AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0021-9 © AUTEX

DEVELOPMENT OF CARBOXYMETHYL CELLULOSE/ POLYPHENOLS GELS FOR TEXTILE APPLICATIONS

Hana Krizova, Jakub Wiener

Technical University of Liberec, Faculty of Textile Engineering, Studentska 2, Liberec 46117, Czech Republic E-mail: [email protected], [email protected]

Abstract:

The aim of this study was to determine release rate and changes in polyphenols’ content, which were sorbed to carboxymethyl cellulose gel and subsequently desorbed. An aqueous extract of blue marc vine variety Fratava was used as a source of polyphenols. The gel was dried into a solid film and polyphenols were then desorbed again by dissolving this film in saline (isotonic) solution. Further, the influence of different times of high temperature (180°C) of drying gel on change in the amount of released polyphenols and also kinetics of their release in re-transfer of the film on the gel and solution was studied. The process simulates the possible use of carboxymethyl cellulose/ polyphenols film sorbed on textile materials and its contact with the tissues and body fluids such as course of wound healing.

Keywords:

Carboxymethyl cellulose, polyphenols, desorption, thermal crosslinking

1. Introduction 1.2.1 Hydrolyzable tannins

1.1 Polyphenols (PF) Their basic monomer unit is gallic or ellagic acid and their molecular weight ranges from 500 to 3000. They are well Polyphenols are a very varied group of chemically diverse soluble in water, hydrolyze due to heat, weak acids or weak compounds that contain hydroxyl groups bound to the bases. They are also easily decomposed by digestive enzymes aromatic ring. They are easily oxidizable substances with a low of mammals. Among these is e.g. oenothein present in the redox potential which are able to reduce some radicals (e.g. wine or tannic (Figure 1) [1] contained in fruits and bark of oak, superoxide, peroxyl and hydroxyl ones) with oxidative effects. chestnut or in leaves of sicilian sumac [1]. Polyphenols are a broad group of plant bioactive substances able to protect cells from oxidative damage due to their strong 1.2.2 Condensed tannins (proanthocyanidins) antioxidant and antiradical activities. PF include for example amino acids (tyrosine), essential oils, phenolic acids (e.g. vanil, Their basic unit of condensed tannins is a monomeric flavan-3-ol gallic, coumaric and ferulic ones), flavonoids (e.g. catechins, (Figure 2) [1], and according to the degree of polymerization quercetin, rutin, anthocyanidins) and tannins. their molecular weight also reaches over 20,000. Condensed tannins contain strong bonds between carbons, and are 1.2 Tannins therefore not easily hydrolyzable and in the tract of mammals hardly decompostable. An example of condensed tannins is Tannins are oligomeric and polymeric polyphenol compounds procyanidin or prodelphinidin. Condensed tannins accumulate contained mainly in the leaves and bark of trees, but also in seeds, herbal stems, tea, oak apples, fruits, vegetables and vine (especially in the red one). Tannins are used to protect plants against pests, parasites and adverse conditions. They are substances with a wide spectrum of biogenic effects. Often it is a bitter substance and adstringens (drugs with astringent effect) inhibiting glandular secretion, act local vasoconstriction and has antidiarrheal effect. Tannins form through their hydroxyl and carboxyl groups complexes with various ingredients – especially with proteins (coagulation proteins which are based on the process of tanning of skin tannins), amino acids and alkaloids. They form complexes with metal ions, carbohydrates and fats. These chemical properties also lead to antimicrobial effects of tannins as complexation of enzymes and ions may subsequently inhibit proliferation of microbes and some molds. Tannins are generally divided into two large groups. Figure 1. Gallic acid and tannic acid. http://www.autexrj.com 33 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0021-9 © AUTEX mainly in vacuoles and in epidermal and subepidermal layer of leaves and fruit. Their richest source is the bark of various trees, especially very hard South American wood quebracho or acacia wood. A higher content of condensed tannins in dark fruits, vegetables (red beans, cocoa beans, blue grapes) relates to the content of anthocyanins, which are also substances of flavonoid nature and have similar synthesis, as well asin seeds, where they are incorporated together with flavonoids into a comprehensive polymer in the ovary that protects the embryo of the plants from drying [1].

1.3 Carboxymethyl cellulose (CMC)

Figure 2. Flavan-3-ol and condensed tannin. Carboxymethyl cellulose is a cellulose derivative whose skeleton consists of glucopyranose polymer, often used as the sodium salt (Figure 3). Some of its hydroxyls are substituted by carboxymethyl groups. CMC is widely used in many industries, especially as a thickener (viscosity change), stabilizer and emulsifier. It is water-soluble, non- toxic, hypoallergenic and shows high swelling. This ballast aditivive is known in the food industry as E466 and it is added e.g. to ice cream, beverages and spreads. CMC stabilizes in acidic dairy products’ milk proteins during pasteurization. In addition to food products CMC is also included in cosmetics, eye drops, lubricants, tablets, coatings etc. The interactions of CMC and polyphenols are currently under study such as Figure 3. Carboxymethyl cellulose. the actual research of biogenic activity of polyphenols [2]. It is for example shown that CMC has from all the food industry tested polysaccharides the highest ability to mask the bitter 2.2 Used methods taste of polyphenols and tannins in beverages enriched with antioxidants so that it reduces their astringent effect on 2.2.1 Extraction of polyphenols the salivary glands [3,4]. CMC is used to stabilize wine by preventing the precipitation of pottasium bitartrate (tartar) Pomace of blue grape vine were after the pressing of macerated and to prevent the formation of sediment in bottled wines [5]. and fermented mash immediately freezed, then dried at 70°C CMC can also be used as a protective layer for encapsulation to a constant weight, and eventually homogenized. 2 g of of polyphenols for oral use as CMC housing protects these crushed dried pomace (mixed peels, seeds and stems with the substances against the effects of digestive enzymes, and weight ratio 15:9:1) were extracted (in a dye cartridge of dyeing in addition these substances are safely transported to the apparatus Ahiba Nuance ECO) with 100 ml of distilled water at place of their maximum resorption in the colon. Only here 100°C for 90 minutes. is the CMC pouch disrupted by the activities of the cellulase enzymes present in intestinal bacteria. CMC is also used 2.2.2 Preparation of CMC gels and films as a carrier for active substances and drugs for surface application. Moreover, CMC is part of dressings for treating 3 g of CMC were dissolved in the extract of pomace by formation particular kinds of wound including a mixture of hydrogels of gel. The gel was homogenized, spilled onto glass plate and and different substances for the stimulation of wound healing. dried at 60°C to film of constant weight. Subsequently, one These substances include enzymatic agents, activated third of the film was crosslinked at 180°C for 1 minute, one third carbon, silver ions or antibiotics [6]. was crosslinked at 180°C for 3 minutes to achieve the partial insolubility and one third stayed non-crosslinked [7].

2. Materials and Methods 2.2.3 Determination of total polyphenols

2.1 Materials The total polyphenol content was measured spectrophotometrically using the Folin-Ciocalteu reagent. This Blue grape pomace of Fratava variety (Lobkowicz castle winery reaction is based on colorimetric redox reaction of phenols Roudnice nad Labem, Ltd.) [8]. To 1 ml of distilled water and 1 ml of Folin-Ciocalteu Gallic acid (monohydrate) (Sigma-Aldrich) reagent (diluted 1:9 with distilled water) was added 200 μl Powdered sodium carboxymethyl cellulose, medium viscosity, of skimmed sample (60 revolutions/minute for 3 minutes). molecular weight 250 000 (Fluka) 1 ml 0.75 M solution of anhydrous sodium carbonate was Folin-Ciocalteau reagent (Penta Chrudim) added after 5 minutes. Parallelly, a control sample (a blank Anhydrous sodium carbonate (Lachema) and NaCl p.a. (Lach-Ner) one) was also prepared containing 200 μl of distilled water, http://www.autexrj.com 34 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0021-9 © AUTEX and calibration series of solutions of gallic acid (GA) with crosslinking of CMC occurs resulting in less swelling of CMC. increasing concentrations from 0.01 to 0.06 mg/ml (Figure 4). This shortens the diffusion path of substances’ molecules The presence of polyphenols causes after 50 minutes a which are in the closed path (CMC is inert and does not react chemical reaction accompanied by a visual color change of the chemically with PF – it is only a mechanical sorption) and PF solution from yellow to blue. Afterwards, the absorbance was can thus quickly desorb to the place of lower concentration). measured by the means of UV/VIS spectrophotometer (Helios Second, it is expected that a thermal hydrolysis of polymeric epsilon) in the absorption maximum at 765 nm. The resulting polyphenols (tannins) occur so that smaller PF molecules can concentrations of samples (extracts prior to sorption into CMC again rapidly diffuse from the gel to the solution. The problem gel and after the desorption of CMC) were calculated on the is a total thermolability of PF, wherein at 180°C their content is basis of calibration curve of gallic acid and expressed in mg declining rapidly; that is why it is important to choose a time- GA/ml of solution, respectively in g/liter. temperature compromise, where their content is still maintained and at the same time their optimum release is under way. 2.2.4 Desorption of polyphenols Figure 7 shows a percentage expression of decrease of 0.5 g of each of CMC/PF film was immersed in 80 ml saline polyphenols and also percentage expression of decrease of (0.9% NaCl) and dissolved using a magnetic stirrer at 37°C. half-time speed of their release from CMC, depending on the A sample was collected each time for the spectrophotometric determination of polyphenols (at intervals 5, 10, 15, 30, 45 and 60 minutes) to ascertain the kinetics of release of polyphenols from CMC/PF gels. The process simulates the contact with the tissues and body fluids such as the course of wound healing.

