Nanosilver leverage on reactive dyeing of cellulose fibers: Color shading, color fastness and biocidal potentials

Carbohydrate Polymers 186 (2018) 310–320

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Carbohydrate Polymers journal homepage: www.elsevier.com/locate/carbpol

Nanosilver leverage on reactive dyeing of cellulose fibers: Color shading, color fastness and biocidal potentials ⁎

T

⁎

Hanan B. Ahmeda, , Hossam E. Emamb, , Hamada M. Mashalyc, Mohamed Rehanb a

Chemistry Department, Faculty of Science, Helwan University, Ain-Helwan, Cairo 11795, Egypt Department of Pretreatment and Finishing of Cellulosic Fibers, Textile Research Division, National Research Centre, Scopus Affiliation ID 60014618, 33 EL Buhouth St., Dokki, Giza 12622, Egypt c Department of Dyeing, Printing and Auxiliaries, Textile Research Division, National Research Centre, Scopus Affiliation ID 60014618, 33 EL Buhouth St., Dokki, Giza 12622, Egypt b

A R T I C L E I N F O

A B S T R A C T

Keywords: Viscose Immediate AgNPs Color shading Release Biocidal properties

The current approach focuses on studying the leverage of nanosilver (AgNPs) incorporation on the dyeing process of viscose fibers by blue reactive dye. Nanosilver was straightway incorporated into viscose fibers using sodium citrate as nanogenerator. Owing to AgNPs incorporation, color of fibers was turned to greenish-blue and darker greenish color was observed with low Ag content (< 1 g/kg). Regardless to the processes sequencing, color strength of fibers was magnified by increasing in Ag content. The constancy of fibers color was not affected by AgNPs inclusion, whatever the processes sequencing and Ag content. Release property of Ag from fibers into water was considerably depended on the processes sequencing. By incorporation of AgNPs firstly, the lowest Ag release value was estimated (0.25 g/kg after 24 h). Antimicrobial activities were significantly improved by AgNPs incorporation. Reduction in bacteria and fungi was reached 92.4% and 67.9% after 24 h contact time, respectively.

1. Introduction Textile industrialization is one of leading industries in which nanotechnology is being implemented with full enthusiasm (Ahmed & Emam, 2016; Emam, Mowafi, Mashaly, & Rehan, 2014; Emam, Rehan, Mashaly, & Ahmed, 2016; Emam, Saleh, Nagy, & Zahran, 2015, 2016; Mowafi, Rehan, Mashaly, Abou El-Kheir, & Emam, 2017; Rehan, Mashaly, Mowafi, El-Kheir, & Emam, 2015). Nanotech-textiles become one of the most popular textiles with their multi-functional properties, as one of the most important advantageous properties of nanotechtextiles is their protective properties. The characteristic properties of different metal nanoparticles and their applications in manufacturing functional textiles were extensively studied in literatures (Ahmed, ElRafie, & Zahran, 2015; Ahmed & Emam, 2016; El-Rafie, Ahmed, & Zahran, 2014; Emam, El-Hawary, & Ahmed, 2017; Emam, El-Rafie, Ahmed, & Zahran, 2015; Emam et al., 2013; Emam, Mowafi et al., 2014; Emam, Rehan et al., 2016; Emam, Saleh et al., 2015, 2016; Emam & Zahran, 2015; Junyan, 2003; Mowafi et al., 2017; Qian, 2004; Qian & Hinestroza, 2004; Rehan et al., 2017; Rehan, Hartwig, Ott, Gätjen, & Wilken, 2013; Rehan et al., 2015; Smith & Block, 1982; Trotman, 1984; Zahran, Ahmed, & El-Rafie, 2014). Nowadays, numerous researches are interested in reducing or inhibiting those infections caused by antibiotic-resistant bacterial species ⁎

which survived on hospital textiles (Neely & Maley, 2000; Slaughter et al., 1996). Consequently, these demonstrate a great demand for antimicrobial textiles and materials (quaternary ammonium compounds, chitosan, triclosan, metals/metal oxides nanoparticles and bioactive plant-based extracts) that are capable of protection against major pathogens (Ahmed et al., 2015; Ahmed & Emam, 2016; Alemdar & Agaoglu, 2009; Ali, Joshi, & Rajendran, 2011; El-Rafie et al., 2014; Emam, El-Hawary et al., 2017; Emam, El-Rafie et al., 2015; Emam, Manian et al., 2014; Emam et al., 2013; Ilić et al., 2009; Jeong, Hwang, & Yi, 2005; Joshi, Ali, & Rajendran, 2007; Kalyon & Olgun, 2001; Ki, Kim, Kwon, & Jeong, 2007; Liang et al., 2006; Pinto, Vale-Silva, Cavaleiro, & Salgueiro, 2009; Sójka-Ledakowicz et al., 2009; Sun, Li, Qiu, & Qing, 2005; Worley & Sun, 1996; Worley, Williams, & Crawford, 1988; Zahran et al., 2014). Silver nanoparticles (AgNPs) have been widely used due to its broad spectrum of antimicrobial activities and low toxicity toward mammalian cells (Gaonkar, Sampath, & Modak, 2003; Kim et al., 2009). Nano-silver as one of the different nanomaterials used to impart antimicrobial activities in textile materials, can impart antimicrobial properties as well as characteristic colors such as brown, cream, yellow, dark green or purple according to the size and shape of AgNPs incorporated in textile matrices. Chattopadhyay and Patel reported that treatment with AgNPs could improve the tensile strength and color

Corresponding authors. E-mail addresses: [email protected] (H.B. Ahmed), [email protected] (H.E. Emam).

https://doi.org/10.1016/j.carbpol.2018.01.074 Received 1 October 2017; Received in revised form 20 December 2017; Accepted 20 January 2018 0144-8617/ © 2018 Elsevier Ltd. All rights reserved.

