DEVELOPMENT OF CARBOXYMETHYL … Krizova, Jakub Wiener ... and has antidiarrheal effect. Tannins form through their hydroxyl ... used as a source of polyphenols.Published in: 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 RepublicE-mail: [email protected], [email protected]

1. Introduction

1.1 Polyphenols (PF)

Polyphenols are a very varied group of chemically diverse compounds that contain hydroxyl groups bound to the aromatic ring. They are easily oxidizable substances with a low redox potential which are able to reduce some radicals (e.g. superoxide, peroxyl and hydroxyl ones) with oxidative effects. Polyphenols are a broad group of plant bioactive substances able to protect cells from oxidative damage due to their strong antioxidant and antiradical activities. PF include for example amino acids (tyrosine), essential oils, phenolic acids (e.g. vanil, gallic, coumaric and ferulic ones), flavonoids (e.g. catechins, quercetin, rutin, anthocyanidins) and tannins.

1.2 Tannins

Tannins are oligomeric and polymeric polyphenol compounds 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.

1.2.1 Hydrolyzable tannins

Their basic monomer unit is gallic or ellagic acid and their molecular weight ranges from 500 to 3000. They are well soluble in water, hydrolyze due to heat, weak acids or weak bases. They are also easily decomposed by digestive enzymes of mammals. Among these is e.g. oenothein present in the wine or tannic (Figure 1) [1] contained in fruits and bark of oak, chestnut or in leaves of sicilian sumac [1].

1.2.2 Condensed tannins (proanthocyanidins)

Their basic unit of condensed tannins is a monomeric flavan-3-ol (Figure 2) [1], and according to the degree of polymerization their molecular weight also reaches over 20,000. Condensed tannins contain strong bonds between carbons, and are therefore not easily hydrolyzable and in the tract of mammals hardly decompostable. An example of condensed tannins is procyanidin or prodelphinidin. Condensed tannins accumulate

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

Figure 1. Gallic acid and tannic acid.

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

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2.2 Used methods

2.2.1 Extraction of polyphenols

Pomace of blue grape vine were after the pressing of macerated and fermented mash immediately freezed, then dried at 70°C to a constant weight, and eventually homogenized. 2 g of crushed dried pomace (mixed peels, seeds and stems with the weight ratio 15:9:1) were extracted (in a dye cartridge of dyeing apparatus Ahiba Nuance ECO) with 100 ml of distilled water at 100°C for 90 minutes.

2.2.2 Preparation of CMC gels and films

3 g of CMC were dissolved in the extract of pomace by formation of gel. The gel was homogenized, spilled onto glass plate and dried at 60°C to film of constant weight. Subsequently, one third of the film was crosslinked at 180°C for 1 minute, one third was crosslinked at 180°C for 3 minutes to achieve the partial insolubility and one third stayed non-crosslinked [7].

2.2.3 Determination of total polyphenols

The total polyphenol content was measured spectrophotometrically using the Folin-Ciocalteu reagent. This reaction is based on colorimetric redox reaction of phenols [8]. To 1 ml of distilled water and 1 ml of Folin-Ciocalteu reagent (diluted 1:9 with distilled water) was added 200 μl of skimmed sample (60 revolutions/minute for 3 minutes). 1 ml 0.75 M solution of anhydrous sodium carbonate was added after 5 minutes. Parallelly, a control sample (a blank one) was also prepared containing 200 μl of distilled water,

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 as in 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)

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 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 taste of polyphenols and tannins in beverages enriched with antioxidants so that it reduces their astringent effect on the salivary glands [3,4]. CMC is used to stabilize wine by preventing the precipitation of pottasium bitartrate (tartar) and to prevent the formation of sediment in bottled wines [5]. CMC can also be used as a protective layer for encapsulation of polyphenols for oral use as CMC housing protects these substances against the effects of digestive enzymes, and in addition these substances are safely transported to the place of their maximum resorption in the colon. Only here is the CMC pouch disrupted by the activities of the cellulase enzymes present in intestinal bacteria. CMC is also used as a carrier for active substances and drugs for surface application. Moreover, CMC is part of dressings for treating particular kinds of wound including a mixture of hydrogels and different substances for the stimulation of wound healing. These substances include enzymatic agents, activated carbon, silver ions or antibiotics [6].

2. Materials and Methods

2.1 Materials

Blue grape pomace of Fratava variety (Lobkowicz castle winery Roudnice nad Labem, Ltd.) Gallic acid (monohydrate) (Sigma-Aldrich) Powdered sodium carboxymethyl cellulose, medium viscosity, molecular weight 250 000 (Fluka) Folin-Ciocalteau reagent (Penta Chrudim) Anhydrous sodium carbonate (Lachema) and NaCl p.a. (Lach-Ner)

Figure 2. Flavan-3-ol and condensed tannin.

Figure 3. Carboxymethyl cellulose.



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crosslinking of CMC occurs resulting in less swelling of CMC. This shortens the diffusion path of substances’ molecules which are in the closed path (CMC is inert and does not react chemically with PF – it is only a mechanical sorption) and PF can thus quickly desorb to the place of lower concentration). Second, it is expected that a thermal hydrolysis of polymeric polyphenols (tannins) occur so that smaller PF molecules can again rapidly diffuse from the gel to the solution. The problem is a total thermolability of PF, wherein at 180°C their content is declining rapidly; that is why it is important to choose a time-temperature compromise, where their content is still maintained and at the same time their optimum release is under way.

Figure 7 shows a percentage expression of decrease of polyphenols and also percentage expression of decrease of half-time speed of their release from CMC, depending on the

and calibration series of solutions of gallic acid (GA) with increasing concentrations from 0.01 to 0.06 mg/ml (Figure 4). The presence of polyphenols causes after 50 minutes a chemical reaction accompanied by a visual color change of the solution from yellow to blue. Afterwards, the absorbance was measured by the means of UV/VIS spectrophotometer (Helios epsilon) in the absorption maximum at 765 nm. The resulting concentrations of samples (extracts prior to sorption into CMC gel and after the desorption of CMC) were calculated on the basis of calibration curve of gallic acid and expressed in mg GA/ml of solution, respectively in g/liter.

2.2.4 Desorption of polyphenols

0.5 g of each of CMC/PF film was immersed in 80 ml saline (0.9% NaCl) and dissolved using a magnetic stirrer at 37°C. 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 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 film decreases. This leads to two outcomes: first, a thermal

Figure 4. Spectrophotometric calibration of gallic acid.

Figure 5. Release of PF from CMC films: non-crosslinked and partially thermal crosslinked CMC.