3. Experimental Details

3.1 Content of PF The measured content of polyphenols in the extract was about 0,5 g of PF/liter (respectively gallic acid equivalent), which is 2,5% of the weight of the dried pomace. The theoretical content in 100 ml of extract would be therefore 50 mg of PF. After adding of 3 g of CMC, drying, removing 0,5 g sample and dissolving Figure 4. Spectrophotometric calibration of gallic acid. in 80 ml of saline, each solution should include ideally about 0,1 mg of PF/ ml of saline. However, it is necessary to take into account that the CMC hygroscopic powder contained 5 wt.% water and in 100 ml of extract was present (in addition to 50 mg of PF) about 0,5 g of the dry matter (e.g. dissolved sugars and minerals), and the real content of PF must be less than the theoretical one (Table 1).

3.2 Release of PF from CMC/PF films

Figure 5 shows the release of PF from CMC/PF films in saline at 37°C using the magnetic stirrer, for 1 hour. The increasing content of PF was measured in the centrifuged samples which were collected at intervals of 5, 10, 15, 30, 45 and 60 minutes. All samples were measured in triplicate and the averages were calculated.

Figure 6 indicates that with the increasing degree of crosslinking of CMC, the half-time release of polyphenols from CMC Figure 5. Release of PF from CMC films: non-crosslinked and partially film decreases. This leads to two outcomes: first, a thermal thermal crosslinked CMC.

Table 1. PF content in the samples due to the dry matter.

Total dry matter (dry Content of PF in 0,5 g PF concentration of the Content of CMC matter+CMC+PF) samples resulting 80 ml saline

3 g 3,40 g 7,35 mg 0,092 mg/ml http://www.autexrj.com 35 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0021-9 © AUTEX

Figure 6. Half time of release of PF from CMC, depending of the Figure 7. Decrease of PF content and of their half-time release degree of crosslinking. depending time of crosslinking at 180°C. time of thermal crosslinking. It is obvious that, for example, a References distance between the two curves is the largest after 1 min. of crosslinking. At this point the release of PF is already short [1] Schofield, P., Mbugua, D.M., Pell, A.N.: Analysis of enough while maintaining a high content of PF. condensed tannins: a review. Animal Feed Science and Technology 91 (2001), p.21-40 [2] Serrano-Cruz, M.R. et al.: Controlled release and 4. Conclusion antioxidant activity of Roselle (Hibiscus sabdariffa L.) extract encapsulated in mixtures of carboxymethyl cellulose, whey protein, and pectin. Food Science and This research was aimed at the kinetics of release of Technology 50/2 (2013), p. 554-561 polyphenols from carboxymethyl cellulose film which was thermal crosslinked at 180°C for 1 and 3 minutes and the [3] Troszyńska,A. et al.:The effect of polysaccharides on the astringency induced by phenolic compounds. Food Quality results were compared with the completely soluble non- and Preference 21 (2010), p.463–469 crosslinked CMC. Thermolabile PF are partially protected by CMC and the short high temperatures decreased their content [4] Smith A., K., June, H., Noble, A.C.: Effects of viscosity on the bitterness and astringency of grape seed tannin. Food to 85% of the initial content (and to 70% respectively). After Quality and Preference 7 (1996), p.161-166 one hour in saline, the CMC/PF gels were dissolved in 92, 36 and 24%. Depending on the degree of crosslinking, the rate of [5] Bosso, A. et al.:Carboxymethylcellulose for the tartaric stabilization of white wines, in comparison with other release increased because partial crosslinking of CMC reduces oenological additives. Vitis 49/2 (2010), p.95–99 its swelling, reducing the diffusion path. [6] Skórkowska-Telichowska, K. et al.: The local treatment and available dressings designed for chronic wounds. Measurement results show that CMC can be used as a carrier Journal of the American Academy of Dermatology (2011), of polyphenols and their release can be influenced by degree In press of crosslinking and solubility of CMC. [7] Borůvková, K., Wiener, J., Kukreja, S.: Thermal self cross- linking of carboxymethylcellulose. ACC Journal XVIII/1 (2012), pp. 6-13 Acknowledgment [8] Singleton V.L., Orthofer R., Lamuela-Raventós R.M.: Analysis of total phenols and other oxidation substrates The paper has been supported by the grant project SGS 48008 and antioxidants by means of folin-ciocalteu reagent. (provided by Faculty of Textile of Technical University of Liberec) Methods in Enzymology 299, 1999, p.152-178 and TACR program ALFA TA01010244 (Czech republic).

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A NEW METHOD OF DETERMINATION OF COLLAGEN CONJUGATED WITH KERATIN

Marta Safandowska, Krystyna Pietrucha

Department of Material and Commodity Sciences and Textile Metrology, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland E-mail: [email protected]

Abstract:

The paper describes the possibility of using Sirius red dye for the determination of collagen conjugated with keratin of wool. Sirius red assay was shown to be feasible for collagen detection, which was enzymatically coupled onto wool fibers and woven fabric. The effectiveness of combination of keratin protein with collagen was evaluated .

Keywords:

Collagen, Sirius red, keratin

1. Introduction detection of collagen on keratin substrates has not been reported previously. The capability of tyrosinase to catalyze Collagen is the major component of the extracellular matrix the oxidation of tyrosine residues of keratin and for coating (ECM) and is the most abundant mammalian protein collagen on wool materials has to be assessed. accounting for about 20–30% of the total body proteins. The unique biocompatibility due to its biological characteristics, such as biodegradability and weak antigenicity, made collagen 2. Materials and methods the primary resource in medical applications [1]. Collagen can also be used to modify the surface of various types of synthetic 2.1. Materials polymers. For example, coating polypropylene meshes with collagen results in their improved bio- and cytocompatibility; Wool fibers and woven fabric (twill weave) were chosen for modification of polyester vascular prosthesis by collagen preparation of the samples. Fibers from sheep wool was increases their leak-proof properties [2-4]. Furthermore, cleaned by Soxhlet extraction using dichloromethane to collagen displayed bacteriostatic properties against remove fatty matters (t=14 h, 6 transfers to 1 h). Collagen type Staphylococcus epidermidis and b-hemolytic Streptococcus I was prepared from fresh skin of silver carp and supplied by [5], and therefore it can impart antibacterial properties to AAG Sp. z o.o. (Poland). natural textile fibers [6]. Tyrosinase from mushroom (EC 1.14.18.1, ≥1000 unit/mg A multitude of applications of collagen indicates that it is solid) and Sirius red F3BA were purchased from Sigma–Aldrich very appropriate to use a rapid and precise method for its (Sigma, St. Louis, MO, USA). All other chemicals of analytical determination. Many physicochemical methods, such as grade were obtained from POCh–Gliwice (Poland). X-ray photoelectron spectroscopy (XPS), chromogenic reactions (hydroxyproline assay, amine dyes: ninhydrin or 2.2. Preparation of samples Rhodamine B isothiocyanate), molecular weight comparisons (gel electrophoresis, chromatography), radioactive procedures Samples of wool fibers and fabric were modified with enzyme (radioactive labeling of proline) and immunological reactions and collagen in accordance with a method [6]. For this purpose, (enzymeimmunoassays using specific antibodies) are used to 0.5 g wool was placed in 50 ml 0.1 M phosphate buffer (pH=6.5) estimate the amount of collagen [2,3]. The most precise and containing tyrosinase (2000 U/g). In addition, ascorbic acid specific method of collagen determination is based on the solution at 0.42 mg/ml was added. After 1 h, collagen solution in quantitation of its hydroxyproline content; unfortunately, it is 1% CH3COOH was added to the buffer/wool incubation mixture a complex and time consuming procedure. Sirius red staining in a final concentration of 2 mg/ml. Incubation was continued at seems to be an excellent alternative technique for quantitative 25 °C for 24 h. To terminate the enzymatic reaction, the pH was or qualitative measurement of collagen. It is a fast and non- raised to pH 9 using 0.1M KOH. Then, the sample was rinsed in destructive method, which has been used for histological distilled water and 1% CH3COOH, and air-dried. staining of collagen in tissue sections from many years [7]. 2.3. Characterization of the products The goal of this study is to elaborate a simple and accurate method of collagen examination. In this work, the method of Color measurements. In order to determine the enzyme- Sirius red staining was applied to assay collagen conjugated catalytic modification effect on the wool-derived keratin, the with keratin of wool. The application of Sirius red dye for the reflectance measurements were evaluated by using Datacolor http://www.autexrj.com 37 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0024-6 © AUTEX