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depth on cotton, wool and silk fabric (Chattopadhyay & Patel, 2009; Gulrajani, Gupta, Periyasamy, & Muthu, 2008). Recently, the efficiency of AgNPs direct synthesis in multi-functionalization of natural and synthetic fibers/fabrics was investigated, as all the treated fabrics acquired new decorative color, antimicrobial and UV-resistance properties (Ahmed & Emam, 2016; Emam, El-Hawary et al., 2017; Emam, Mowafi et al., 2014; Emam, Rehan et al., 2016; Emam, Saleh et al., 2015, 2016; Mowafi et al., 2017; Rehan et al., 2015). The authority of nanosilver incorporation on the textile dyeing process was previously studied for dispersed dye, sulfur dye, vat dye, acid dye and direct dye (Gorenšek & Recelj, 2009; Gulrajani et al., 2008; Ki et al., 2007; Maneerung, Tokura, & Rujiravanit, 2008; Perelshtein et al., 2008; Saengkiettiyut, Rattanawaleedirojn, & Sangsuk, 2008). Disperse dyeing of cotton and cotton/polyester blend fabrics in the presence of AuNPs was reported by using a binder, and the treated fabrics were exhibited excellent antimicrobial activity against E. coli, S. aureus and the fungus of C. albicans (Perelshtein et al., 2008; Saengkiettiyut et al., 2008). Additionally, the laundering durability and changing in color of fabrics were monitored. A combination treatment of wool fabric with sulfur dye and AgNPs was studied to produce mothproofing, antimicrobial and antistatic fabrics (Ki et al., 2007; Maneerung et al., 2008). Inspiration of AgNPs on cotton and wool fabrics dyed with vat dye were demonstrated through antibacterial activities and color differences (Gorenšek & Recelj, 2009). Pretreatment of wool fabrics with nanosilver composites was shown to increase the acid dye up-take (Mashaly, Moursy, Kamel, Taher, & Farahat, 2014). Additionally, the presence of nanosilver was showed to effect on the color strength and manifest the antimicrobial properties of cotton, silk and wool fibers which were finished with direct dyes (Chattopadhyay & Patel, 2009). Cellulosic based textiles are shown to be mostly dyed with reactive dyes, as reactive dyes are characterized by production of a wide range of bright colors with excellent wash fastness. Herein, the leverage of nanosized silver on color shading, color fastness and augmentation of biocidal properties of reactive dyed viscose fibers was systematically studied. AgNPs were directly synthesized using citrate as a reducing agent. The effect of silver salt concentration, dye percentage in reaction liquor and the reaction sequences were monitored. SEM images and EDX data were represented to confirm the successive incorporation of nanosilver on the treated fibers. Absorbance spectra, color coordinates, color strength and the color fastness were all estimated for treated fibers to check the influence of AgNPs incorporation on the coloration process. Release behavior of silver ions and biocidal properties of treated fibers were both evaluated to measure the effect of dyeing on the application of fibers incorporated silver.

Table 1 Experimental conditions for treatment of viscose fibers. Samples

Ag Conc. (mg/L)

Dye Conc. (%)

Process ordering

Blank A B 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

0 0 0 40 200 800 40 200 800 40 200 800 40 200 800 40 200 800 40 200 800 40 200 800

0 1% 5% 0 0 0 1% 1% 1% 5% 5% 5% 1% 1% 1% 5% 5% 5% 1% 1% 1% 5% 5% 5%

Dyeing Dyeing AgNPs AgNPs AgNPs AgNPs followed by dyeing AgNPs followed by dyeing AgNPs followed by dyeing AgNPs followed by dyeing AgNPs followed by dyeing AgNPs followed by dyeing Dyeing followed by AgNPs Dyeing followed by AgNPs Dyeing followed by AgNPs Dyeing followed by AgNPs Dyeing followed by AgNPs Dyeing followed by AgNPs Concurrently Concurrently Concurrently Concurrently Concurrently Concurrently

incorporation and blue reactive dye. These processes are represented in direct incorporation of AgNPs followed by dyeing, dyeing followed by incorporation of AgNPs and concurrently combination of AgNPs incorporation and dyeing. The experimental conditions of the fibers treatment were summarized in Table 1. The treated samples are named as Ag – Dye, Dye – Ag and Dye/Ag, respectively. Each process can be described briefly as follows: 2.2.1. Incorporation of AgNPs 5 g of viscose fibers were submerged in AgNO3 solution (40, 200 and 800 mg/L) using 1:50 material to liquor ratio and then the mixture was heated till boiling under continuous stirring. A 10 mL from 3% tri-sodium citrate as reducer was drop wisely added to every 100 mL of silver nitrate solution. The reaction mixture was kept at boiling temperature under constant stirring for 30 min and then the fibers were removed and rinsed twice by tap water. The treated fibers were then dried at 80 °C prior to analyses/characterizations and dyeing process. 2.2.2. Dying process Dyeing with the reactive dye was performed for fibers and AgNPsfibers using the CI reactive blue19 dye. The dyeing was carried out by dissolving of dye (1% and 5% (owf)) in distilled water then 5 g viscose fibers was added to dye solution using material to liquor ratio of 1:50. To this dye bath, 30 g/L sodium sulfate was added at 40 °C and after 30 min, 20 g/L sodium carbonate was drop wisely added. Then the temperature was raised to 60 °C and dyeing process was preceded for a further 60 min. At the end of dyeing, the dyed samples were rinsed with tap water and then dried on air prior to analyses/characterizations and/ or AgNPs incorporation.