Content of CMC Total dry matter (dry matter+CMC+PF)

Content of PF in 0,5 g samples

PF concentration of the resulting 80 ml saline

3 g 3,40 g 7,35 mg 0,092 mg/ml

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



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References

[1] Schofield, P., Mbugua, D.M., Pell, A.N.: Analysis of condensed tannins: a review. Animal Feed Science and Technology 91 (2001), p.21-40

[2] Serrano-Cruz, M.R. et al.: Controlled release and antioxidant activity of Roselle (Hibiscus sabdariffa L.) extract encapsulated in mixtures of carboxymethyl cellulose, whey protein, and pectin. Food Science and Technology 50/2 (2013), p. 554-561

[3] Troszyńska,A. et al.:The effect of polysaccharides on the astringency induced by phenolic compounds. Food Quality and Preference 21 (2010), p.463–469

[4] Smith A., K., June, H., Noble, A.C.: Effects of viscosity on the bitterness and astringency of grape seed tannin. Food Quality and Preference 7 (1996), p.161-166

[5] Bosso, A. et al.:Carboxymethylcellulose for the tartaric stabilization of white wines, in comparison with other oenological additives. Vitis 49/2 (2010), p.95–99

[6] Skórkowska-Telichowska, K. et al.: The local treatment and available dressings designed for chronic wounds. Journal of the American Academy of Dermatology (2011), In press

[7] Borůvková, K., Wiener, J., Kukreja, S.: Thermal self cross-linking of carboxymethylcellulose. ACC Journal XVIII/1 (2012), pp. 6-13

[8] Singleton V.L., Orthofer R., Lamuela-Raventós R.M.: Analysis of total phenols and other oxidation substrates and antioxidants by means of folin-ciocalteu reagent. Methods in Enzymology 299, 1999, p.152-178

time of thermal crosslinking. It is obvious that, for example, a distance between the two curves is the largest after 1 min. of crosslinking. At this point the release of PF is already short enough while maintaining a high content of PF.

4. Conclusion

This research was aimed at the kinetics of release of polyphenols from carboxymethyl cellulose film which was thermal crosslinked at 180°C for 1 and 3 minutes and the results were compared with the completely soluble non-crosslinked CMC. Thermolabile PF are partially protected by CMC and the short high temperatures decreased their content to 85% of the initial content (and to 70% respectively). After one hour in saline, the CMC/PF gels were dissolved in 92, 36 and 24%. Depending on the degree of crosslinking, the rate of release increased because partial crosslinking of CMC reduces its swelling, reducing the diffusion path.

Measurement results show that CMC can be used as a carrier of polyphenols and their release can be influenced by degree of crosslinking and solubility of CMC.

Acknowledgment

The paper has been supported by the grant project SGS 48008 (provided by Faculty of Textile of Technical University of Liberec) and TACR program ALFA TA01010244 (Czech republic).

Figure 6. Half time of release of PF from CMC, depending of the degree of crosslinking.

Figure 7. Decrease of PF content and of their half-time release depending time of crosslinking at 180°C.



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A NEW METHOD OF DETERMINATION OF COLLAGENCONJUGATED WITH KERATIN

Marta Safandowska, Krystyna Pietrucha

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

1. Introduction

Collagen is the major component of the extracellular matrix (ECM) and is the most abundant mammalian protein 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 the primary resource in medical applications [1]. Collagen can also be used to modify the surface of various types of synthetic polymers. For example, coating polypropylene meshes with collagen results in their improved bio- and cytocompatibility; modification of polyester vascular prosthesis by collagen increases their leak-proof properties [2-4]. Furthermore, collagen displayed bacteriostatic properties against Staphylococcus epidermidis and b-hemolytic Streptococcus [5], and therefore it can impart antibacterial properties to natural textile fibers [6].

A multitude of applications of collagen indicates that it is very appropriate to use a rapid and precise method for its determination. Many physicochemical methods, such as X-ray photoelectron spectroscopy (XPS), chromogenic reactions (hydroxyproline assay, amine dyes: ninhydrin or Rhodamine B isothiocyanate), molecular weight comparisons (gel electrophoresis, chromatography), radioactive procedures (radioactive labeling of proline) and immunological reactions (enzymeimmunoassays using specific antibodies) are used to estimate the amount of collagen [2,3]. The most precise and specific method of collagen determination is based on the quantitation of its hydroxyproline content; unfortunately, it is a complex and time consuming procedure. Sirius red staining seems to be an excellent alternative technique for quantitative or qualitative measurement of collagen. It is a fast and non-destructive method, which has been used for histological staining of collagen in tissue sections from many years [7].

The goal of this study is to elaborate a simple and accurate method of collagen examination. In this work, the method of Sirius red staining was applied to assay collagen conjugated with keratin of wool. The application of Sirius red dye for the

detection of collagen on keratin substrates has not been reported previously. The capability of tyrosinase to catalyze the oxidation of tyrosine residues of keratin and for coating collagen on wool materials has to be assessed.

2. Materials and methods

2.1. Materials

Wool fibers and woven fabric (twill weave) were chosen for preparation of the samples. Fibers from sheep wool was cleaned by Soxhlet extraction using dichloromethane to remove fatty matters (t=14 h, 6 transfers to 1 h). Collagen type I was prepared from fresh skin of silver carp and supplied by AAG Sp. z o.o. (Poland).

Tyrosinase from mushroom (EC 1.14.18.1, ≥1000 unit/mg solid) and Sirius red F3BA were purchased from Sigma–Aldrich (Sigma, St. Louis, MO, USA). All other chemicals of analytical grade were obtained from POCh–Gliwice (Poland).

2.2. Preparation of samples

Samples of wool fibers and fabric were modified with enzyme and collagen in accordance with a method [6]. For this purpose, 0.5 g wool was placed in 50 ml 0.1 M phosphate buffer (pH=6.5) containing tyrosinase (2000 U/g). In addition, ascorbic acid solution at 0.42 mg/ml was added. After 1 h, collagen solution in 1% CH3COOH was added to the buffer/wool incubation mixture in a final concentration of 2 mg/ml. Incubation was continued at 25 °C for 24 h. To terminate the enzymatic reaction, the pH was raised to pH 9 using 0.1M KOH. Then, the sample was rinsed in distilled water and 1% CH3COOH, and air-dried.

2.3. Characterization of the products

Color measurements. In order to determine the enzyme-catalytic modification effect on the wool-derived keratin, the reflectance measurements were evaluated by using Datacolor

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



37

to the corresponding quinones, which possess fluorescence properties [8]. These o-quinones may either condense with each other or react with free amino groups, resulting in the formation of covalent keratin-collagen crosslinks (Figure 2) [8,9].