Int. PAGE: Spectraflash 2 500 spectrophotometer with dataMaster to the corresponding quinones, which possess fluorescence software.COLUMN: Results left were expressed by the CIE whiteness (W) properties [8]. These o-quinones may either condense with LINE: 6, 7, 8 according to the ISO 105-J02:1999 method and CIELab color each other or react with free amino groups, resulting in the IS: values and color difference (ΔE) at D65/10º. The degree of formation of covalent keratin-collagen crosslinks (Figure 2) SHOULD BE: The quality of equation 1 in the proof is too poor, so please replace it with this, which I PAGE: 2 whitenesspresent (W) below: was calculated using the following equation: [8,9]. COLUMN: left LINE: 6, 7, 8 (1) IS: PAGE: 2 SHOULD BE: The quality of equation 1 in the proof is too poor, so please replace it with this, which I where:COLUMN: left 20 present below: W is theLINE: whiteness; 18, 19, 20 Y the trichromatic component of the sample; x, y theIS: chromaticity coordinates of the samples, 0.3138 and 0.3310SHOULD the chromaticity BE: The quality coordinatesof equation 2 in x the and proof y respectively is too poor, so forplease the replace it with15 this, which I PAGE: 2 perfectpresent light below: scattered. COLUMN: left 10 LINE: 18, 19, 20 The color difference - ΔE - was calculated according to the W-CIE D65/10 IS: SHOULD BE: The qualityformula of equation of Commission 2 in the proof Internationale is too poor, so please de l’Eclairage replace it with – this,CIE which Lab I 5 present below: in relation to an unmodified sample: PAGE: 2 WOOL/TYROSINASE/COLLAGEN UNTREATED WOOL COLUMN: right WOOL/TYROSINASE (2) 0 LINE: 15 wool fabric IS: Figure 4 A, B, D wool fibres where:SHOULD BE: Figure 3 A, B, D, E PAGE: 2 ΔE is the color difference expressed in CIELab units; ΔL the Figure 1. CIE whitenessFigure of1. samplesCIE whiteness of wool of-derived samples keratin. of wool-derived keratin. COLUMN: right difference in lightness; Δa the difference in the chromaticity LINE: 15 coordinate, green/red axis; Δb the difference in the chromaticity IS: Figure 4 A, B, D In addition, the quality of figures which have been submitted is too poor, so please replace them to coordinate, blue/yellow axis. As can be seen from Table 1 the enzyme treatment also had a SHOULD BE: Figure 3 A, thoseB, D, E that, which I present below: slight impact on the color difference (ΔE) and color depth (K/S). Sirius red staining. The presence of collagen onto the surface In addition, the qualitylayer of figures of wool-derived which have been keratin submitted was is too poor, evaluated so please byreplace staining them to The presence of collagen on surfaces of wool was confirmed those that, which withI present Sirius below: red F3BA dye, in accordance with the procedure by using the staining of collagen with Sirius red F3BA. As described by [7]. Tyrosinase-treated sample in the presence can be seen from the pictures (Figure 3), all samples are and absence of collagen were incubated with water solution of stained; however, only those wool samples which have been 0.5% Sirius red at room temperature for 30 minutes. Thereafter, enzymatically treated and simultaneously coated with collagen the samples were washed extensively for 30 minutes in distilled were characterized by a higher intensity of staining. The water, and air-dried. The color measurements were made by uncoated samples of keratin (Figure 3 A, B, D, E) did not bind sensory impairments. Figure 3. Surfacethe images Sirius of wooldye andfibers gave (A, B, only C) and a weakwoven background. fabric (D, E, F) stained with Sirius red (A, D) before enzyme treatment, (B, E) after tyrosinase treatment, (C, F) after tyrosinase treatment and simultaneousTable 1. CIELLAB coating colorwith collagen.difference (ΔE) and color depth (K/S) of wool 3. Results samples. PAGE: 2 As revealed in Figure 1, the CIE whiteness (W-CIE D65/10) Samples ΔE K/S of keratin samples (wool fibers and woven fabric)Proponuję treated przenieśćby akapit z kolumny lewej (line: 47-50) do kolumny prawej, tak aby kolumna prawa Wool fibers - 0,4976 tyrosinase in comparison with untreated samples increasedwyglądała by następująco: 15% and 4%, respectively. The increase in whiteness was also Wool woven fabric - 0,5058 observed for the samples which were subjected Line: to enzyme 1-8: Enzyme-treated fibers 1,58 0,4613 treatment and simultaneous coating with collagen. The increase in the value of whiteness may be related to the Enzyme-treated fabricfact that tyrosine 0,67 residues of0,4879 keratin under reducing The increase in the value of whiteness may be related to Enzyme/collagen-treatedconditions fibres and under1,98 the influence0,4543 of the enzyme are the fact that the tyrosine residues of keratin under reducing oxidized to the corresponding quinones, which possess conditions and under the influence of the enzyme are oxidized Enzyme/collagen-treated fabric 1,24 0,4756

collagen- NH OH 1/2 O2 O 2 OH O OH

tyrosinase N H keratin keratin collagen keratin Figure 2. Tyrosinase-catalyzed oxidation of tyrosine and subsequent nonenzymatic reactions of the quinone with collagen.

http://www.autexrj.com 38 20

15

10 W-CIE D65/10

5 WOOL/TYROSINASE/COLLAGEN UNTREATED WOOL WOOL/TYROSINASE 0 wool fabric wool fibres

AUTEXFigure Research 1. Journal, CIE whiteness Vol. 13, No 2, Juneof samples 2013, DOI: 10.2478/v10304-012-0024-6of wool-derived keratin. © AUTEX

Figure 3. Surface images of wool fibers (A,B,C) and woven fabric (D,E,F) stained with Sirius red (A, D) before enzyme treatment, (B, E) after Figuretyrosinase 3. Surface treatment, images (C, F) of after wool tyrosinase fibers treatment(A, B, C) andand simultaneous woven fabric coating (D, with E, F) collagen. stained with Sirius red (A, D) before enzyme treatment, (B, E) after tyrosinase treatment, (C, F) after tyrosinase treatment 4. Conclusionsand simultaneous coating with collagen. cytocompatibility of human endothelial cells, Biomacromolecules 2, 1312-1319, 2002. The PAGE:obtained 2 results demonstrate that Sirius red staining is a [3] Jou C.H.; Lin S.M.; Yun L.; Hwang M.C.; Yu D.G.; Chou specific and simple method for the determination of collagen W.L.; Lee J.S.; Yang M.C.: Biofunctional properties of coated onto wool-derived keratin. Reflectance measurements Proponuję przenieść akapit z kolumny lewej (line: 47-50) dopolyester kolumny fibresprawej, graftedtak aby kolumna with chitosan prawa and collagen, showed that the whiteness of the wool samples after enzyme Polymers for Advanced Technology 18, 235–239, 2007. treatmentwyglądała increases, następująco: which means that tyrosinase activates [4] Pietrucha K., New collagen implant as dural substitute, the tyrosine residues in keratin to the quinone forms, which Biomaterials 12, 320-323, 1991. reactLine: further 1- 8: nonenzymatically with primary amino groups of [5] Carlson G. A., Dragoo J. L., Samimi B., Bruckner D. A., collagen. The increase in Bernardthe value G. of W., whiteness Hedrick M.,may Benhaim be related P., Bacteriostaticto the fact that tyrosineproperties residues of biomatrices of keratin against under common reducing orthopaedic pathogens, Biochemical and biophysical Research Acknowledgment conditions and Communications under the influence 321, 472-478, of the2004. enzyme are oxidized to [6] the Jus corresponding S.; Kokol V.; Guebitz quinones, G.M.: which Tyrosinase-Catalysed possess The work was partially supported by the National Science coating of wool fibers different protein-based biomaterials, Centre via Grant No. DEC-2011/03/B/ST8/05867. Journal of Biomaterials Science 20, 253-269, 2009. [7] Junquiera L.C.U.; Bignolas G.; Brentani R.R.: A simple References and sensitive method for the quantitative estimation of collagen, Analytical Biochemistry 94, 96-99, 1979. [1] Lee C.H., Singla A., Lee Y., Biomedical applications of [8] Jus S.: Kokol V.; Guebitz G.M.: Tyrosinase-catalysed collagen, International Journal of Pharmaceutics 221, coupling of functional molecules onto protein fibres, 1–22, 2001. Enzyme and Microbial Technology 42, 535-542, 2008. [2] Zhu Y.; Gao C.; Liu X., Shen J.: Surface modification [9] Thalmann C.R., Lotzbeyer T., Enzymatic cross-linking of proteins of polycaprolactone membrane via aminolysis and with tyrosinase, EUR Food Res Technol 214, 276-281, 2002. biomacromolecule immobilization for promoting

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USE OF SHORT FIBERS AS A FILLER IN RUBBER COMPOUNDS

Natalia Meissner1, Władysław M. Rzymski2

1Lodz University of Technology, Faculty of Material Technologies and Textile Design, Department of Material and Commodity Sciences and Textile Metrology 2Lodz University of Technology, Faculty of Chemistry, Institute of Polymer and Dye Technology E-mail: [email protected], [email protected]

Abstract:

In this work, composites made from styrene-butadiene rubber and short fibers were prepared by mixing and investigated. The influence on the vulcanization process and tensile strength properties has been studied and compared with compounds filled with carbon black. The presence of fibers gave shorter curing time and led to a slight increase in tensile strength but decreased the elongation at break of the compound.

Keywords:

Styrene-butadiene rubber (SBR), fibers, composites, reinforcement, mechanical properties.