2. Experimental 2.1. Materials and chemicals Silver nitrate (99.5%, from Panreac, Barcelona – Spain), Trisodium citrate (99% from Sigma, Aldrich – Germany), CI Reactive Blue19 (RB19) (C22H16N2Na2O11S3, DyStar Colours, Frankfurt – Germany), sodium hydroxide (99%, from s.d. fine Chemical Limited, Mumbai – India), Sodium sulfate anhydrous (99%, El Nasr Pharmaceutical Chemicals, Cairo – Egypt) and Sodium carbonate anhydrous (97%, El Nasr Pharmaceutical Chemicals, Cairo – Egypt) were used as received. Viscose as regenerated cellulose fibers (Lenzing Viscose®) with length of 38 mm and linear density of 1.3 dtex, was kindly supplied from Lenzing AG (Lenzing, Austria). Fibers did not have been spanned and were used without further treatment.

2.2.3. Concurrently combination process In this process, combination between fibers dyeing and AgNPs incorporation was concurrently performed. AgNO3 was added in the solution mixture during the dyeing operation. A 5 g viscose fibers was added to dye solution (1% and 5% (owf)) using 1:50 material to liquor ratio and then sodium sulfate (30 g/L) was added at 40 °C. After 30 min sodium carbonate (20 g/L) was drop wisely added to dye bath, followed by addition of AgNO3 solution (40, 200 and 800 mg/L) and tri-sodium citrate (10 mL, 3%). The temperature of mixture was then raised to 60 °C and the process was performed for further 60 min under

2.2. Procedure The current study concluded three different process carried out for viscose fibers to acquire green color based on combination of AgNPs 311

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continuous stirring. At the end of process, the samples were rinsed with tap water and then dried on air prior to analyses and characterizations.

two concentrations was calculated and then normalized to the initial concentration of dye, to obtain the percentage of dye content on fibers.

2.3. Measurements

2.3.7. Release behavior Release of silver ions from treated fibers (Ag, Ag–Dye, Dye–Ag and Dye/Ag) was performed in distilled water (Emam, Ahmed, & Bechtold, 2017). In details, an exact weight from dried treated fibers (0.5 g) was immersed in 100 mL of distilled water at room temperature for 24 h. After different interval contact time (1, 3, 7 and 24 h), samples were withdrawn from solution. Silver contents in the taken solutions were measured via using flame atomic absorption spectrophotometer (Agilent 200 series AA systems, 240FS AA, Agilent technologies, USA) attached with atomizer of GTA 120 graphite tube. To calculate Ag release (g/kg), content of the measured Ag was normalized to the dry mass of the tested fibers.

2.3.1. Scanning electron microscopy (SEM) The surface of untreated and treated viscose fibers was examined by high resolution scanning electron microscopy (SEM Quanta FEG 250 with field emission gun, FEI Company – Netherlands). The chemical composition of the manufactured composites was analyzed using surface Energy dispersive X-ray spectroscopy (EDX) (EDAX AMETEK analyzer) attached with the electron microscope. Particle size of nanosilver was measured from micrographs by using 4 Pi software analysis program. 2.3.2. Attenuated total reflection – Fourier transformation infrared (ATRFTIR) Fiber samples were subjected to high resolution JASCO FT/IR – 4700 spectroscopy (JASCO Analytical Instruments, Easton, USA). The spectroscopy instrument was attached with a deuterated triglycine sulfate (TGS) detector and conducted with ATR unit. The spectra were collected in the wavenumber range of 4000–500 cm−1 using transmission mode (T%).

2.3.8. Biological activity Biological activities of treated fibers were tested quantitatively against different microbes using ASTM test method E2149-01 for Microbial Counting (E-2149-01, 2004). Escherichia coli ATCC-25922 (G −ve bacteria), Staphylococcus aureus ATCC 47077 (G +ve bacteria), Candida albicans ATCC 10231 (fungi) and Saccharomyces cerevisiae ATCC-9763 (fungi) were all used in this test as microbes pathogens. Suspensions from the different pathogens (ca. 2.4–3.0 × 107 CFU/mL) were synthesized in KH2PO4 buffer solution with pH 7.2 for bacteria and pH 6 for fungi. A 0.2 g fibers was submerged in 20 mL of microbial suspension at 25 °C and then vigorously shaken. After 24 h, a 1 mL was withdrawn from microbial suspensions and plated on nutrient agar and then incubated at 37 °C for bacteria and at 30 °C for fungi. Survived microbial colonies after 4 and 24 h were counted and the microbial activities of treated fibers were estimated by the reduction percentage in microbial colonies using Eq. (1).