Int. Spectraflash 500 spectrophotometer with dataMaster software. Results were expressed by the CIE whiteness (W) according to the ISO 105-J02:1999 method and CIELab color values and color difference (ΔE) at D65/10º. The degree of whiteness (W) was calculated using the following equation:

(1)

where:W is the whiteness; Y the trichromatic component of the sample; x, y the chromaticity coordinates of the samples, 0.3138 and 0.3310 the chromaticity coordinates x and y respectively for the perfect light scattered.

The color difference - ΔE - was calculated according to the formula of Commission Internationale de l’Eclairage – CIE Lab in relation to an unmodified sample:

(2)

where:ΔE is the color difference expressed in CIELab units; ΔL the difference in lightness; Δa the difference in the chromaticity coordinate, green/red axis; Δb the difference in the chromaticity coordinate, blue/yellow axis.

Sirius red staining. The presence of collagen onto the surface layer of wool-derived keratin was evaluated by staining with Sirius red F3BA dye, in accordance with the procedure described by [7]. Tyrosinase-treated sample in the presence and absence of collagen were incubated with water solution of 0.5% Sirius red at room temperature for 30 minutes. Thereafter, the samples were washed extensively for 30 minutes in distilled water, and air-dried. The color measurements were made by sensory impairments.

3. Results

As revealed in Figure 1, the CIE whiteness (W-CIE D65/10) of keratin samples (wool fibers and woven fabric) treated by tyrosinase in comparison with untreated samples increased by 15% and 4%, respectively. The increase in whiteness was also observed for the samples which were subjected to enzyme treatment and simultaneous coating with collagen.

The increase in the value of whiteness may be related to the fact that the tyrosine residues of keratin under reducing conditions and under the influence of the enzyme are oxidized

OH

keratin

O2 OO

keratin

OH

keratin

OH

NHcollagen

NH21/2

tyrosinase

collagen-

Samples ΔE K/S

Wool fibers - 0,4976

Wool woven fabric - 0,5058

Enzyme-treated fibers 1,58 0,4613

Enzyme-treated fabric 0,67 0,4879

Enzyme/collagen-treated fibres 1,98 0,4543

Enzyme/collagen-treated fabric 1,24 0,4756

Table 1. CIELLAB color difference (ΔE) and color depth (K/S) of wool samples.

Figure 1. CIE whiteness of samples of wool-derived keratin.

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

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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 tyrosinase treatment, (C, F) after tyrosinase treatment and simultaneous coating with collagen.

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The increase in the value of whiteness may be related to the fact that tyrosine residues of keratin under reducing conditions and under the influence of the enzyme are oxidized to the corresponding quinones, which possess

As can be seen from Table 1 the enzyme treatment also had a slight impact on the color difference (ΔE) and color depth (K/S).

The presence of collagen on surfaces of wool was confirmed by using the staining of collagen with Sirius red F3BA. As can be seen from the pictures (Figure 3), all samples are stained; however, only those wool samples which have been enzymatically treated and simultaneously coated with collagen were characterized by a higher intensity of staining. The uncoated samples of keratin (Figure 3 A, B, D, E) did not bind the Sirius dye and gave only a weak background.



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cytocompatibility of human endothelial cells, Biomacromolecules 2, 1312-1319, 2002.

[3] Jou C.H.; Lin S.M.; Yun L.; Hwang M.C.; Yu D.G.; Chou W.L.; Lee J.S.; Yang M.C.: Biofunctional properties of polyester fibres grafted with chitosan and collagen, Polymers for Advanced Technology 18, 235–239, 2007.

[4] Pietrucha K., New collagen implant as dural substitute, Biomaterials 12, 320-323, 1991.

[5] Carlson G. A., Dragoo J. L., Samimi B., Bruckner D. A., Bernard G. W., Hedrick M., Benhaim P., Bacteriostatic properties of biomatrices against common orthopaedic pathogens, Biochemical and biophysical Research Communications 321, 472-478, 2004.

[6] Jus S.; Kokol V.; Guebitz G.M.: Tyrosinase-Catalysed coating of wool fibers different protein-based biomaterials, Journal of Biomaterials Science 20, 253-269, 2009.

[7] Junquiera L.C.U.; Bignolas G.; Brentani R.R.: A simple and sensitive method for the quantitative estimation of collagen, Analytical Biochemistry 94, 96-99, 1979.

[8] Jus S.: Kokol V.; Guebitz G.M.: Tyrosinase-catalysed coupling of functional molecules onto protein fibres, Enzyme and Microbial Technology 42, 535-542, 2008.

[9] Thalmann C.R., Lotzbeyer T., Enzymatic cross-linking of proteins with tyrosinase, EUR Food Res Technol 214, 276-281, 2002.

4. Conclusions

The obtained results demonstrate that Sirius red staining is a specific and simple method for the determination of collagen coated onto wool-derived keratin. Reflectance measurements showed that the whiteness of the wool samples after enzyme treatment increases, which means that tyrosinase activates the tyrosine residues in keratin to the quinone forms, which react further nonenzymatically with primary amino groups of collagen.

Acknowledgment

The work was partially supported by the National Science Centre via Grant No. DEC-2011/03/B/ST8/05867.

References

[1] Lee C.H., Singla A., Lee Y., Biomedical applications of collagen, International Journal of Pharmaceutics 221, 1–22, 2001.

[2] Zhu Y.; Gao C.; Liu X., Shen J.: Surface modification of polycaprolactone membrane via aminolysis and biomacromolecule immobilization for promoting

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 tyrosinase treatment, (C, F) after tyrosinase treatment and simultaneous coating with collagen.

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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 tyrosinase treatment, (C, F) after tyrosinase treatment and simultaneous coating with collagen.