1. Introduction fibers can be added to rubber to improve or modify certain properties, such as green strength, creep resistance, hardness, Styrene-butadiene rubbers (SBR) are the most commonly used aging resistance, dynamic mechanical properties, dimensional synthetic rubbers today. They are produced by copolymerization stability during fabrication, and real-time service, and to reduce of butadiene and styrene. The majority of conventional fillers the cost of fabricated articles. It is well known that blending used in rubber industries are silica and carbon black because of two or more fibers or/and fillers gives the potential for of their relatively high reinforcing efficacy. Generally, a silica- preparing new materials with specific and improved properties reinforced rubber shows a similar tensile strength to one [16]. Recently, studies of the synergistic effects of short reinforced with carbon black, but the modulus is relatively lower fibers and particulate fillers compounded with miscellaneous [1]. Currently, the necessity for reinforcing fillers from renewable polymeric matrices on the physicomechanical properties of resources, such as plant-based natural fibers, for the production hybrid composites have been reported [17,18]. These studies of biosustainable composite materials is increasing in research showed promising results, in which the improvement of specific areas and manufacturing because of their ease of processing, properties was observed together with additional environmental low cost, low density, biodegradability, and good mechanical and cost benefits. Therefore, it is expected that the combined properties. Fillers exist in a variety of systems, including use of both short natural fibers and silica will enable one to biological, organic, and polymeric materials [2,3]. In polymer connect the beneficial effects of individual reinforcement for the systems, fillers not only reduce the cost of the compound but development of materials with desirable properties. In expedient also improve the mechanical and dynamic properties of the applications, such as for automobile tires, the combined use of material. Fiber-reinforced polymer composites are now used natural fibers and silica has been applied widely to improve as alternative low cost materials for structural and nonstructural processability, dimensional stability, and mechanical balance applications, such as automotive applications, packaging, between abrasion resistance and rolling characteristics [19,20]. building products, furniture, and consumer goods. In the past, a Tire-tread compounds containing short natural fibers together diversity of short fibers was merged into natural rubber, and their with silica are used to enhance ice traction for icy roads [21]. In reinforcement was discussed [4-9]. It was found that they did not this study, the primary objective was to examine the effect of the provide a similar level of reinforcement compared to carbon black ratio of short fibers on the curing/rheological characteristic and and silica. That is, the tensile strength and elongation at break tensile properties of styrene-butadiene rubber. of natural rubber based composites substantially decreased with the addition of fibers. In many cases, the loading of fibers that gave optimal fiber orientation and acceptable mechanical 2. Experimental properties was found to be 20-30 phr [5,7,8]. Many authors have shown the effect of fiber surface modifications, using bonding 2.1 Materials agents, NaOH treatment, acetylation, and mercerization on the interfacial adhesion of natural fiber and rubber matrix [10-15]. KER 1500, styrene-butadiene rubber (SBR), bound styrene The authors also analyzed the dynamic mechanical behavior of content 23, 5 %, was obtained from Synthos S.A. (Oświęcim, natural-fiber-reinforced rubber and curing characteristics of the Poland). Short fibers were obtained from Z. W. Biliński Sp. J. compounds. They found that composite performance can be (Konstantynów Łódzki, Poland). These fibers are very short enhanced by chemically treating the fibers. Moreover, natural (less than 1 cm long). The rubber compounding ingredients, http://www.autexrj.com 40 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0025-5 © AUTEX including zinc oxide (ZnO; SlovZink, a.s., Slovakia), stearic 2.5 Mechanical measurement acid (AarhusKarlshamn, Sweden), sulfur (POCH, Poland), carbon black (IRB-7), N-tert-butyl-2-benzothiazyl sulfonamide The tensile testing was performed on a testing machine (TBBS; Lanxess, Germany) were commercial grade. (ZWICK Z005 TH All-round-Line) according to ASTM D 412. The dumbbell-shaped test specimens were cut from vulcanized 2.2 Preparation of the composites rubbers. The specimens were stretched at room temperature (25 ± 2 °C). The average tensile properties for each composite The compounding of the styrene-butadiene rubber, carbon were determined from five specimens. Hardness (Shore A) of black, fibers, and rubber additives was carried out with a the samples was also measured. laboratory two-roll mill at room temperature. The formulation of hybrid composites is given in Table 1. The rubber was first masticated on the mill, and the compounding ingredients were 3. Results and discussion added in the following order: sulfur, stearic acid, fillers (carbon black or fibers), ZnO and TBBS. The loading ratio of fibers and 3.1 Processing properties carbon black was varied keeping the contents of the remaining components constant. The cure characteristic and Mooney viscosity [ML (1+4), 100°C] of the composites were determined as a function of 2.3 RPA measurement the fibers and the carbon black content. The results are given

in Table 2. Minimum torque (ML) obtained from RPA testing is The cure characteristics of the rubber compounds were normally related to the viscosity of a rubber compound. The measured on a Rotorless Shear Rheometer (RPA; Rubber ML value of fiber-filled compounds was higher than that of the Process Analyzer RPA2000, Alpha Technologies). The carbon black-filled compounds and that of the control sample. measurement was according to ASTM D 6204 at 160 °C. The presence of fibers increases the viscosity of the mixes. The increment in torque values with increasing filler loading 2.4 Mooney viscosity [ML (1+4), 100 °C] measurement indicates that as more and more filler incorporated into the rubber matrix, the mobility of the macromolecular chains of the The Mooney viscosity of the rubber compounds was rubber decreases resulting in more rigid vulcanizate. It is seen measured with Mooney viscometer (Mooney MV2000, Alpha that the mix containing fillers provides a higher torque value Technologies) according to the testing procedure described in indicating higher crosslinking. From Table 2 it is observed that ASTM D 1646. The Mooney viscosity was recorded after the the optimum cure time slightly decreases with the increase sample was preheated for 1 min with total testing time of 4 min. of fiber loading and the change in scorch time is also slight. The test temperature was set at 100 °C. In case of carbon black, optimum cure time and the scorch time decreases with increase of filler loading. In both cases the

Table 1. Formulation of styrene-butadiene rubber composites.

Ingredient Parts per hundred rubber (phr) A 1CB 2CB 3CB 1SF 2SF 3SF SBR 100 100 100 100 100 100 100 Sulfur 1.75 1.75 1.75 1.75 1.75 1.75 1.75 Stearic acid 1 1 1 1 1 1 1 TBBS 1 1 1 1 1 1 1 ZnO 3 3 3 3 3 3 3 Carbon black - 10 20 30 - - - Short fibers - - - - 10 20 30

Table 2. Effect of various filler content on the cure characteristics and Mooney viscosity of styrene-butadiene rubber composites.

Sample ML MH Ts2 Tc90 Cure rate ML(1+4) (dN m) (dN m) (min) (min) (dN m min-1) 100 °C A 0.60 7.64 11.3 19.2 0.18 34.4 1CB 0.71 9.60 7.0 14.7 0.32 38.1 2CB 0.97 12.01 6.0 12.7 0.36 43.7 3CB 1.29 14.51 5.2 11.9 0.61 50.5 1SF 0.93 10.69 8.7 16.4 0.31 39.6 2SF 1.3 13.98 7.9 16.7 0.20 48.1 3SF 1.84 18.71 7.3 15.1 0.46 57.6 http://www.autexrj.com 41 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0025-5 © AUTEX optimum cure time, as well as the scorch time, have decreased reinforced fiber composite is subjected to load, the fibers act compared to the control formulation. The reason behind the as carriers of load and stress is transferred from matrix along increase in curing rate of the filled compounds over the control the fibers leading to effective and uniform stress distribution. compound can be mostly attributed to the influence of pH of the The uniform distribution of stress is dependent on two factors, fillers. The pH of carbon black is about 10, and the pH of the the population and orientation of fibers. At high fiber loadings, fibers is about 9. It is known that additives having alkaline pH tear strength is found to decrease as the increased strain in promote vulcanization by sulfur, accelerator and accelerator the matrix between closely packed fibers increases tearing and activator [22,23]. Crosslink formation between rubber chains reduces the tear strength. The value of elongation at break occurs by sequences of reactions involving sulfur, accelerator shows a reduction with increasing fiber loading. Increased and accelerator activator, which form an active sulfurating fiber loading in the rubber matrix resulted in the composite complex [24]. The concentration effect of the curatives in becoming stiffer and harder. This will reduce the composite’s the filled compounds may be an additional reason for higher resilience and toughness and lead to lower elongation at break. curing rate of mixes. From Table 2 it is found that the optimum cure time is higher for fiber-filled composites than that for carbon black-filled composites. This is due to the fact that with 4. Conclusions increasing size of filler, incorporation and dispersion become difficult. Therefore, compounded rubbers become stiff and The obtained results show that short fibers can be used as extent of cure value increases. The Mooney viscosity, taken as interesting modifier of rubber blends, but for their application a measure of rubber compound viscosity, for the composites some specific aspects must be considered. The presence showed an increase with increasing both short fibers and of fibers in compounds has advantageous influence on carbon black. the vulcanization process and on formation of cross links in the elastomeric matrix. Therefore for the application of 3.2 Tensile properties short fibers it is necessary to modify also the composition of the vulcanization system to ensure optimal vulcanization In the present study the behavior of composites containing parameters. The nature of the elastomeric matrix must be fibers and carbon black were analyzed. The tensile properties taken in to account as well. The mechanical properties of the and hardness value of rubber compounds containing various composites with carbon black are superior to those with fibers. amounts of fillers are shown in Table 3. From the data in Table 3 Addition of short fibers (in compare with reference sample) it is seen that with an increase in the proportion of carbon led to slight increase of tensile strength but decreased the black loading, the 100%, 200% and 300% moduli increase in elongation at break of the compound. Addition of fibers also the case of carbon black-rubber composites. It is known for a leads to increase in hardness and stiffness of the compounds. very long time that carbon black is enhancing the mechanical The use of silica and carbon black combined with different properties of rubber compounds. fiber sizes to reinforce the hybrid rubber composite will be the subject of future investigations. The data in Table 3 show that the elongation at break increases when the carbon black loading is increased. It is known that mechanical properties of short fiber reinforced rubber Acknowledgements composites depends on several factors such as structural aspect ratio and orientation of fibers in the final part, the degree Financial support for this research was provided by Synthos of interfacial bonding between fiber and rubber matrices, the S.A., Oświęcim, Poland. The authors greatly appreciated the proper dispersion of fibers, and a balanced processability/ experimental support from Mr. A. Carr and Mr. P. Kwaczała at stiffness/ flexibility relationship for the products [25]. When the Synthos S.A.

