. Polym. Sci. 2017, 134, 44987-44996. (18) Liu, X.; Li, C.; Fang, K.; Shu, D. A Novel Approach for Apocynum Venetum/Cotton Blended Fabrics Modification by Cationic Polymer Nanoparticles. Chin. Chem. Lett. 2017, 28, 955-959. (19) Liu, X.; Li, C.; Fang, K.; Shu, D.; Guo, Z. Coloration of Apocynum Venetum/Cotton Blends with an Acid Dye through Combined Pretreatment using Cationic Nanoparticles. Color. Technol. 2017, 133, 293-299. (20) Li, M.; Zhang, L.; An, Y.; Ma, W.; Fu, S. Relationship between Silk Fabric Pretreatment, Droplet Spreading, and Ink-jet Printing Accuracy of Reactive Dye Inks. J Appl Polym Sci, 2018, 135, 46703-46714.

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(21) Farooq, S.; Yousufani, S. A. Effect of Inter Yarn Fabric Porosity on Dye Uptake of Reactive Dyed cotton Woven Fabric. Mehran U Res J Eng Techn. 2015, 3, 265-272. (22) Bae, J. H.; Hong, K. H.; Lamar, T. M. Effect of Texture on Color Variation in Inkjet‐printed Woven Textiles. Color Res Appl. 2015, 40, 297-303. (23) Li, M.; Zhao, Y.; Zhang, L.; Zhang, Y.; Fu, S. Factors Influencing Printing Accuracy of Digital Printing for Knitted Polyester Fabric. J Text Res. 2018, 39, 62-66. (24) Fang, K.; Liu, Z.; Chen, W.; Zhang, J.; Liu, X.; Cai, Y. Effect of Fabric Surface Treatment on Ink-jet Printing With Reactive Dyes. J Text Res. 2015, 32, 128-132. (25) An, Y.; Li, M.; Du, C.; Tian, A.; Zhang, Y.; Fu, S. Diffusion Behavior of Micro Droplet on Silk Woven Fabrics. J Text Res. 2018, 39, 87-92. (26) Teli, M.; Pandit, P. Novel Method of Ecofriendly Single Bath Dyeing and Functional Finishing of Wool Protein with Coconut Shell Extract Biomolecules. ACS Sustain Chem. Eng. 2017, 5, 8323-8333.

(27) Fang, K.; Xia, X.; Cai, Y.; Hao, L.; Zhang, J.; Zhao Y. Blue Core–shell Nanospheres Prepared by Dyeing Poly(styrene‐co‐methacrylic acid) Dispersions. Color. Technol. 2016, 131, 458-463. (28) Abdali, H.; Ajji, A. Preparation of Electrospun Nanocomposite Nanofibers of Polyaniline/poly(methyl

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(31) Bulut, M.O.; Akar, E. Ecological Dyeing with Some Plant Pulps on Woolen Yarn and Cationized Cotton Fabric. J. Clean. Prod. 2012, 32, 1-9. (32) Ben, T.M.; Haddar, W.; Meksi, N.; Guesmi, A.; Mhenni, M.F. Improving Dyeability of Modified Cotton Fabrics by the Natural Aqueous Extract from Red Cabbage using Ultrasonic Energy. Carbohydr. Polym. 2016, 154, 287-295. (33) Ovando, V.; Vizcaino, J.; Omar Gonzalez, O.; Garza, R.; Martinez, H. Synthesis of α‐cellulose/polypyrrole Composite for the Removal of Reactive Red Dye from Aqueous Solution: Kinetics and Equilibrium Modeling. Polym Composite. 2015, 36, 312-321. (34) Froberg, J. C.; Rojas, O. J.; Claesson, P. M. Surface Forces and Measuring Techniques. Int. J. Miner. Process. 1999, 56, 1-30. (35) Ding, Y.; Shamey, R.; Chapman, L. P.; Freeman, H. S. Pretreatment Effects on Pigment-based Textile Inkjet Printing - Colour Gamut and Crockfastness Properties. Color Technol. 2018, 135, 1-10. (36) Gong J.; Ren Y.; Fu R.; Li, Z.; Zhang J. pH-mediated Antibacterial Dyeing of Cotton with Prodigiosins Nanomicelles Produced by Microbial Fermentation. Polymers. 2017, 9, 468-452. (37) Patel, A.; Heussen, P.; Dorst, E.; Hazekamp, J.; Velikov, K. Colloidal Approach to Prepare Colour Blends from Colourants with Different Solubility Profiles. Food Chem. 2013, 141, 1466-1471. (38) Cai, Y.; Huang, Y.; Liu, F.; He, L.; Lin, L.; Zeng, Q. Liquid Ammonia Dyeing of Cationic Ramie Yarn with Triazinyl Reactive Dyes. Cellulose. 2014, 21, 3841-3849. (39) Romdhani, Z.; Baffoun, A.; Hamdaoui, M.; Roudesli, S. Experimental Study and Mathematical Model to Follow the Spreading Diameter on Coated Woven Cotton Fabric. Fibers Polym. 2017, 18, 2454-2461.

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Figure 1. Three cotton fabrics shown on the weaving paper (a), three-dimensional (b), and fabric photographs (c).

Figure 2. The polymerization for preparing the cationic P(St-BA-VBT) nanospheres.

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Figure 3. TEM images of P(St-BA-VBT) nanospheres (a), size distributions of P(St-BA-VBT) nanospheres (b), Zeta potential of P(St-BA-VBT) nanospheres (c), and DSC curve of P(St-BA-VBT) nanospheres (d).