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The increase in the value of whiteness may be related to the fact that tyrosine residues of keratin under reducing conditions and under the influence of the enzyme are oxidized to the corresponding quinones, which possess



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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 Metrology2Lodz University of Technology, Faculty of Chemistry, Institute of Polymer and Dye Technology

E-mail: [email protected], [email protected]

1. Introduction

Styrene-butadiene rubbers (SBR) are the most commonly used synthetic rubbers today. They are produced by copolymerization of butadiene and styrene. The majority of conventional fillers used in rubber industries are silica and carbon black because of their relatively high reinforcing efficacy. Generally, a silica-reinforced rubber shows a similar tensile strength to one reinforced with carbon black, but the modulus is relatively lower [1]. Currently, the necessity for reinforcing fillers from renewable resources, such as plant-based natural fibers, for the production of biosustainable composite materials is increasing in research areas and manufacturing because of their ease of processing, low cost, low density, biodegradability, and good mechanical properties. Fillers exist in a variety of systems, including biological, organic, and polymeric materials [2,3]. In polymer systems, fillers not only reduce the cost of the compound but also improve the mechanical and dynamic properties of the material. Fiber-reinforced polymer composites are now used as alternative low cost materials for structural and nonstructural applications, such as automotive applications, packaging, building products, furniture, and consumer goods. In the past, a diversity of short fibers was merged into natural rubber, and their reinforcement was discussed [4-9]. It was found that they did not provide a similar level of reinforcement compared to carbon black and silica. That is, the tensile strength and elongation at break 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 properties was found to be 20-30 phr [5,7,8]. Many authors have shown the effect of fiber surface modifications, using bonding agents, NaOH treatment, acetylation, and mercerization on the interfacial adhesion of natural fiber and rubber matrix [10-15]. The authors also analyzed the dynamic mechanical behavior of natural-fiber-reinforced rubber and curing characteristics of the compounds. They found that composite performance can be enhanced by chemically treating the fibers. Moreover, natural

fibers can be added to rubber to improve or modify certain properties, such as green strength, creep resistance, hardness, aging resistance, dynamic mechanical properties, dimensional stability during fabrication, and real-time service, and to reduce the cost of fabricated articles. It is well known that blending of two or more fibers or/and fillers gives the potential for preparing new materials with specific and improved properties [16]. Recently, studies of the synergistic effects of short fibers and particulate fillers compounded with miscellaneous polymeric matrices on the physicomechanical properties of hybrid composites have been reported [17,18]. These studies showed promising results, in which the improvement of specific properties was observed together with additional environmental and cost benefits. Therefore, it is expected that the combined use of both short natural fibers and silica will enable one to connect the beneficial effects of individual reinforcement for the development of materials with desirable properties. In expedient applications, such as for automobile tires, the combined use of natural fibers and silica has been applied widely to improve processability, dimensional stability, and mechanical balance between abrasion resistance and rolling characteristics [19,20]. Tire-tread compounds containing short natural fibers together with silica are used to enhance ice traction for icy roads [21]. In this study, the primary objective was to examine the effect of the ratio of short fibers on the curing/rheological characteristic and tensile properties of styrene-butadiene rubber.

2. Experimental

2.1 Materials

KER 1500, styrene-butadiene rubber (SBR), bound styrene content 23, 5 %, was obtained from Synthos S.A. (Oświęcim, Poland). Short fibers were obtained from Z. W. Biliński Sp. J. (Konstantynów Łódzki, Poland). These fibers are very short (less than 1 cm long). The rubber compounding ingredients,

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.



40

2.5 Mechanical measurement

The tensile testing was performed on a testing machine (ZWICK Z005 TH All-round-Line) according to ASTM D 412. The dumbbell-shaped test specimens were cut from vulcanized rubbers. The specimens were stretched at room temperature (25 ± 2 °C). The average tensile properties for each composite were determined from five specimens. Hardness (Shore A) of the samples was also measured.

3. Results and discussion

3.1 Processing properties

The cure characteristic and Mooney viscosity [ML (1+4), 100°C] of the composites were determined as a function of the fibers and the carbon black content. The results are given in Table 2. Minimum torque (ML) obtained from RPA testing is normally related to the viscosity of a rubber compound. The ML value of fiber-filled compounds was higher than that of the carbon black-filled compounds and that of the control sample. The presence of fibers increases the viscosity of the mixes. The increment in torque values with increasing filler loading indicates that as more and more filler incorporated into the rubber matrix, the mobility of the macromolecular chains of the rubber decreases resulting in more rigid vulcanizate. It is seen that the mix containing fillers provides a higher torque value indicating higher crosslinking. From Table 2 it is observed that the optimum cure time slightly decreases with the increase of fiber loading and the change in scorch time is also slight. In case of carbon black, optimum cure time and the scorch time decreases with increase of filler loading. In both cases the

including zinc oxide (ZnO; SlovZink, a.s., Slovakia), stearic acid (AarhusKarlshamn, Sweden), sulfur (POCH, Poland), carbon black (IRB-7), N-tert-butyl-2-benzothiazyl sulfonamide (TBBS; Lanxess, Germany) were commercial grade.

2.2 Preparation of the composites

The compounding of the styrene-butadiene rubber, carbon black, fibers, and rubber additives was carried out with a 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 added in the following order: sulfur, stearic acid, fillers (carbon black or fibers), ZnO and TBBS. The loading ratio of fibers and carbon black was varied keeping the contents of the remaining components constant.

2.3 RPA measurement

The cure characteristics of the rubber compounds were measured on a Rotorless Shear Rheometer (RPA; Rubber Process Analyzer RPA2000, Alpha Technologies). The measurement was according to ASTM D 6204 at 160 °C.

2.4 Mooney viscosity [ML (1+4), 100 °C] measurement

The Mooney viscosity of the rubber compounds was measured with Mooney viscometer (Mooney MV2000, Alpha Technologies) according to the testing procedure described in ASTM D 1646. The Mooney viscosity was recorded after the sample was preheated for 1 min with total testing time of 4 min. The test temperature was set at 100 °C.

Ingredient Parts per hundred rubber (phr)A 1CB 2CB 3CB 1SF 2SF 3SF

SBR 100 100 100 100 100 100 100Sulfur 1.75 1.75 1.75 1.75 1.75 1.75 1.75

Stearic acid 1 1 1 1 1 1 1TBBS 1 1 1 1 1 1 1ZnO 3 3 3 3 3 3 3

Carbon black - 10 20 30 - - -Short fibers - - - - 10 20 30

Table 1. Formulation 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 34.41CB 0.71 9.60 7.0 14.7 0.32 38.12CB 0.97 12.01 6.0 12.7 0.36 43.73CB 1.29 14.51 5.2 11.9 0.61 50.51SF 0.93 10.69 8.7 16.4 0.31 39.62SF 1.3 13.98 7.9 16.7 0.20 48.13SF 1.84 18.71 7.3 15.1 0.46 57.6

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



41

reinforced fiber composite is subjected to load, the fibers act as carriers of load and stress is transferred from matrix along the fibers leading to effective and uniform stress distribution. The uniform distribution of stress is dependent on two factors, the population and orientation of fibers. At high fiber loadings, tear strength is found to decrease as the increased strain in the matrix between closely packed fibers increases tearing and reduces the tear strength. The value of elongation at break shows a reduction with increasing fiber loading. Increased fiber loading in the rubber matrix resulted in the composite becoming stiffer and harder. This will reduce the composite’s resilience and toughness and lead to lower elongation at break.