Table 3. Tensile properties of fiber and carbon black reinforced styrene-butadiene rubber compounds.

Mechanical properties A 1CB 2CB 3CB 1WF 2WF 3WF 100% Modulus (MPa) 0.81 1.04 1.43 1.9 1.93 - - 200% Modulus (MPa) 1.16 1.71 3.02 5.0 2.03 - - 300% Modulus (MPa) 1.57 3.03 6.13 10.1 - - - Tensile strength (MPa) 1.82 5.85 16.8 22.0 2.07 2.85 2.96 Elongation at break (%) 345 408 496 480 240 87 69 Hardness, Shore A 40.9 46.2 51.4 57.0 55.3 65.2 75.1

References [2] Zhang Y. et al., Effect of Carbon Black and Silica Fillers in Elastomer Blends, Macromolecules, 34, 2001, 7056-7065. [1] Hashim A.S. et al., Silica reinforcement of epoxidized [3] Kalaprasad G.N. et al., Crab Shell Chitin Whisker Reinforced natural rubber by the sol-gel method. Journal of Sol-Gel Natural Rubber Nanocomposites. 1. Processing and Science and Technology, 5, 1995, 211-218. Swelling Behavior, Biomacromolecules, 4, 2003, 657-665. http://www.autexrj.com 42 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0025-5 © AUTEX

[4] De D. et al., The effect of grass fiber filler on curing [14] De D. et al., Curing Characteristics and Mechanical characteristics and mechanical properties of natural Properties of Alkali-Treated Grass-Fiber-Filled Natural rubber, Polymer for Advances Technologies, 15, 2004, Rubber Composites and Effects of Bonding Agent, Journal 708-715. of Applied Polymer Science, 101, 2006, 3151-3160. [5] Geethamma V.G. et al., Composite of short coir fibres and [15] Mohan T.P. et al., Chemical treatment of sisal fiber using natural rubber: effect of chemical modification, loading and alkali and clay method, Composites Part A, 43, 2012, orientation of fibre; Polymer, 39, 1998, 1483-1491. 1989-1998. [6] Hanafi I. et al., Oil palm wood flour reinforced epoxidized [16] Mishraa S. et al., Studies on mechanical performance natural rubber composites: The effect of filler content and of biofibre/glass reinforced polyester hybrid composites, size, European Polymer Journal, 33, 1997, 1627-1632. Composites Science and Technology, 63, 2003, 1377- [7] Maya J. et al., Mechanical properties of sisal/oil palm hybrid 1385. fiber reinforced natural rubber composites, Composites [17] Haqa M. et al., Hybrid bio-based composites from blends Science and Technology, 64, 2004, 955-965. of unsaturated polyester and soybean oil reinforced with [8] Lopattananon N. et al., Performance of pineapple leaf nanoclay and natural fibers, Composites Science and fiber-natural rubber composites: The effect of fiber surface Technology, 68, 2008, 3344-3351. treatments, Journal of Applied Polymer Science, 102, [18] Hudaa M.S. et al., The effect of silane treated- and 2006, 1974-1984. untreated-talc on the mechanical and physico-mechanical [9] Zhang W. et al., Mechanochemical preparation of surface- properties of poly(lactic acid)/newspaper fibers/talc hybrid acetylated cellulose powder to enhance mechanical composites, Composites Part B: Engineering, 38, 2007, properties of cellulose-filler-reinforced NR vulcanizates, 367-379. Composites Science and Technology, 68, 2008, 2479-2484. [19] Kikuchi N., Composition for tread rubber of tires, U.S. [10] Lovely M. et al., Mechanical Properties of Short-Isora- Patent 5852097, 1998. Fiber-Reinforced Natural Rubber Composites: Effect of [20] Takase K. Rubber composition for pneumatic tire, Fiber Length, Orientation, and Loading; Alkali Treatment; Japanese Patent JP2006282790, 2006. and Bonding Agent; Journal of Applied Polymer Science, [21] Agostini L.D. et al., Tire tread for ice traction, U.S. Patent 103, 2007, 1640-1650. 5967211, 1999. [11] Martins M.A. et al., Tire Rubber-Sisal Composites: Effect of [22] Schmidt A.X. et al., Principles of High Polymer Theory and Mercerization and Acetylation on Reinforcement, Journal Practice: Fibers, Plastics, Rubbers, Coatings, Adhesives, of Applied Polymer Science, 89, 2003, 2507-2515. Mc Graw Hill, 1948. [12] Hanafi I. et al, Bamboo fibre filled natural rubber [23] Hofmann W., Rubber Technology Handbook, Hanser composites: the effect of filler loading and bonding agent, Publishers, 1989. Polymer Testing, 21, 2002, 139-144. [24] Eirich FR., Science and Technology of Rubber, Academic [13] Hanafi I. et al., The effects of a silane coupling agent Press, 1978. on curing characteristics and mechanical properties of bamboo fibre filled natural rubber composites, European [25] Goettler L.A. et al., Short Fiber Reinforced Elastomers, Polymer Journal, 38, 2002, 39-47. Rubber Chemistry and Technology, 56, 1983, 619-638.

http://www.autexrj.com 43 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0022-8 © AUTEX

MATHEMATICAL MODELING OF THE SYSTEM SHEDDING MOTION – HEALD – WARP

Martin Bílek, Josef Skřivánek

Department of Textile Machine Design of Technical University of Liberec, Studentská 2, Czech Republic E-mail: [email protected], [email protected]

Abstract:

The paper is concerned with the description of a mathematical model meant for an analysis of the movement of healds during the weaving cycle. The referred model consists of a mathematical description of shedding motion, coupled with the solution of the heald model of a weaving loom. Principal designing elements of this component have been considered while devising this model. The affected calculations show a high value of acceleration of the heald produced after its drop upon the supporting wire. The referred model allows for analyzing a considerable part of designs of heald shaft that are employed in weaving looms nowadays.

Keywords:

Weaving loom, heald, mathematical model, analysis

1. Introduction quantities on individual elements of mechanism that depend on mass parameters (rigidity, moment of inertia, mass) and on In general, the shedding mechanism can be classified into two clearances in kinematic pairs of the mechanism (Figure 1). sections: the driving section and the transforming section. The transforming section of the shedding mechanism consists of This system is a complicated one as for the number of joint mechanisms usually, which convert the rotational motion elements and the kinematic pairs. Mathematical model of the of the driving section into a feed reverse motion of the heald shedding mechanism has been formulated with the following shaft. The course of load exerted upon the heald shaft depends assumptions: upon the design of the parts of mechanism a) mass of heald shaft and elements 7, 8, 9 are reduced to the The heald shaft is the frame in which there are fastened the joints of the elements 4 and 6, healds governing warp threads. The healds are fastened in this frame with a necessary designing play. Because of textile technology reasons, this play must allow axial displacement of the loom along the support wire. As the heald shaft performs feed reverse movement, the system of healds gets transferred during the weaving cycle. This transfer produces a load on the supporting wire upon which the healds drop down, bringing as a consequence an increased stress of the whole shedding mechanism. During the weaving process the heald is always coupled with one of the pair of main beams of the heald shaft only.

2. Mathematical model of the shedding motion

In view of the fact that the lifting section of the shedding motion is a joint mechanism, a number of procedures and methods can be employed for the modeling of the above structure. It is possible to apply successfully the description of a mechanism based upon the method of devising motion equations by means of Lagrangian equations of the 2nd type according to [1,2].

In the model, the motion of healds considering clearances between healds and the heald rod, in heald eye between the heald and warp thread during one turn of looms’ main shaft, is analyzed. The results are represented by graphs of kinematic Figure 1. Scheme of mathematical model of the shedding motion. http://www.autexrj.com 44 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0022-8 © AUTEX

b) mass of elements 3, 5 are replaced by two masses it exerts an important effect upon its dynamic loading. Some concentrated in points and are considered as rigid, analyses have been dealt with in this process experimentally [9,10]. Because of this reason, it also constitutes one of c) rocking levers of elements 2, 4, 6 are rigid and are mutually the limiting elements impeding to increase its operational joined by torsical rods , revolutions. In order to be able to describe the behavior of the heald during the weaving process, it is necessary to devise d) clearances in kinematic pairs are considered in elements 2 a suitable mathematical model that will describe its behavior and 4, and during the operating cycle with a defined precision. The heald is influenced by a number of forces, which determine with which e) viscous damping in individual elements is also considered supporting wire it will be coupled. The most important ones are in the model. the dynamic force of the heald, the warp forces in the sense of movement of the shaft and the weight of the heald [11,12]. Equations of motion of the system are formulated using Lagrange’s equation of the type II in the form An important designing element influencing the behavior of the heald is the play in its fastening in the frame of the heald d  dK  K U R       (1) shaft. In the mathematical model, this play can be defined by dt  dqi  qi qi qi means of the difference of positions of the upper and lower where i = 2, 4, 6. (K - kinetic energy, U - potential energy, R - support wires. The distance of the lower support wire is shifted dissipative function.) with respect to the position of the upper one by the extent of the fastening play. Thanks to this play, the forces in the warp Substituting different parameters K, U, and R in equation (1), threads are transmitted upon one of the couplings of the rods we obtain the following equations of motion: of the heald shaft only. For analysis of movement of the heald,