2.3.3. Colour measurements The colorimetric analysis (L, a*, b*) of viscose fibers before and after treatment was recorded using a spectrophotometer with pulsed xenon lamps as light source (UltraScan Pro, Hunter Lab, USA). The spectrophotometer was adjusted at 10° observer with D65 illuminant, d/2 viewing geometry and 2 mm measurement area. L is lightness (0–100) from black to white, a* (+/−) is a red/green ratio and b* (+/−) is yellow/blue ratio (Chattopadhyay & Patel, 2010; Zollinger, 2003). The corresponding color strength (K/S) and absorbance were both measured. All measurements were performed two times and the mean value was conducted.

R% =

B−A × 100 B

(1)

Where R% is the reduction percentage of microbial colonies, A is the number of microbial colonies remaining on the agar plate with treated fabrics, and B is the number of microbial colonies remaining on the agar plate for control

2.3.4. Fastness properties Fastness properties were tested for all treated fibers according to reference methods (“BS 1006, Standard Methods for Determination of the Color Fastness of Textile and Leathers, 5th ed Society of Dyes and Colorists publication,” 1990). The rubbing, washing and perspiration fastness were measured in accordance with the method of ISO 105-X12 (1987), ISO 105-C02 (1989) and ISO 105-E04 (1989), respectively using the Grey-scale. Meanwhile the light fastness was evaluated by using ISO 105-B02 (1988) via Blue-scale.

3. Results and discussion In spite of the AgNPs incorporation in dyeing bath for textile finishing was widely studied (Baban, Yediler, & Ciliz, 2010; Gorenšek & Recelj, 2009; Gulrajani et al., 2008; Ki et al., 2007; Maneerung et al., 2008; Perelshtein et al., 2008; Saengkiettiyut et al., 2008; Wu, Zhang, Tao, Zhang, & Fong, 2010), but there are no reported studies on the synergism between AgNPs within viscose textiles’ dyeing/printing using reactive dye. Additionally, no studies were concerned with direct incorporation of AgNPs and dyeing in one pot, as well as monitoring the effect of reaction sequencing. Therefore, the leverage of direct synthesized AgNPs on color change, color fastness and antimicrobial efficiency for reactive dyeing viscose fibers was the focus of this study. Direct incorporation of AgNPs was performed using citrate based on a previous work (Emam, Rehan et al., 2016; Mowafi et al., 2017; Rehan et al., 2015). The current work was designed to include three different processes; dyeing followed by AgNPs incorporation (dye–Ag), AgNPs incorporation followed by dyeing (Ag–dye) and concurrent dyeing/AgNPs incorporation (dye/ Ag). Different silver concentrations and dye percentages were used to achieve the fulfill goal.

2.3.5. Silver contents Contents of silver in fibers were measured for the extracted solution using the recent methods from literatures (Emam & Bechtold, 2015; Emam, El-Hawary et al., 2017; Emam, Manian et al., 2014; Emam et al., 2013; Emam, Mowafi et al., 2014). The extraction of silver was performed by using 15% (w/v) nitric acid and the used material to liquor ratio was 1:100. The extracted silver in solution was analysed with flame atomic absorption spectrophotometer (Agilent 200 series AA systems, 240FS AA, Agilent technologies, USA) attached with GTA 120 graphite tube atomizer. The contents of silver with g/kg were calculated based on the masses of extracted samples. If required, dilution was performed for high concentrated samples and the dilution factor was considered. 2.3.6. Dye contents The content of dye onto fibers after dyeing process, was expressed as the consumed dye percentage by fibers which can calculated by exhaustion method. The concentration of dye in dyeing bath was photometrically measured before and after treatment using UV–vis spectrophotometer (UV-1201, Shimadzu – Japan). The difference between the

3.1. SEM and EDX images The surface morphology of the dyed, dye–Ag, Ag-dyed, Ag/dye and Ag-viscose fibers specimens were examined under electron microscope 312

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Fig. 1. SEM images and EDX analysis for treated viscose fibers: [a] dyed viscose, [b] AgNPs-viscose, [c] AgNPs-dyed viscose (Ag-Dye), [d] dyed AgNPs-viscose (Dye-Ag) and [e] AgNPs/dyed viscose concurrently (Ag/Dye).

sequencing on the optical characters of the dyed viscose fibers, the UV–vis absorption spectra of treated viscose fibers were detected and presented in Fig. 2. For untreated fibers, no absorbance peaks were recorded. For Ag-fibers, an absorbance peak at 420 nm was detected for the yellow color, corresponding to the surface plasmon resonance (SPR) of AgNPs (Ahmed & Emam, 2016; Emam & Bechtold, 2015; Emam, Rehan et al., 2016; Emam, Saleh et al., 2015, 2016). While for the dyed fiber, an absorbance peak was appeared at 640 nm which characterized for the blue color of dye used. Incorporation of AgNPs into the dyed samples resulted in appearance of two significant peaks; (at 420 nm) signified for nanosilver and other one for the reactive dye (at 640 nm). Incorporation of AgNPs before the dyeing process, reflected in decrement in the SPR peak intensity of AgNPs. However, the direct incorporation of AgNPs lately, is driven to extensively increasing in the intensity of AgNPs SPR peak and marginal decrement in absorbance peak intensity of dye. These observations are in agreement with that of SEM data and further confirmed the argumentation presented in SEM data, as dyeing of fibers after AgNPs incorporation, retards the detection of AgNPs by forming a masking layer. The interchanging of the peak intensity for the dye is signing for color change of specimens by the effect of nanosilver incorporation. Direct incorporation of nanosilver is accompanied by changing of fiber's color to greenish color, whatever the processes sequences applied. The green color was clearly seen by naked eye and the image of fibers (Fig. 2) was further confirmed this surveillance.