4. Conclusions

The obtained results show that short fibers can be used as interesting modifier of rubber blends, but for their application some specific aspects must be considered. The presence of fibers in compounds has advantageous influence on the vulcanization process and on formation of cross links in the elastomeric matrix. Therefore for the application of short fibers it is necessary to modify also the composition of the vulcanization system to ensure optimal vulcanization parameters. The nature of the elastomeric matrix must be taken in to account as well. The mechanical properties of the composites with carbon black are superior to those with fibers. Addition of short fibers (in compare with reference sample) led to slight increase of tensile strength but decreased the elongation at break of the compound. Addition of fibers also leads to increase in hardness and stiffness of the compounds. The use of silica and carbon black combined with different fiber sizes to reinforce the hybrid rubber composite will be the subject of future investigations.

Acknowledgements

Financial support for this research was provided by Synthos S.A., Oświęcim, Poland. The authors greatly appreciated the experimental support from Mr. A. Carr and Mr. P. Kwaczała at Synthos S.A.

optimum cure time, as well as the scorch time, have decreased compared to the control formulation. The reason behind the increase in curing rate of the filled compounds over the control compound can be mostly attributed to the influence of pH of the fillers. The pH of carbon black is about 10, and the pH of the fibers is about 9. It is known that additives having alkaline pH promote vulcanization by sulfur, accelerator and accelerator activator [22,23]. Crosslink formation between rubber chains occurs by sequences of reactions involving sulfur, accelerator and accelerator activator, which form an active sulfurating complex [24]. The concentration effect of the curatives in the filled compounds may be an additional reason for higher 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 increasing size of filler, incorporation and dispersion become difficult. Therefore, compounded rubbers become stiff and extent of cure value increases. The Mooney viscosity, taken as a measure of rubber compound viscosity, for the composites showed an increase with increasing both short fibers and carbon black.

3.2 Tensile properties

In the present study the behavior of composites containing fibers and carbon black were analyzed. The tensile properties and hardness value of rubber compounds containing various amounts of fillers are shown in Table 3. From the data in Table 3 it is seen that with an increase in the proportion of carbon black loading, the 100%, 200% and 300% moduli increase in the case of carbon black-rubber composites. It is known for a very long time that carbon black is enhancing the mechanical properties of rubber compounds.

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 composites depends on several factors such as structural aspect ratio and orientation of fibers in the final part, the degree of interfacial bonding between fiber and rubber matrices, the proper dispersion of fibers, and a balanced processability/stiffness/ flexibility relationship for the products [25]. When the

Mechanical properties A 1CB 2CB 3CB 1WF 2WF 3WF100% 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 2.96Elongation 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

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

References

[1] Hashim A.S. et al., Silica reinforcement of epoxidized natural rubber by the sol-gel method. Journal of Sol-Gel Science and Technology, 5, 1995, 211-218.

[2] Zhang Y. et al., Effect of Carbon Black and Silica Fillers in Elastomer Blends, Macromolecules, 34, 2001, 7056-7065.

[3] Kalaprasad G.N. et al., Crab Shell Chitin Whisker Reinforced Natural Rubber Nanocomposites. 1. Processing and Swelling Behavior, Biomacromolecules, 4, 2003, 657-665.



42

[14] De D. et al., Curing Characteristics and Mechanical Properties of Alkali-Treated Grass-Fiber-Filled Natural Rubber Composites and Effects of Bonding Agent, Journal of Applied Polymer Science, 101, 2006, 3151-3160.

[15] Mohan T.P. et al., Chemical treatment of sisal fiber using alkali and clay method, Composites Part A, 43, 2012, 1989-1998.

[16] Mishraa S. et al., Studies on mechanical performance of biofibre/glass reinforced polyester hybrid composites, Composites Science and Technology, 63, 2003, 1377-1385.

[17] Haqa M. et al., Hybrid bio-based composites from blends of unsaturated polyester and soybean oil reinforced with nanoclay and natural fibers, Composites Science and Technology, 68, 2008, 3344-3351.

[18] Hudaa M.S. et al., The effect of silane treated- and untreated-talc on the mechanical and physico-mechanical properties of poly(lactic acid)/newspaper fibers/talc hybrid composites, Composites Part B: Engineering, 38, 2007, 367-379.

[19] Kikuchi N., Composition for tread rubber of tires, U.S. Patent 5852097, 1998.

[20] Takase K. Rubber composition for pneumatic tire, Japanese Patent JP2006282790, 2006.

[21] Agostini L.D. et al., Tire tread for ice traction, U.S. Patent 5967211, 1999.

[22] Schmidt A.X. et al., Principles of High Polymer Theory and Practice: Fibers, Plastics, Rubbers, Coatings, Adhesives, Mc Graw Hill, 1948.

[23] Hofmann W., Rubber Technology Handbook, Hanser Publishers, 1989.

[24] Eirich FR., Science and Technology of Rubber, Academic Press, 1978.

[25] Goettler L.A. et al., Short Fiber Reinforced Elastomers, Rubber Chemistry and Technology, 56, 1983, 619-638.

[4] De D. et al., The effect of grass fiber filler on curing characteristics and mechanical properties of natural rubber, Polymer for Advances Technologies, 15, 2004, 708-715.

[5] Geethamma V.G. et al., Composite of short coir fibres and natural rubber: effect of chemical modification, loading and orientation of fibre; Polymer, 39, 1998, 1483-1491.

[6] Hanafi I. et al., Oil palm wood flour reinforced epoxidized natural rubber composites: The effect of filler content and size, European Polymer Journal, 33, 1997, 1627-1632.

[7] Maya J. et al., Mechanical properties of sisal/oil palm hybrid fiber reinforced natural rubber composites, Composites Science and Technology, 64, 2004, 955-965.

[8] Lopattananon N. et al., Performance of pineapple leaf fiber-natural rubber composites: The effect of fiber surface treatments, Journal of Applied Polymer Science, 102, 2006, 1974-1984.

[9] Zhang W. et al., Mechanochemical preparation of surface-acetylated cellulose powder to enhance mechanical properties of cellulose-filler-reinforced NR vulcanizates, Composites Science and Technology, 68, 2008, 2479-2484.

[10] Lovely M. et al., Mechanical Properties of Short-Isora-Fiber-Reinforced Natural Rubber Composites: Effect of Fiber Length, Orientation, and Loading; Alkali Treatment; and Bonding Agent; Journal of Applied Polymer Science, 103, 2007, 1640-1650.

[11] Martins M.A. et al., Tire Rubber-Sisal Composites: Effect of Mercerization and Acetylation on Reinforcement, Journal of Applied Polymer Science, 89, 2003, 2507-2515.

[12] Hanafi I. et al, Bamboo fibre filled natural rubber composites: the effect of filler loading and bonding agent, Polymer Testing, 21, 2002, 139-144.