26



Figure 4. SEM images of different fabrics cationized with nanospheres, cationized plain fabrics (a), cationized twill fabrics (b) and cationized honeycomb fabrics (c). SEM images and EDS spectra (face sweep) of untreated cotton fabrics (d), cationized cotton fabrics (e), ink-jet printed

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cotton fabrics (f), steamed cotton fabrics (g) and washed cotton fabrics (h). FTIR spectrums of untreated and treated cotton fabrics with different weave structures (i). XPS survey of cotton fabrics at different stages of ink-jet printing (j).

Figure 5. SEM images showing the top surface view of non-coated (a) and coated (b, c, d, e, f) woven cotton fabrics with 0.22 g/m2 (b), 0.34 g/m2 (c), 0.49 g/m2 (d), 0.62 g/m2 (e), and 0.75 g/m2 (f) of cationic nanospheres.

28



Figure 6. Roughness(a-c), porosity(d), thickness(e), water contact angle (f), Zeta potential (g), color strength (K/S) values (h), fixation rates (i) outline sharpness of warp direction (j), outline sharpness of weft direction (k) and apparent color images (l) of the woven cotton fabrics with different concentrations of cationic nanospheres.

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Figure 7. Diffusion pattern of the ink-jet printed lines of 1 mm on plain weave fabrics (a), twill weave fabrics (b) and honeycomb weave fabrics (c), 1-cyan, 2-magenta, 3-yellow, 4-black.

Figure 8. Ink drops on ink-jet printed plain weave fabrics (a), twill weave fabrics (b) and honeycomb weave fabrics (c), 1-cyan, 2-magenta, 3-yellow, 4-black. The color coverage was 20%.

30



Figure 9. K/S curve and reflectance curve of the ink-jet printed fabrics with different structures, cyan (A), magenta (B), yellow (C) and black (D), 1-K/S value, 2-reflectance, all fabrics were printed at a resolution of 720 × 720 dpi and a color coverage of 100%. The printed fabrics 31


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were steamed at (102 ± 1) ℃ for 6 min with saturated steam.

Figure 10. The mechanism of nanospheres modification and ink-jet printing of untreated cotton fabric (a), cationized cotton fabric (b) and ink-jet printed cotton fabrics (c).

32


ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 33


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Page 35 of 37 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 11. Scanned images of ink-jet printed plain fabrics(a), twill weave fabrics (b) and honeycomb weave fabrics (c). All fabrics were padded through modification fluid (1 g/L of nanospheres and 10 g/L of sodium bicarbonate) steamed at (102 ± 1) ℃ for 6 min. Table 1. Contact angles and surface energy of the untreated and pretreated fabrics with different structures a Contact angles (°) Pretreatment

Untreated

Treated

Fabric

Surface energy (mJ/m2)

i

j

 Sd

 Sp

S

Plain

11.5

22.7

35.21

38.59

73.80

Twill

13.4

24.6

34.66

38.52

73.18

Honeycomb

15.7

26.5

34.09

38.28

72.36

Plain

47.2

78.7

10.74

41.18

51.92

Twill

51.4

82.1

9.57

39.12

48.69

Honeycomb

54.5

85.2

8.50

38.83

47.33

34



a

Page 36 of 37

The contact angles were measured at 20 ± 2 °C and 67 ms after the probe liquid had been

dropped on the fabrics;  i and

 j are the contact angles of distilled water and diiodomethane

respectively. Table 2. Colorimetric values of the ink-jet printed cotton fabrics with different structures.a Ink

Fabric

Cyan

Magenta

Yellow

Black

a

Apparent color

L*

a*

b*

C*

h°

Plain

54.5

-33.5

-32.3

46.5

223.9

Twill

53.4

-34.3

-33.3

47.7

224.1

Honeycomb

52.6

-34.1

-33.4

47.8

224.4

Plain

43.3

56.6

-5.0

55.9

354.9

Twill

42.1

55.8

-3.5

56.8

356.4

Honeycomb

41.3

58.3

-1.7

58.4

358.3

Plain

86.0

-12.1

78.2

79.1

98.8

Twill

83.9

-8.5

87.3

86.2

95.5

Honeycomb

82.5

-10.4

85.5

87.7

97.0

Plain

20.5

-0.2

-3.0

2.6

276.7

Twill

19.9

-0.3

-2.6

3.0

276.1

Honeycomb

18.8

-0.5

-2.9

3.0

276.8

The fabrics were printed at a resolution of 720 × 720 dpi and a color coverage of 100%. The

printed fabrics were steamed at (102 ± 1) ℃ for 6 min with saturated steam. Table 3. Color fastness of ink-jet printed cotton fabrics with different structures. a

Ink

Cyan

Fabric

Rubbing fastness

Washing fastness

Dry

Wet

SW

CC

SC

Plain

4-5

3-4

4-5

4-5

4-5

Twill

4-5

3-4

5

5

5

Honeycomb

4-5

4

5

5

5

35


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Magenta

Yellow

Black

a

Plain

4-5

3-4

4-5

4-5

4-5

Twill

4-5

3-4

5

5

5

Honeycomb

4-5

4

5

5

5

Plain

4-5

3-4

4-5

4-5

4-5

Twill

4-5

3-4

5

5

5

Honeycomb

4-5

4

5

5

5

Plain

4-5

3-4

4-5

4-5

4-5

Twill

4-5

3-4

5

5

5

Honeycomb

4-5

4

5

5

5

Color change (CC), Staining on cotton fabric (SC), Staining on wool fabric (SW).

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High-Quality Images Inkjetted on Different Woven Cotton Fabrics

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