(SEM), and the micrographs are shown in Fig. 1. The dyed fiber was observed clear and smooth under microscope as seen in Fig. 1a. For fibers incorporated by AgNPs (Fig. 1b), micrograph showed that spherical AgNPs were uniformly integrated with the surface of viscose fibers. This confirmed the compatibility of viscose with cellulosic skeleton (stabilizer) to combine with citrate (reducer) as NPs’ synthesizers (Emam, Rehan et al., 2016; Rehan et al., 2015). The presence of AgNPs on the surface of fibers was confirmed using the EDX analysis and signal of Ag element was existed on the EDX spectrum in all samples treated with silver. Sizes of nanosilver on the fibers were measured from the electron micrographs by using software analysis program of 4 Pi and size distribution was presented in the supplementary file (Fig. S1). Micrographs presented in Fig. 1c–e showed the effect of procedure sequencing on the topographical features of viscose specimens dyed and incorporated with AgNPs. It was found that, evidently, incorporation of AgNPs firstly resulted in larger sized nanosilver (93.7 nm) than that of incorporated nanosilver alone (83.2 nm). Insignificant appearance of nanosilver (Fig. 1c) could be explained due to the deposition of dye molecules over the AgNPs–fibers forming covered layer and masking the observation of nanoparticles to be insensible under microscope. The notable deposited AgNPs on the surface of fibers was observed for the dye–Ag fibers (Fig. 1d) which further confirmed the former argumentation. Incorporation of AgNPs lately is accompanied by the clear appearance of AgNPs with the smallest size (71.5 nm) onto the surface of fibers which may reflect the role of dye molecules in the reduction of silver. However, some dense agglomeration of NPs was obviously visible on the surface of fibers (107.8 nm), when the fibers were dyed and incorporated with NPs concurrently (Ag/dye) (Fig. 1e). This could be attributed to two factors: (i) the high competition between fiber cellulosic skeleton and dye macromolecules for NPs stabilization through coordination binding. (ii) The thermo-migration of NPs under high temperature and in the presence of dye macromolecules in reaction bath (Mouxiou, Eleftheriadis, Nikolaidis, & Tsatsaroni, 2008).

3.3. FTIR ATR-FTIR spectra of untreated fibers, dyed fibers and AgNPs treated fibers are shown in Fig. 3. Pristine viscose as cellulosic fibers, displayed two significant bands at 1648 cm−1and 3333 cm−1, identical to C]O of carboxyl group and OeH stretching, respectively (Emam, Ahmed, & Bechtold, 2017; Emam, El-Hawary et al., 2017; Emam, El-Zawahry, & Ahmed, 2017). Also, the a symmetric stretching of aliphatic CeH is recorded at 2880 cm−1 and the peaks placed in 1314–1373 cm−1 are characterized for bending vibrations of CeH and CeC bonds. However, the peak which is notified at 1172 cm−1 is referred to the CeOeC

3.2. UV–vis spectra To declare the effect of nanosilver incorporation and the reaction 313

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Fig. 1. (continued)

glycosidic ether bond and at 1015 cm−1 is characteristic for (CeOH) 1° alcohol, where, which appeared at 891 cm−1 is significant peak for symmetrical (CeOeC) in plane (Garside & Wyeth, 2000; Mascarenhas, Dighton, & Arbuckle, 2000). These characteristic peaks are related to the cellulose which is the main constituent of viscose fibers. In case of fibers treated with dye only, two new IR bands were detected at 2916 and 1076 cm−1 which are referred to aromatic CeH stretch and CeN stretching for the dye molecules, respectively. In addition to the aliphatic CeH band was shifted to 2848 cm−1. These spectral data confirmed the interaction between dye molecules and cellulose fibers. Regardless to the sequences of additions, the intensity of the so-mentioned peaks were significantly lowered by incorporation of AgNPs in the dyed fibers, this indicates a decrease in such bond strength (Trivedi, Patil, Shettigar, Bairwa, & Jana, 2015). This observation gives an assignment for the employment of dye molecules for sharing cellulose macromolecules in coordination and stabilization of AgNPs. Referring to the spectral data of the treated samples, except that of dyed fiber only, IR band which is detected at 665 cm−1 confirmed the presence of O-Ag bond (Goudarzi, Mir, Mousavi-Kamazani, Bagheri, & Salavati-Niasari, 2016). Additionally, regardless to the treatment sequencing, intensities of all transmission peaks for cellulose were increased after treatment, such like the peaks recorded at 1172 cm−1 (CeOeC glycosidic ether bond) and at 1015 cm−1 (CeOH 1° alcohol). Increment in the intensities of the as-mentioned bands is attributed to the occupation of such groups in the interaction with dye and nanosilver (Das, Bakshi, & Bhattacharya, 2014, 2016; Ibrahim & Reda, 2015). However, insignificant increment in the intensities of these