[13] Hanafi I. et al., The effects of a silane coupling agent on curing characteristics and mechanical properties of bamboo fibre filled natural rubber composites, European Polymer Journal, 38, 2002, 39-47.



43

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 RepublicE-mail: [email protected], [email protected]

1. Introduction

In general, the shedding mechanism can be classified into two sections: the driving section and the transforming section. The transforming section of the shedding mechanism consists of joint mechanisms usually, which convert the rotational motion of the driving section into a feed reverse motion of the heald shaft. The course of load exerted upon the heald shaft depends upon the design of the parts of mechanism

The heald shaft is the frame in which there are fastened the 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

quantities on individual elements of mechanism that depend on mass parameters (rigidity, moment of inertia, mass) and on clearances in kinematic pairs of the mechanism (Figure 1).

This system is a complicated one as for the number of elements and the kinematic pairs. Mathematical model of the shedding mechanism has been formulated with the following assumptions:

a) mass of heald shaft and elements 7, 8, 9 are reduced to the joints of the elements 4 and 6,

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

Figure 1. Scheme of mathematical model of the shedding motion.



44

it exerts an important effect upon its dynamic loading. Some analyses have been dealt with in this process experimentally [9,10]. Because of this reason, it also constitutes one of the limiting elements impeding to increase its operational revolutions. In order to be able to describe the behavior of the heald during the weaving process, it is necessary to devise a suitable mathematical model that will describe its behavior during the operating cycle with a defined precision. The heald is influenced by a number of forces, which determine with which supporting wire it will be coupled. The most important ones are 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].

An important designing element influencing the behavior of the heald is the play in its fastening in the frame of the heald shaft. In the mathematical model, this play can be defined by means of the difference of positions of the upper and lower support wires. The distance of the lower support wire is shifted 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 threads are transmitted upon one of the couplings of the rods of the heald shaft only. For analysis of movement of the heald, we will assume that the frame of the shaft is absolutely rigid. In the mathematical model, this presumption will be reflected by the unchanging distance of both supporting wires in the course of the whole calculation, corresponding to the solution of movement of a heald fastened in the vicinity of the edge of a heald shaft. At present, the deformation of the main beams of the heald shaft during the working process are minimized by employing new types of composite rods.

As mentioned in the introduction, nowadays flat healds are employed that are made of a flat steel band by the pressing process. On the body of the heald, there are a number of orifices and stampings that serve e.g. for drawing-in machines or for other technological purposes. These shape parameters influence the strength and rigidity of the heald. Some healds have a stamping in the position of one suspension eye, which ought to provide for mutual spacing of healds; however, it reduces the rigidity of the suspension eye at the same time. Because of this reason, mathematical models are needed keeping in mind different rigidities of the upper and lower sections of the heald. In the mathematical model of the heald, we employ the Newtonian impact theory. The description of the fall of the heald upon the supporting wire employs the presumption of a perfectly elastic impact. We presume the velocity of the fall of the heald upon supporting wire up to 1 m.s-1.

The following part of the text describes the assembly of the model of a heald, by means of which we are able to find with 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 equations of the shedding motion. In all compiled models, the mass of the heald mn is concentrated in one mass point. The force To from the warp operates in the position of the thread eyelet. The mechanical properties of the yarn which is determined by the force of the warp in the mathematical model were determined experimentally [13-15]. The point

b) mass of elements 3, 5 are replaced by two masses concentrated in points and are considered as rigid,

c) rocking levers of elements 2, 4, 6 are rigid and are mutually joined by torsical rods ,

d) clearances in kinematic pairs are considered in elements 2 and 4, and

e) viscous damping in individual elements is also considered in the model.

Equations of motion of the system are formulated using Lagrange’s equation of the type II in the form

(1)

where i = 2, 4, 6. (K - kinetic energy, U - potential energy, R - dissipative function.)

Substituting different parameters K, U, and R in equation (1), we obtain the following equations of motion:

(2)

(3)

(4)

(5)

Clearances occurring in the kinematic pairs of the chains are replaced by angular differences of elements 2 and 4, which are incorporated into the model under the following conditions:

(6)

(7)

(8)

here i = 2, 4.

An experimental verification of the employed model of mechanical structure of the joint mechanism is described in [3]. The referred universal mathematical model of the shedding motion can be modified in a simple manner by entering the time-dependent lift dependence on the driving element, defining the course of its angular displacement. For example, it is possible to realize in this manner a calculation of the movement of a rotational dobby which is described in [4-8].

3. Mathematical model of the heald

3.1 Description of the heald problem

The studies realized up to now have shown that the heald is one of the most important parts of the shedding motion and

iiii qR

qU

qK

qddK

dtd

)()(

)()(...)(

44244222

442442222224244

224422

PP

PPPPP

bbkkIII

(2)

)()()()(...)(

66466444

664664442446466

246644

LLP

LLPPP

bbkkIII

(3)

LLNLLLLLLLL LFMbkI 44444444444 cos)()( (4)


0 iiPiiiP (6)

iiiPiiPiiiP (7)

iiiPiiPiiiP (8)

)()(

)()(...)(

44244222

442442222224244

224422

PP

PPPPP

bbkkIII

(2)

)()()()(...)(

66466444

664664442446466

246644

LLP

LLPPP

bbkkIII

(3)



0 iiPiiiP (6)

iiiPiiPiiiP (7)

iiiPiiPiiiP (8)



45

The individual phases of the solution of the concerned model can be resolved by means of equations (10) − (13). The start of the solution proceeds from the motion equation (10).

(10)

In the moment of equality (11), the heald leaves the upper supporting wire, and there follows a transfer of the heald between the main beams, which is solved according to equation (12).

(11)

(12)

The transfer is completed when the conditions (14) or (15) are fulfilled. The first potential state is the return of the heald on the upper rod (the condition 15 is fulfilled). In such a case, the movement of the heald is solved again according to equation (10).

If condition (14) has been fulfilled, the heald is entrapped on the lower supporting wire and the acceleration of the heald is solved according to relation (13).

(13)

(14)

(15)

The separation of the heald from the lower supporting wire will start in the moment when equality (11) is fulfilled. This transfer is again solved by means of motion equation (12). Once again, it is necessary to check two limit states. The first one is the return of the heald onto the lower rod (condition 14 has been satisfied), the second limit state is entrapping of the heald on the upper support wire (condition 15 has been fulfilled). If condition (14) is fulfilled, the solution of the motion of the heald will be realized employing motion equation (13). If condition (15) has been fulfilled, the movement of the heald is solved by the equation motion in form (10).

of application of this force is located in one mass point. It is possible to disregard the bowing of the heald due to its lateral loading. The devised models proceed from the assumption that the movement of the mass point substituting the heald is carried out on a straight line. In the solution of the system, the positions of the upper supporting wire (yh) and of the lower one (yd), position of the heald (yn), and position of the warp thread (yo) were established. The extent of the play in the fastening of the heald on the support wire is determined by the parameter f. The compiled models of the heald also consider the effect of the dimension of the thread eyelet J upon the course of the force in the warp.