we will assume that the frame of the shaft is absolutely rigid. 2 2        2     2         2P (I 2P I 4 24 )  I(4I. 24. I24. 2)P kI2 (.2P . .2) k4 k24(( 4P  4)  k) ((2)  In the)  mathematical model, this presumption will be reflected   2P 2P 4 24 4 24 24 2P 2 2P 2 4 24 4P 4 (2)  (2)  b2 ( 2P   2 )  b424 ( 4P   4 ) by the unchanging distance of both supporting wires in the  b2 ( 2P   2 )  b424 ( 4P   4 ) course of the whole calculation, corresponding to the solution 2 2        2     2           4P (I 4 I6 46 )  I6(.I 46. I46. 4)P  kI4 (.4P . 4. ) kk(6L 46 ( 6L )6 k )  ( of movement )  of a heald fastened in the vicinity of the edge of 4P 4 6 46 6 46 46 4P 4 4P 4 6L 46 6L 6 (3)   (3)  b4 ( 4P   4 )  b6L46 ( 6L   6 )  b4 ( 4P   4 )  b6L46 ( 6L   6 ) (3) a heald shaft. At present, the deformation of the main beams of the heald shaft during the working process are minimized by 4L I4L  k4L (4L 4  ) b4L ( 4L  4 )  M 4L  FNLL4L cos4L (4) 4L I4L  k4L (4L 4  ) b4L ( 4L  4 )  M 4L  F NLL4L cos 4L (4) (4) employing new types of composite rods.  I  k (   ) b (  )  M  F L cos (5) 6L 6L 6L 6L I 6  k 6(L 6L  6 ) b6L ( NL6L )  M6L  F L cos  (5) 6L 6L 6L 6L 6 6L 6L 6 6L NL 6L 6L (5) As mentioned in the introduction, nowadays flat healds are employed that are made of a flat steel band by the pressing Clearances occurring in the kinematic pairs of the chains are process. On the body of the heald, there are a number of replaced by angular differences of elements 2 and 4, which are orifices and stampings that serve e.g. for drawing-in machines incorporated into the model under the following conditions: or for other technological purposes. These shape parameters influence the strength and rigidity of the heald. Some healds iP  i  i  iP i 0      (6) iP i i iP i 0 (6) have a stamping in(6) the position of one suspension eye, which            ought to provide for mutual spacing of healds; however, it iP i i iP i  iP i i       (7) (7) iP i i iP i iP i i (7) reduces the rigidity of the suspension eye at the same time.             iP i i  iP  i  iP i i       Because (8) of this (8) reason, mathematical models are needed iP i i iP i iP i i (8) keeping in mind different rigidities of the upper and lower here i = 2, 4. sections of the heald. In the mathematical model of the heald,

we employ the Newtonian impact theory. The description of An experimental verification of the employed model of the fall of the heald upon the supporting wire employs the mechanical structure of the joint mechanism is described in presumption of a perfectly elastic impact. We presume the [3]. The referred universal mathematical model of the shedding velocity of the fall of the heald upon supporting wire up to motion can be modified in a simple manner by entering the time- 1 m.s-1. dependent lift dependence on the driving element, defining the course of its angular displacement. For example, it is possible The following part of the text describes the assembly of the to realize in this manner a calculation of the movement of a model of a heald, by means of which we are able to find with rotational dobby which is described in [4-8]. which supporting wire the heald is coupled in a given moment. The motion equations describing the movement of the heald during the weaving process are complemented with motion 3. Mathematical model of the heald equations of the shedding motion. In all compiled models, the mass of the heald mn is concentrated in one mass point. 3.1 Description of the heald problem The force To from the warp operates in the position of the thread eyelet. The mechanical properties of the yarn which The studies realized up to now have shown that the heald is is determined by the force of the warp in the mathematical one of the most important parts of the shedding motion and model were determined experimentally [13-15]. The point

http://www.autexrj.com 45 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0022-8 © AUTEX of application of this force is located in one mass point. It is The individual phases of the solution of the concerned model possible to disregard the bowing of the heald due to its lateral can be resolved by means of equations (10) − (13). The start of loading. The devised models proceed from the assumption the solution proceeds from the motion equation (10). that the movement of the mass point substituting the heald is T T k k b b   o o  nH nH   nH nH      carried out on a straight line. In the solution of the system, the yn yn  g g  ( y h( yhyn )yn )  ( yh( yhyn )y n ) (10) mnmn mnmn mnmn positions of the upper supporting wire (yh) and of the lower one T k b  o   nH    nH    (yd), position of the heald (yn), and position of the warp thread In the moment ofy n equalityg (11), the( y h healdyn ) leaves( y theh y uppern ) mn mn mn (yo) were established. The extent of the play in the fastening of supporting wire, and there follows a transfer of the heald the heald on the support wire is determined by the parameter between the main beams, which is solved according to f. The compiled models of the heald also consider the effect equation (12). of the dimension of the thread eyelet J upon the course of the mnm nyn ynTo Tomnm gn g0 0 (11()11 ) force in the warp.

To Tomn  yn To  mn  g  0 (11) (11) yn yn   g g (12()12 ) The initial conditions of the solution proceed from the mnmn presumption that the heald is entrapped on the upper supporting To yn   g (12) wire, and both its velocity and acceleration are identical with mn (12) those of the upper supporting wire. The transfer is completed when the conditions (14) or (15) are The solution of individual mathematical models has been fulfilled. The first potential state is the return of the heald on realized by means of a devised software program. The solution the upper rod (the condition 15 is fulfilled). In such a case, the of compiled differential equations describing the shedding motion movement of the heald is solved again according to equation (10). coupled with an analysis of the movement of heald during the weaving cycle has been affected by the Runge-Kutt method of If condition (14) has been fulfilled, the heald is entrapped on the 4th order. During the calculation, the courses of the principal the lower supporting wire and the acceleration of the heald is kinematic and force quantities of the system have been studied. solved according to relation (13).

To To kn kn bn bn 3.2 Solution of the heald problem yn yn   g g  ( y n( yn yd y)d )  ( yn( yn yd y)d ) (13) (13()13 ) mnmn mnmn mnmn To kn bn The system subject to solution can be represented schematically y n   g  ( yn  yd )  ( yn  yd ) (13) y y y y   m m m (14()14 ) according to Figure 2. The body of the heald is modeled by n n h h n n n (14) means of the Kelvin-Voigt visco-elastic rheologic model with the yn yn yh y h y n  y h   (15 (15) ) (14) rigidity knH and co-efficient of viscous damping bnH in the upper (15) part, and the rigidity k and co-efficient of viscous damping b nD nD y  y (15) in the lower part of the heald. A general motion equation of this The separation of then healdh from the lower supporting wire will model can be written as start in the moment when equality (11) is fulfilled. This transfer is again solved by means of motion equation (12). Once again, m  y  T  m  g  H.k (y  y )  H.b (y  y )  n n o n nH h n nH h n (9) it is necessary to check two limit states. The first one is the  D.k (y  y )  D.b (y  y ) nD n d nD n d return of the heald onto the lower rod (condition 14 has been The conditions for the solution of the concerned equation follow satisfied), the second limit state is entrapping of the heald from an equilibrium of forces on the heald, and – as mentioned on the upper support wire (condition 15 has been fulfilled). If above − they consider the play in the fastening of the heald on condition (14) is fulfilled, the solution of the motion of the heald the supporting wire. The control constants H and D assume will be realized employing motion equation (13). If condition the values 0 and 1, and they determine which members of the (15) has been fulfilled, the movement of the heald is solved by equation will be employed in the calculation. the equation motion in form (10).

Figure 2. Schematic model of the system shedding mechanism – heald. http://www.autexrj.com 46 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0022-8 © AUTEX

The effect of the thread eyelet is included in the calculation by between individual supporting wires. In this mathematical means of the following conditions: model, it is possible to ascertain the moment of separation of the heald from the supporting wire as well as the time of transfer  of the heald between main beams of the heald shaft. By means yn   yO  0 2 of this model, it is possible to determine the loads exerted upon   (16) individual end eyelets of the heald. The affected calculations yn   yO  yn  (16) 2 2 show a high value of acceleration of the heald produced after   its drop upon the supporting wire. The referred model allows for yn    yO  yn  2 2 analyzing a considerable part of designs of the heald shaft that are employed in weaving looms nowadays.

3.3 Results From the detailed analysis of theoretical calculation obtained for different operating frequencies, it has been found that The control algorithm of the calculation checks the position of the moments of the drop or of the separation of the heald the heald with respect to the supporting wire of the heald shaft. from the supporting wire are comparable with records of the As mentioned above, four possible states can arise which have acceleration. From the record, the behavior of the heald upon been studied and on the basis of the realized calculation of the the supporting wire depending upon the operating frequency movement of the heald. An example of calculated dependencies can be seen. An important factor, which can be evaluated, is is given in Figure 3, showing the principal kinematic courses of the number of bounces of the heald after the drop upon the the supporting wire and of the heald. The calculation has been supporting wire, after the transfer between the main beams of realized for the velocity of the shedding motion 300 r.p.m. An the heald shaft. example of the course of calculation in case of this model is given in Figure 4. This coincidence of experimental results and calculated

values obtained from the mathematical model constitutes a basic condition for a more extensive analysis of the system, 4. Conclusion with the aim to describe the behavior of the heald during weaving cycle and to propose possible adaptations of the For the generation of a real mathematical model, the model design. with the rigidity substitution of the heald by means of the Kelvin- Voigt visco-elastic model has proved suitable. The referred Dedication: The paper has been elaborated with financial enhancement allows for determining the number and extent of support of TUL in the framework of specific university research bounces of the heald from the supporting wire after its transfer competition.

path of the relative moment of the heald – calculation (model 2) [mm] 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.50.00 3.14 6.28 9.42 12.56 15.70 18.84 angle of rotation [rad] path of moment of the relative the heald [mm]

Figure 3. Relative movement of the heald with respect to upper supporting wire, operating velocityfáze of the pohybu shedding nitěnky motion [-] 300 r. p.m. 4

Table 1. Maximal value of acceleration after its transfer between individual supporting wires.