peaks was observed in case of performing the concurrent process, which could be attributed to the interaction between dye molecules and AgNPs rather than their interaction with cellulose fibers. 3.4. Colorimetric results In order to approve the authority of nanosilver incorporation on the color changing, color coordinates (L*, a* and b*) and color strength (K/ S) of fibers were measured and the data presented in Table S1 (Supplementary data) and Fig. 4. From these color data, can be recognized that: i) AgNPs incorporation into fibers, led to greatly increment in both of a* and b* values in the positive direction, which was reflected in the color changing to the reddish-yellow owing to the presence of nanosilver (Emam, Mowafi et al., 2014; Emam, Rehan et al., 2016; Emam, Saleh et al., 2015, 2016; Mowafi et al., 2017; Rehan et al., 2015). Due to the dyeing with blue dye, fibers acquired a deep bluish color via the extensive increment in the b* values in the negative direction. ii) Greenish color was appeared for the dyed fibers after AgNPs incorporation, regardless to the sequences of the process. The appeared greenish color is corresponding to the mixture between blue color of due and yellow color of AgNPs as seen in the absorbance spectra. iii) Increasing in the Ag content in fibers was accompanied by paleness in the green color and the darker greenish color was recorded at low 314

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Fig. 2. [upper] Absorbance spectra of treated viscose fibers and [down] photographic images of corresponding fibers. (For interpretation of the references to colour in the text legend, the reader is referred to the web version of this article.)

color shading of fibers and this hypothesis can be explained by two main reasons as follows: (1) Owing to the yellow color of AgNPs with different shades depending on Ag concentration, its combination with the blue dye resulted in changing in the color shade of dyed fibers. (2) Nanosilver can act as mordant in the dyeing process and leads to increment in the dye affinity, reflected in more opportunities for binding between dye molecules and the fibers backbone producing different color shades. Besides, the increment in K/S values along with increment in Ag salt concentration is further affirmed the role of nanosilver in color shading. Impregnation of AgNPs directly into viscose fibers was improved the color strength of reactive dye with higher level than that after addition of AgNPs colloidal solution to direct dyeing bath of cotton fibers (Chattopadhyay & Patel, 2009). Likewise for AgNPs colloidal added to the reactive dye bath of polyamide (Gorenšek & Recelj, 2009), the growth in color strength was showed much less than that recorded in the current study for viscose fibers. Moreover, the color shade of both of dyed cotton fibers and dyed polyamide wasn’t changed by AgNPs addition.

Fig. 3. FTIR spectra for treated viscose fibers.

3.5. Synergistic effect

Ag content (< 1 g/kg). Augmentation of dye percentage from 1% to 5% had no obvious trend on the color shading. iv) Whatever, the sequences of process, color strength (K/S) values were showed enlarged dramatically with raising both of Ag content in fibers and dye percentage used.

Effect of AgNPs incorporation and dyeing on their corresponding contents in fibers were studied through measuring Ag and dye contents in treated fibers (Table S1 & Fig. 4c). For the samples incorporated with AgNPs only, increment in Ag salt concentration was reflected logically in increasing of Ag content. Dyeing process after AgNPs incorporation

All of these foundations confirmed the leading role of nanosilver in 315

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derivatives) are firstly adsorbed on fibers’ surfaces and then diffuse within the fiber intermolecular spaces, where they are uniformly distributed. However, when the dyeing process is finished, it is necessary that the color acquired by the fibers must have some degree of resistance for removing out. This requirement could be described as fastness properties that are consequently important to be measured for investigating the influence of AgNPs incorporation on the color fastness of dyed specimens. Cellulosic fibers colored with reactive dyes as one of the most applicable dyes are characterized by high fastness. From the data shown in Supplementary data (Table S2), it could catch sight of that all fastness parameters (rubbing, washing, perspiration and light) were graded as good for the dyed fibers whatever the dye percentage. Regardless the process sequences and silver concentration, incorporation of nanosilver was not affected the stability of dye on fibers and the fastness properties was still with nearly the same rate. Thus the impregnation of AgNPs directly into the fibers before, after or during the dyeing process, wasn’t only employed in color shading but also did not showed any negative effects on the color fastness. Marija et al. added colloidal AgNPs to the reactive dyeing bath of polyamide and comparable fastness properties were observed (Gorenšek & Recelj, 2009). While color fastness for the Ag-dyed viscose was showed better results than that for cotton fibers dye with direct dye in presence of nanosilver (Chattopadhyay & Patel, 2009). 3.7. Release behavior Due to the strong relationship between Ag release and its biological activity, studying of Ag release profile from the dyed fibers is quite important issue. For examining the effect of dye on the release behavior, the Ag released from AgNPs incorporated fibers was tested in distilled water medium up to 24 h. Four different samples treated with the same Ag salt concentration (200 mg/L) were selected (2, 5, 11 and 17) based on processes sequences and with different Ag contents (0.58–1.63 g/kg). The release profile of Ag from the different samples into distilled water was studied at different durations of 1–24 h. The released Ag was estimated related to fiber weight via detection of Ag concentration in the surrounding using AAS. Data in Fig. 5 showed that a progressive release of Ag ions was detected from fibers and the release profile was obvious affected by the processes sequences. Similar Ag release behavior was appeared when AgNPs incorporated firstly and the dyeing process resulted in decrement of Ag release. The dye molecules could be aided in much stabilization of AgNPs into fibers and consequently decrease its leaching out. The maximum release of Ag was detected (0.31 g/kg for Ag-sample and 0.21 g/kg for Ag-dyed sample) after 3 h contact time only and further increment in time wasn’t resulted in a substantial increasing in Ag release. The lower Ag release reflected the better fastness to wash off and affirmed the good binding between AgNPs and dyed fibers. In case of dyeing firstly (dye-Ag sample) and the concurrent process