The initial conditions of the solution proceed from the presumption that the heald is entrapped on the upper supporting wire, and both its velocity and acceleration are identical with those of the upper supporting wire.

The solution of individual mathematical models has been realized by means of a devised software program. The solution of compiled differential equations describing the shedding motion coupled with an analysis of the movement of heald during the weaving cycle has been affected by the Runge-Kutt method of the 4th order. During the calculation, the courses of the principal kinematic and force quantities of the system have been studied.

3.2 Solution of the heald problem

The system subject to solution can be represented schematically according to Figure 2. The body of the heald is modeled by means of the Kelvin-Voigt visco-elastic rheologic model with the rigidity knH and co-efficient of viscous damping bnH in the upper part, and the rigidity knD and co-efficient of viscous damping bnD in the lower part of the heald. A general motion equation of this model can be written as

(9)

The conditions for the solution of the concerned equation follow from an equilibrium of forces on the heald, and – as mentioned above − they consider the play in the fastening of the heald on the supporting wire. The control constants H and D assume the values 0 and 1, and they determine which members of the equation will be employed in the calculation.

Figure 2. Schematic model of the system shedding mechanism – heald.

)(.)(.)(.)(.

dnnDdnnD

nhnHnhnHnonn

yybDyykDyybHyykHgmTym

)()( nhn

nHnh

n

nH

n

on yy

mbyy

mkg

mTy

0 gmTym nonn (11)

gmT

yn

on (12)

)()( dnn

ndn

n

n

n

on yy

mbyy

mkg

mTy (13)

hn yy (14)

hn yy (15)

)()( nhn

nHnh

n

nH

n

on yy

mbyy

mkg

mTy

0 gmTym nonn (11)

gmT

yn

on (12)

)()( dnn

ndn

n

n

n

on yy

mbyy

mkg

mTy (13)

hn yy (14)

hn yy (15)

)()( nhn

nHnh

n

nH

n

on yy

mbyy

mkg

mTy

0 gmTym nonn (11)

gmT

yn

on (12)

)()( dnn

ndn

n

n

n

on yy

mbyy

mkg

mTy (13)

hn yy (14)

hn yy (15)



46

between individual supporting wires. In this mathematical 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 of this model, it is possible to determine the loads exerted upon individual end eyelets of the heald. 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 the heald shaft that are employed in weaving looms nowadays.

From the detailed analysis of theoretical calculation obtained for different operating frequencies, it has been found that the moments of the drop or of the separation of the heald from the supporting wire are comparable with records of the acceleration. From the record, the behavior of the heald upon the supporting wire depending upon the operating frequency can be seen. An important factor, which can be evaluated, is the number of bounces of the heald after the drop upon the supporting wire, after the transfer between the main beams of the heald shaft.

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, with the aim to describe the behavior of the heald during weaving cycle and to propose possible adaptations of the design.

Dedication: The paper has been elaborated with financial support of TUL in the framework of specific university research competition.

The effect of the thread eyelet is included in the calculation by means of the following conditions:

(16)

3.3 Results

The control algorithm of the calculation checks the position of the heald with respect to the supporting wire of the heald shaft. As mentioned above, four possible states can arise which have been studied and on the basis of the realized calculation of the movement of the heald. An example of calculated dependencies is given in Figure 3, showing the principal kinematic courses of the supporting wire and of the heald. The calculation has been realized for the velocity of the shedding motion 300 r.p.m. An example of the course of calculation in case of this model is given in Figure 4.

4. Conclusion

For the generation of a real mathematical model, the model with the rigidity substitution of the heald by means of the Kelvin-Voigt visco-elastic model has proved suitable. The referred enhancement allows for determining the number and extent of bounces of the heald from the supporting wire after its transfer

22

22

02

nOn

nOn

On

yyy

yyy

yy

(16)

Shedding motion rpm150 rpm 300 rpm 450 rpm

Maximal value of acceleration of heald after its transfer on upper rod [m.s-2] 1220 1340 1477

Maximal value of acceleration of heald after its transfer on lower rods [m.s-2] 671 906 1080

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

Figure 3. Relative movement of the heald with respect to upper supporting wire, operating velocity of the shedding motion 300 r. p.m.

-0 .5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

0.00 3.14 6.28 9.42 12.56 15.70 18.84

angle of rotation [rad]

path

of t

he re

lativ

e m

omen

t of t

he h

eald

[mm

]

path of the relative moment of the heald – calculation (model 2)[mm]

1

2

3

4

0.00 3.14 6.28 9.42 12.56 15.70 18.84úhel pootočení [rad]

fáze

poh

ybu

nitě

nky

[-]

fáze pohybu nitěnky [-]



47

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.

-1500

-1000

-500

0

500

1000

0.00 3.14 6.28 9.42 12.56 15.70 18.84


acce

lera

tion

[m.s

-2]

a ccelera tion o f the hea ld zrych len í nosného drá tu

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

0.00 3.14 6.28 9.42 12.56 15.70 18.84


velo

city

[ms-

1]

veloc ity o f the hea ld veloc ity o f the supporting w ire

-0.06

-0.04

-0.02

0.00

0.02

0.04

0.06

0.00 3.14 6.28 9.42 12.56 15.70 18.84


disp

lace

men

ent [

m]

l i ft o f upper supporting w ire lift o f low er supporting w ire m ovem ent o f the hea ld



48

[6] Terentyev, V.I., Smirnov, B.N. Dynamics of a shedding mechanism with flexible links. Izvestiya Vysshikh Uchebnykh Zavedenii, Seriya Teknologiya Tekdtil´noi Promyshlennosti - Issue 2, 2011, Pages 80-83. Russia

[7] Korolev, P.A., Lohmanov, V.N. Kinematics of connections of the shedding mechanism of a circular loom TKP-110-U. Izvestiya Vysshikh Uchebnykh Zavedenii, Seriya Teknologiya Tekstil´noi Promyshlennosti - Issue 4, 2011, Pages 116-119. Russia

[8] Kapucu, S., Das, M., T., Kilic, A. Cam Motion tuning of Shedding Mechanism for Vibration Reduction of Heald frame. Gazi University Journal of Science – Volume 23, Issue 2, 2010, Pages 227-232. Turkey

[9] Akamura, T., Kinari, T., Shimokawa, T., Miyashita, D., Mochizuki, Y., Shintaku, S. Jumping behavior of heald in a shedding motion of loom. Journal of Textile Engineering , Volume 52, Issue 2, 2006, Pages 87-92. Japan

References

[1] Mrázek, J.: Theoretical analysis of dynamics four-bar beat up mechanisms of a loom. In.: Mechanism and machine theory, Pergamon Press, 1992, pp. 125-136. USA

[2] Bílek, M.; Mrázek, J. Dynamic Stress of Heald Shaft of Weaving Looms. Vlákna a textil, 1998, no.3, pp. 131-134, Slovakia.