3 Shedding motion rpm 150 rpm 300 rpm 450 rpm 2 Maximal value of acceleration of heald after its transfer on upper rod [m.s-2] 1220 1340 1477 fáze pohybu nitěnky [-] nitěnky pohybu fáze

-2 Maximal value of acceleration1 of heald after its transfer on lower rods [m.s ] 671 906 1080 0.00 3.14 6.28 9.42 12.56 15.70 18.84 http://www.autexrj.com úhel pootočení47 [rad] AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0022-8 © AUTEX

0.06

0.04

0.02 angle of rotation [rad]

0.00 0.00 3.14 6.28 9.42 12.56 15.70 18.84

-0.02 displacemenent [m]

-0.04

lift of upper supporting wire lift of lower supporting wire movement of the heald -0.06

2.0

1.5

1.0

0.5 angle of rotation [rad] 0.0 0.00 3.14 6.28 9.42 12.56 15.70 18.84

velocity [ms-1]-0.5

-1.0

-1.5

-2.0 velocity of the heald velocity of the supporting wire

1000

500

0 0.00 3.14 6.28 9.42 12.56 15.70 18.84

angle of rotation [rad]

acceleration [m.s-2] -500

-1000

acceleration of the heald zrychlení nosného drátu -1500

Figure 4. Courses of kinematic quantities of the supporting wire of the heald shaft and of the heald, operating velocity of the shedding motion 300 r. p.m. http://www.autexrj.com 48 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0022-8 © AUTEX

Table 2. Table of the used symbols.

Symbols Description Unit w Angular velocity rad.s-1 F Clearance in a joint rad α, β, γ Angles between the parts of the shedding mechanism rad n Working speed mechanism r-p-m -1 bnH Viscous damping coefficient of heald upper part N.s.m -1 bnD Viscous damping coefficient of heald bottom part N.s.m -1 bOZ Viscous damping coefficient of warp N.s.m -1 knH Stiffness of heald upper part N.m -1 knD Stiffness of heald bottom part N.m -1 kOZ Stiffness of warp yarn N.m

TO Force component acting in the warp direction of healdshaft N J Height of yarn guides m f Clearance in the attachment between supporting wire and heald m g Gravity acceleration m.s-2 y Height of shed m l Displacement of warp-line m

FNL Load of healdshaft N

mn Weight of heald Kg K Kinetic energy J U Potential energy J R Dissipative function J D Dissipative energy J U Dissipative work J -1 k2, k4, k6l Torsional stiffness N.m.rad -1 b2, b4, b6l Viscous damping torsional coefficient N.m.s.rad 2 I2P, I4, I4l, I6, I6L Moment of inertia kg.m j j iP, iP Rotation of parts of the mechanism rad ϕ& ϕ& -1 iP, iP Angular velocity of parts of the mechanism rad.s

ϕ&& ϕ&& -2 iP, iP Angular acceleration of parts of the mechanism rad.s

M4L, M6L Weight of heald-frame and parts of the mechanism used for its stroke kg

FNL Load of the heald-frame N

References

[1] Mrázek, J.: Theoretical analysis of dynamics four-bar beat [6] Terentyev, V.I., Smirnov, B.N. Dynamics of a shedding up mechanisms of a loom. In.: Mechanism and machine mechanism with flexible links. Izvestiya Vysshikh theory, Pergamon Press, 1992, pp. 125-136. USA Uchebnykh Zavedenii, Seriya Teknologiya Tekdtil´noi Promyshlennosti - Issue 2, 2011, Pages 80-83. Russia [2] Bílek, M.; Mrázek, J. Dynamic Stress of Heald Shaft of Weaving Looms. Vlákna a textil, 1998, no.3, pp. 131-134, [7] Korolev, P.A., Lohmanov, V.N. Kinematics of connections Slovakia. of the shedding mechanism of a circular loom TKP- 110-U. Izvestiya Vysshikh Uchebnykh Zavedenii, Seriya [3] Beran J.; Bílek M. Matematické modelování základních Teknologiya Tekstil´noi Promyshlennosti - Issue 4, 2011, mechanismů tkacího stroje. In TRANSFER 2000. Trenčín: Pages 116-119. Russia TnU, Slovensko, 2000. s 25-30. [8] Kapucu, S., Das, M., T., Kilic, A. Cam Motion tuning of [4] Recep E.; Gülcan Ö.; Yildiray T.: Kinematics of Rotary Shedding Mechanism for Vibration Reduction of Heald Dobby and Analysis of Heald Frame Motion in Weaving frame. Gazi University Journal of Science – Volume 23, Process. Textile Research Journal, 2008 Vol. 78, No. 12, Issue 2, 2010, Pages 227-232. Turkey pp. 1070-1079, USA, [9] Akamura, T., Kinari, T., Shimokawa, T., Miyashita, D., [5] Eren R.; Ozkan G; Mehmet Karahan M.: Comparison of Mochizuki, Y., Shintaku, S. Jumping behavior of heald in a Heald Frame Motion Generated by Rotary Dobby and shedding motion of loom. Journal of Textile Engineering , Crank & Cam Shedding Motions. FIBRES & TEXTILES in Volume 52, Issue 2, 2006, Pages 87-92. Japan Eastern Europe. Vol. 13, No. 4 2005, http://www.autexrj.com 49 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0022-8 © AUTEX

[10] BÍLEK, Martin; KOVÁŘ, Šimon. Record of the movement of [13] TUMAJER, P., URSÍNY, P., BÍLEK, M., MOUČKOVÁ, heald in the weaving loom. In IX. International Conference E.: Use of the vibtex vibration system for testing textiles, on the Theory of Machines and Mechanism in association AUTEX Research Journal, Vol. 11, No2, June 2011, ISSN with the II. CEACM Conference on Computational 1470-9589, Mechanics 2004. Liberec : TUL, 2004, pp. 87-92. [14] Tumajer P., Ursíny P., Bílek M., Moučková E.; Research [11] Bílek, M., Kovář, Š.: Mathematical model of the heald shaft Methods for the Dynamic Properties of Textiles. FIBRES & of the weaving loom. Buletinul institutului polytehnic din TEXTILES in Eastern Europe 2011, Vol. 19, No. 5 (88) pp. Iaşi. Technical University of Iaşi, 2007 Iaşi, fasc. 5, volume 33-39. 1, pp. 375-382. Romania [15] TUMAJER, P., URSÍNY, P., BÍLEK, M., MOUCKOVA, [12] Hong Jun, C., Li Jun, L. Analysis on Warp´s Frictional E., POKORNA M.: Influence of structure of the yarn on Movement in the Heald Eye during Weaving Process. mechanical characteristics of yarns exposed to dynamic Advanced materials Research Volume 175-176, January stress, Autex Research Journal, Volume 12, Issue 2, June 2011, Pages 490-495. 2012, Pages 44-49

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ANTIBACTERIAL DYEING OF POLYAMIDE USING TURMERIC AS A NATURAL DYE

Mohammad Mirjalili1, Loghman Karimi2

1Department of Textile Engineering, Yazd Branch, Islamic Azad University, Yazd, Iran 2Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran E-mail: [email protected], [email protected]

Abstract:

Curcuma longa rhizome (turmeric) is a medicinal plant used for fabric and food coloration. In this study, polyamide (nylon 6.6) fabric was dyed with different mordants at various turmeric concentrations. The dyed fabric was evaluated for bacteriostatic activity against pathogenic strains of Gram-positive (Staphylococcus aureus) and Gram- negative (Escherichia coli) bacteria. The relationship between bacteriostatic activity and turmeric concentration was investigated. Durability of antibacterial activity to laundering is also discussed. Results indicate that the polyamide dyed with turmeric displayed excellent antibacterial activity in the presence of ferric sulfate, cupric sulfate, and potassium aluminum sulfate, and exhibited good and durable fastness properties.

Keywords:

Turmeric, antibacterial, bacteriostatic, mordant, polyamide, Staphylococcus aureus, Escherichia coli

Introduction environmental pollution [15]. For instance, certain fluorocarbon finishes, especially those consisting of eight carbons inthe During the past decades, human health has been seriously perfluoro alkyl chain, can degrade to form perfluorooctanoic threatened by environmental pollution, especially indoor acid. Perfluorooctanoic acid is of environmental concern microbiological contamination (SARS, Influenza, etc.). The because it bioaccumulates in human body [16]. The statistical figures reveal that the total number of deaths caused Environmental Protection Agency has taken measures to limit by bacterial infection exceeds 17 million, about one-third of the use of perfluorooctanoic acid in the industry [17]. world-wide deaths [1]. Textiles can, thus, enhance cross- contamination by pathogenic microorganisms in environments Natural dyes are believed to be safe because of their non-toxic, such as home and hospitals. Textile materials provide an non-allergic, and biodegradable nature. Many of the plants excellent environment for microorganisms to grow, because of used for dye extraction are classified as medicinal, and some their large surface area and ability to retain moisture. Microbial of them have recently been shown to possess remarkable activity can be detrimental to textiles. It can cause unpleasant antibacterial activity [18-22]. Curcuma longa L. known as odor, lead to weakening of the substrate, discoloration, and turmeric, which is used as a coloring agent, has medicinal even contribute to the spread of disease. For this reason, properties [23-25]. Curcuma longa L., which belongs to the antimicrobials have been investigated as a finish for textiles Zingiberaceae family, originates from the Indian sub-continent [2,3]. and possibly neighboring areas of Southeast Asia, but it is nowadays widely grown throughout the tropics. The pigments Antibacterial finishes are applied to textiles for three major in the colorant extracts obtained from Curcuma are collectively reasons: (a) to contain the spread of disease and avoid the known as curcuminoids, the major constituent being curcumin, danger of injury-induced infection, (b) to contain the development along with small amounts of demethoxycurcumin and bis- of odor from aspiration, stains, and soil on textile materials, and demethoxycurcumin (Figure 1) [26]. Turmeric has been isolated (c) to contain the deterioration of textiles caused by mildew, from the rhizome of C. longa, attributing biological activities such particularly fabrics made of natural fibers [4]. Various methods, as antioxidant, anti-inflammatory, wound-healing, anticancer, depending on the active agent and the fiber types, have been developed or are under development to confer antimicrobial activity to textiles. Many methods have been reported, such as fluorocarbon repellent finish, chemical binding of heterocyclic N halamine functional group to polyamide, using plasma, or immobilization of antimicrobial metallic nanoparticles on textiles (TiO2, Ag, Cu, ZnO, etc.) [5-14].