Fig. 4. Colorimetric data and dye uptake for treated viscose fibers as function of silver content on fibers. (For interpretation of the references to colour in the text legend, the reader is referred to the web version of this article.)

was characterized with decrement in silver content, which can be explained by the release of Ag in the dye bath during the dyeing. While, dye uptake was enlarged owing to the role of Ag in crosslinking between dye molecules and fibers. Both of Ag contents and dye uptake weren’t influenced significantly when dyeing process performed firstly. The competition between AgNPs and dye molecules to bind with fibers, reflected in the lowering of Ag content and dye uptake by applying the concurrent process of dyeing and AgNPs integration. These results are in harmony and fit well with that illustrated in SEM micrographs and FTIR spectra.

3.6. Color fastness Fig. 5. Release profile of Ag from treated viscose fibers in distilled water.

In dyeing step, the soluble organic molecules or ions (dyes or dye 316

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reduction of microbial pathogens. Regardless to Ag content in fibers and the processes sequences which are both affected on the amount of Ag release into surrounding, the reduction in microbial viability was not frequently influenced attributed to the sufficient amount of Ag released. Therefore, from the data represented in this section, it can be stated that, nanosilver incorporation into was found to act in augmentation of the resistance against microbial attacked the dyed viscose fibers. According to the higher Ag released, better antimicrobial activity than that observed for Ag-viscose fibers was recorded in case of AgNPs impregnated bacterial cellulose (Maneerung et al., 2008) and AgNPs coated cotton fabrics (Ahmed & Emam, 2016) as the bacterial pathogens were fully reduced by incubation for 24 h. At comparable Ag content, Ag-cellulosic materials (fiber/fabric) showed an analogous antimicrobial data (Rehan et al., 2015). Similar antimicrobial results were observed for the reactive dyed polyamide treated with nanosilver (Gorenšek & Recelj, 2009).

of dyeing and AgNPs incorporation (dye/Ag), the release of Ag was extremely high and increased linearly along with the contact time. The maximum release achieved after 24 h, was 1.25 g/kg for dye-Ag samples followed by 0.87 g/kg for dye/Ag sample. Attributed to the lower Ag content in fiber, the dye/Ag samples showed much lower release compared to that for dye-Ag sample. Whatever the same Ag content (1.6–1.63 g/kg), the dye-Ag sample exhibited considerable high silver release compared to Ag-fiber. Dyeing at the beginning resulted in retarding the stabilization of AgNPs onto the fibers via consuming the binding sites of fibers in the bonding with dye molecules. As an analogy with literature regarding to silver release, excessively higher Ag release from AgNPs impregnated bacterial cellulose in water medium than that showed here was estimated (Maneerung et al., 2008). At using similar release experiment for micro-needles Cu2O-viscose fabric (Emam, Ahmed et al., 2017), much higher Ag release recorded here in all tested samples compared to that for Cu attributed to the higher Ag content on fiber.

3.9. Suggested mechanism 3.8. Antimicrobial activity One of the traditional dyes is reactive dyes, which have been represented to possess five different interlocking features assigning different letters including; color molecule, solubilizing groups, bridging groups linking the reactive part of the molecule, reactive groups and leaving groups. Every group has an effect on the physical properties of the total dye molecule such like dye color, ability to diffuse into fibers’ back bone, solubility in dyeing bath, substantively, salt sensitivity and light fastness (Mouxiou et al., 2008). Herein, RB19, as one of reactive dyes, is composed of amino as solubilizing group, anthraquinone as coloring group, eNHe as bridge group between coloring group and reactive group, PheSO2eCH2eCH2+ as reactive group (electrophilic site), and SO3Na as leaving group. Based on the analysis and data performed formerly, the reaction mechanism of the reactive dyeing of viscose fiber, AgNPs incorporation and dyeing in presence of AgNPs could be suggested as presented in Fig. 6 and can summarized in the following points:

The influence of nanosilver incorporation on the biological activity of the dyed fiber was examined by testing the activity of fibers against different pathogenic microbes using the bacterial counting method. Antimicrobial activities of treated specimens were monitored against gram-negative bacteria (E. coli), gram-positive bacteria (S. aureus), fungi (C. albicans) and fungi (S. cerevisiae) and the data were summarized in Table 2. In this test five different samples were selected including the same samples used in release study (2, 5, 11 and 17) and the dyed one (A) based on using of one dye percentage (1%) and one Ag salt concentration (200 mg/L) but with different process sequences. The untreated viscose fibers was used as blank samples and no microbial reduction was observed even after 24 h contact time. The dyed fibers showed a reduction in the different microbial pathogens and the reduction was increased along with the contact time. The reduction viability in bacterial pathogens was much higher than that for fungal pathogens. The activity of dyed fibers against pathogens is attributed to the dye molecules (Lazić et al., 2012). Regardless to the processes sequences, Incorporation of nanosilver was accompanied by extensive enlargement in the microbial reduction. For bacterial pathogens, the viability reduction was enlarged from 33.9–39.3% and 43.2–48.2% to 56.1–74.2% and 80.2–92.4% by AgNPs incorporation after contact time of 4 and 24 h, respectively. Embedding of AgNPs improved the reduction viability in fungal pathogens and the reduction percentage was increased from 10.1% to 67.9% after 24 h contact time. In spite of, the low diminishing in fungal growth detected after AgNPs incorporation, but, it was still substantial results. For all tested samples, the reduction in viable S. cerevisiae fungi was much higher compared to C. albicans fungi. The increment in metal contents, was commonly cooperated in augmentation of antimicrobial activities, as reported in literature (Emam, Saleh et al., 2015, 2016). But herein, the significant difference in silver content wasn’t exhibited apparent difference in the