Although the synthetic antibacterial agents are very effective against a range of microbes, they are causes of concerns due to health hazards, action on non-target microorganisms and Figure 1. Structures of curcumin and its analogs. http://www.autexrj.com 51 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0023-7 © AUTEX anti-proliferative, antifungal, and antibacterial activity [27]. Color measurements Ghoreishian and coworkers dyed silk fabric with turmeric and proved antibacterial properties to silk fabric [28]. Sundrarajan The dyed polyamide fabrics were individually tested for et al. modified cotton fabrics with enzymes and chitosan, and their color strength. The color strength (K/S) values of the reported the enhancement of dye uptake and washing fastness dyed fabrics were instrumentally determined by reflectance of cotton fabrics dyed with turmeric [29]. spectrophotometer (BYK-Gardner, India, with CIELAB 1976 color space and D65-light source) with Kubelka–Munk equation Polyamide has been one of the most widely used polymers in as follows: various industries such as fiber, film, and plastic. It has major K (1− R)2 = advantages of high modulus and strength, stiffness, stretch, S 2R (1) wrinkle, and abrasion resistances [30]. However, polyamide can be easily attacked by bacteria in vivo. In this study, simultaneous where R is the reflectance of the dyed fabric at the maximum antibacterial and dyed polyamide fabric was prepared by absorption wavelength, S is the scattering coefficient, and K is turmeric natural dyeing in the presence of various mordants, and the absorption coefficient of the dyed fabrics. we also focused on the antibacterial activity of treated fabrics against two common pathogenic bacteria: Escherichia coli Antibacterial test (E. coli) and Staphylococcus aureus (S. aureus). Antibacterial activity against Gram-positive bacteria (S. aureus) and Gram-negative bacteria (E. coli) was tested Experimental section quantitatively by AATCC Test Method 100-1999. The number of viable bacterial colonies on the agar plate before and after Materials dyeing was counted and the results reported as percentages of bacteria reduction according to The polyamide (nylon 6.6) fabric was used with warp density 50 ends/cm and weft density 28 ends/cm. The turmeric was R = (B‑A)/B × 100 (2) purchased from Iranian traditional natural dyers. Mordants such as potassium aluminum sulfate, cupric sulfate, and where R denotes the percentage of reduction of microbial ferric sulfate were purchased from Merck. Escherichia coli, a population; B is the absorbance of the media inoculated with Gram-negative bacterium, was selected due to its popularity microbes and un-dyed fabric; and A shows the absorbance of as a test organism and its resistance to common antimicrobial the media inoculated with microbes and dyed fabric. agents. Staphylococcus aureus, a pathogenic Gram-positive bacterium, was used because it was the major cause of cross- Durability to laundering infection in hospitals and it is the most frequently evaluated species. Cultures of the following microorganisms were used Durability of antimicrobial activity to washing is one of the major in the study: S. aureus ATCC 25922 and E. coli ATCC 25923. concerns of textile researchers and users because textiles are subjected to frequent laundering. The treated samples with Toxicity assay 30% concentration of turmeric were washed under condition of the ISO 105-CO2 Test Method to determine the bacteriostatic Turmeric solution containing 1 g⁄100 ml was prepared and, effect of fabrics after 1, 5, 10 and 20 cycles of laundering. from this stock, different concentrations (50, 75, and 100 ppm) were prepared for testing and were finally applied to sterile 9-cm diameter Whatman No. 1 filter paper disks in Petri dishes. Results and discussion Then 10 surface-disinfected green grams were placed on the wetted paper. After 14 days of incubation at 27±°C, the total Toxicity assay root growth (germination) was measured and compared with the control (untreated sample) and was expressed as root The results demonstrate that turmeric at different concentrations growth inhibition percentage [31]. caused no inhibition to germination and root growth to the green grams and a growth rate of more than 90% was observed. The Dyeing procedure untreated and treated green grams were almost equal in their germination and growth rate. Thus, the turmeric was found to To study the relationship between dye concentration and be non-toxic. antimicrobial activity, 100% polyamide fabrics were dyed with 5, 10, 20, and 30% turmeric on weight of fabric (OWF) with Color strength of polyamide fabrics potassium aluminum sulfate, cupric sulfate, and ferric sulfate mordants, and un-mordant. The polyamide fabric was dyed The majority of natural dyes need a mordant in the form of in an AHIBA dyeing system with turmeric dye. The dye bath a metal salt to create an affinity between the fiber and the comprised dye, 1% acetic acid, and 3% mordant. The liquor pigment. These metals form a ternary complex on one ratio was kept at 40:1. The temperature was raised to 100°C by side with the fiber and on the other side with the dye. Such a thermal gradient of 2°C/min, and dyeing operation continued a strong coordination tendency enhances, the interaction for 60 min. between the fiber and the dye, resulting in high dye uptake. http://www.autexrj.com 52 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0023-7 © AUTEX

Figure 2 shows the graph of treated samples K/S dyed by Bacteriostatic activity turmeric (20%). The result of dyeing samples shows that using mordants considerably increased dye absorption leading to Table 1 shows the photographs of bacterial growths upon higher K/S values in case of mordanted samples than un- treated polyamide fabrics. Figures 3 and 4 exhibit comparative mordanted ones. Ferric sulfate mordant was found to have the diagrams of bacteriostatic activity results for the treated sample most prominent effect on color strength. in the presence of E. coli and S. aureus bacteria. Curcumin

Figure 2. K/S graph of the dyed polyamide fabric samples with 20% turmeric (OWF).

Table 1. Photographs showing the growth of S. aureus and E. coli bacteria upon treated samples.

Turmeric S. aureus concentration (OWF, %) Cupric sulfate Ferric sulfate Potash alum Un-mordanted Raw sample

10

30

E. coli

10

30

http://www.autexrj.com 53 AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0023-7 © AUTEX

Figure 3. Antimicrobial activity of dyed polyamide samples with turmeric in the presence and absence of mordant against S. aureus.

Figure 4. Bacteriostatic activity of dyed polyamide samples with turmeric in the presence and absence of mordant against E. coli. found in turmeric affects RNA and DNA of microorganisms and effects. Hence, it is suggest that the turmeric dye can be used their fights. for dyeing polyamide as an alternative to the very expensive, synthetic, and toxic antibacterial agents. The bacteriostatic activity of treated fabrics was ranked as ferric sulfate > cupric sulfate > potassium aluminum sulfate > un- Washing fastness properties mordant against S. aureus and cupric sulfate > ferric sulfate > potassium aluminum sulfate > un-mordant against Textiles are subjected to frequent washing, rubbing, and E. coli. sweating during their use and the requirement of durability is a very important parameter. Figures 5 and 6 depict the durability Based on the obtained results, specimens showed a better of antibacterial activity after repeated home launderings. efficiency against E. coli in comparison with S. aureus. This As shown, the antibacterial activity reduced with increased can be explained by the difference between thicknesses of the number of washing cycles. The inhibition rate of treated sample cell walls. Staphylococcus aureus has a thicker cell wall [32]. un-mordant was more reduced than the treated sample with They also showed that using mordant had better bacteriostatic mordant after laundering. activity. It is well known that the metallic salts used as mordants exhibit toxic effects against the pathogens. Conclusion Natural dyes are non-toxic, biodegradable, and do not cause pollution and wastewater problems, while synthetic dyes have This is the first report where turmeric, used in polyamide dyeing, been known to cause health hazards due to their carcinogenic has been shown as a source of a natural, non-toxic dye. This http://www.autexrj.com 54

AUTEX Research Journal, Vol. 13, No 2, June 2013, DOI: 10.2478/v10304-012-0023-7 © AUTEX

Figure 5. Bacteriostatic activity of dyed polyamide samples with turmeric in the presence and absence of mordant against S. aureus after laundering.

Figure 6. Bacteriostatic activity of dyed polyamide samples with turmeric in the presence and absence of mordant against E. coli after laundering.

research was conducted to introduce an effective natural dye polyamide presented a strong bacteriostatic activity against to produce an ideal antibacterial polyamide fabric. A common two well-known pathogenic bacteria S. aureus and E. coli. dyeing process provides polyamide with color and antibacterial Turmeric is more effective against E. coli than S. aureus. properties. Since the dyeing process and bacteriostatic Moreover, using mordant had better bacteriostatic activity. The finishing have been conducted in one step and do not require bacteriostatic activity of turmeric mordant-finished polyamide is an additional step, this method is cost-effective. Natural-dyed more durable to home laundering than the un-mordanted ones.

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