I The direct embedding of nanosilver within viscose fibers as cellulosic material was previously illustrated in literature (Emam, Rehan et al., 2016; Mowafi et al., 2017; Rehan et al., 2015). Citrate is reduced Ag ions to AgNPs inside fibers matrix and cellulose macromolecules stabilized the nanocluster from further aggregations. II In case of dying: reactive dye is ionized in the presence of sodium carbonate and the leaving group (SO3Na) is eliminated. The reactive group as an electrophilic site is covalently bonded with cellulosic skeleton of fibers to give blue dyed viscose (Tewari and Vishnoi, 2011) and IR spectral data supported this hypothesis. III In case of dyeing of AgNPs-viscose fibers: Some of the impregnated AgNPs are leached out during the dyeing process as silver content decreased after dyeing and the fixed AgNPs is entrapped within intermolecular spaces of cellulosic chains. The dye macromolecules are supposed to chemically interact within nanosilver fibers through electrophilic substitution reaction between reactive group of dye and cellulosic backbone. Additionally, nanosilver may act as a crosslinker between dye molecules and cellulosic fibers. IV In case of AgNPs incorporation into dyed fibers: Citrate firstly acted as nanogenerator to give nanosilver particles and dye molecules could be contributed in the reduction and stabilization of nanosilver via the amino groups. Due to the lower electronegative nitrogen atom in eNHe rather than the oxygen of eOH, AgNPs could be coordinately bonded with the amino groups of dye macromolecules, as this coordination interaction is supposed to be stronger than that with eOH of cellulose. V In case of concurrently process of dyeing and nanosilver incorporation: dye molecules could be shared in the reduction and stabilization of nanosilver. Moreover, a competition between dye

Table 2 Antimicrobial efficiency of the treated viscose fibers. Samples

Ag content (g/ kg)

Bacteria E. coli

Blank A 2 5 11 17

0.0 0.0 1.60 1.00 1.63 0.58

± ± ± ±

0.34 0.03 0.24 0.10

Fungi S. aureus

C. albicans

S. cerevisiae

4h

24 h

4h

24 h

4h

24 h

4h

24 h

0.0 39.3 64.3 60.7 67.5 66.1

0.0 48.2 85.0 82.9 82.1 83.2

0.0 33.9 67.8 74.2 73.3 65.3

0.0 43.2 92.4 86.4 89.0 85.6

0.0 6.7 32.2 23.5 20.8 26.2

0.0 10.1 49.7 37.6 40.3 39.6

0.0 12.0 38.8 26.1 22.6 20.2

0.0 24.4 67.9 51.0 59.8 45.3

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Fig. 6. Proposed reaction mechanism between dye, Ag and viscose fibers; [a] dyeing process, [b] AgNPs incorporation into fibers, [c] AgNPs incorporation into dyed fibers and [d] dyeing of AgNPs incorporated fibers.

molecules and nanosilver particles towards the fibers polymeric macromolecules may be occurred which in turn resulted in the lower silver and dye contents.

with Ag content, whatever the processes sequencing. Regardless to the experimental conditions, color fastness data confirmed that the stability of dye on fibers was not negatively affected by AgNPs incorporation. The contents and release of Ag were both significantly relied on the process sequencing. The release of Ag into water was quite low when AgNPs incorporated firstly and 0.25 g of Ag was released from 1 kg fiber after 24 h. This observation reflects the stabilization effect of dye for AgNPs onto fibers. Antimicrobial efficiency against different pathogens including bacteria and fungi was largely enhanced by AgNPs inclusion. The percentage reduction after 24 h contact time in bacterial and fungal pathogens was 92.4 and 67.9, respectively. The current work introduces significant findings on the attitude of cellulosic fibers coloration during AgNPs insertion directly. This work has an important advantage presented in opening the way widely for applying nanosilver immediately on the textile industry easily to obtain textiles with desirable functions. Additionally, the current study can be extended for protein and synthetic textiles which are supposed to be of great importance in case of their coloration process.

4. Conclusions The influence of immediate AgNPs incorporation on the reactive dyeing of viscose fibers was systematically studied. Effect of Ag content, dye percentage and the sequencing of processes on the color shading, fastness properties and biological activity of fibers were all studied. Sodium citrate was used to generate and incorporate of AgNPs into viscose fibers. Presence of nanosilver into fibers was confirmed by micrographs and EDX analysis. Results of colorimetric data reveal that the fibers color was changed to greenish-blue color after AgNPs inclusion and the greenish color became darker with Ag content lower than 1 g/kg. Absorbance peaks of AgNPs in the yellow range and blue dye were both appeared in the treated fibers, reflecting the appearance of greenish color. Color strength of treated fibers was significantly grown 318

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Fig. 6. (continued)

Compliance with ethical standards

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