[3] Beran J.; Bílek M. Matematické modelování základních mechanismů tkacího stroje. In TRANSFER 2000. Trenčín: TnU, Slovensko, 2000. s 25-30.

[4] Recep E.; Gülcan Ö.; Yildiray T.: Kinematics of Rotary Dobby and Analysis of Heald Frame Motion in Weaving Process. Textile Research Journal, 2008 Vol. 78, No. 12, pp. 1070-1079, USA,

[5] Eren R.; Ozkan G; Mehmet Karahan M.: Comparison of Heald Frame Motion Generated by Rotary Dobby and Crank & Cam Shedding Motions. FIBRES & TEXTILES in Eastern Europe. Vol. 13, No. 4 2005,

Table 2. Table of the used symbols.

Symbols Description Unitw Angular velocity rad.s-1

F Clearance in a joint radα, b, γ Angles between the parts of the shedding mechanism rad

n Working speed mechanism r-p-mbnH 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-1

TO Force component acting in the warp direction of healdshaft NJ Height of yarn guides mf Clearance in the attachment between supporting wire and heald mg Gravity acceleration m.s-2

y Height of shed ml Displacement of warp-line m

FNL Load of healdshaft Nmn Weight of heald KgK Kinetic energy JU Potential energy JR Dissipative function JD Dissipative energy JU Dissipative work J

k2, k4, k6l Torsional stiffness N.m.rad-1

b2, b4, b6l Viscous damping torsional coefficient N.m.s.rad-1

I2P, I4, I4l, I6, I6L Moment of inertia kg.m2

jiP, jiP Rotation of parts of the mechanism radϕ&

iP, ϕ&

iP Angular velocity of parts of the mechanism rad.s-1

ϕ&&iP,

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

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



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[13] TUMAJER, P., URSÍNY, P., BÍLEK, M., MOUČKOVÁ, E.: Use of the vibtex vibration system for testing textiles, AUTEX Research Journal, Vol. 11, No2, June 2011, ISSN 1470-9589,

[14] Tumajer P., Ursíny P., Bílek M., Moučková E.; Research Methods for the Dynamic Properties of Textiles. FIBRES & TEXTILES in Eastern Europe 2011, Vol. 19, No. 5 (88) pp. 33-39.

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[10] BÍLEK, Martin; KOVÁŘ, Šimon. Record of the movement of heald in the weaving loom. In IX. International Conference on the Theory of Machines and Mechanism in association with the II. CEACM Conference on Computational Mechanics 2004. Liberec : TUL, 2004, pp. 87-92.

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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, Iran2Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran

E-mail: [email protected], [email protected]

Introduction

During the past decades, human health has been seriously threatened by environmental pollution, especially indoor microbiological contamination (SARS, Influenza, etc.). The statistical figures reveal that the total number of deaths caused by bacterial infection exceeds 17 million, about one-third of world-wide deaths [1]. Textiles can, thus, enhance cross-contamination by pathogenic microorganisms in environments such as home and hospitals. Textile materials provide an excellent environment for microorganisms to grow, because of their large surface area and ability to retain moisture. Microbial activity can be detrimental to textiles. It can cause unpleasant odor, lead to weakening of the substrate, discoloration, and even contribute to the spread of disease. For this reason, antimicrobials have been investigated as a finish for textiles [2,3].

Antibacterial finishes are applied to textiles for three major reasons: (a) to contain the spread of disease and avoid the danger of injury-induced infection, (b) to contain the development of odor from aspiration, stains, and soil on textile materials, and (c) to contain the deterioration of textiles caused by mildew, particularly fabrics made of natural fibers [4]. Various methods, 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

environmental pollution [15]. For instance, certain fluorocarbon finishes, especially those consisting of eight carbons in the perfluoro alkyl chain, can degrade to form perfluorooctanoic acid. Perfluorooctanoic acid is of environmental concern because it bioaccumulates in human body [16]. The Environmental Protection Agency has taken measures to limit the use of perfluorooctanoic acid in the industry [17].

Natural dyes are believed to be safe because of their non-toxic, non-allergic, and biodegradable nature. Many of the plants used for dye extraction are classified as medicinal, and some of them have recently been shown to possess remarkable antibacterial activity [18-22]. Curcuma longa L. known as turmeric, which is used as a coloring agent, has medicinal properties [23-25]. Curcuma longa L., which belongs to the Zingiberaceae family, originates from the Indian sub-continent and possibly neighboring areas of Southeast Asia, but it is nowadays widely grown throughout the tropics. The pigments in the colorant extracts obtained from Curcuma are collectively known as curcuminoids, the major constituent being curcumin, along with small amounts of demethoxycurcumin and bis-demethoxycurcumin (Figure 1) [26]. Turmeric has been isolated from the rhizome of C. longa, attributing biological activities such as antioxidant, anti-inflammatory, wound-healing, anticancer,

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

Figure 1. Structures of curcumin and its analogs.



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Color measurements

The dyed polyamide fabrics were individually tested for their color strength. The color strength (K/S) values of the dyed fabrics were instrumentally determined by reflectance spectrophotometer (BYK-Gardner, India, with CIELAB 1976 color space and D65-light source) with Kubelka–Munk equation as follows:

(1)

where R is the reflectance of the dyed fabric at the maximum absorption wavelength, S is the scattering coefficient, and K is the absorption coefficient of the dyed fabrics.

Antibacterial test

Antibacterial activity against Gram-positive bacteria (S. aureus) and Gram-negative bacteria (E. coli) was tested quantitatively by AATCC Test Method 100-1999. The number of viable bacterial colonies on the agar plate before and after dyeing was counted and the results reported as percentages of bacteria reduction according to

R = (B-A)/B × 100 (2)

where R denotes the percentage of reduction of microbial population; B is the absorbance of the media inoculated with microbes and un-dyed fabric; and A shows the absorbance of the media inoculated with microbes and dyed fabric.

Durability to laundering

Durability of antimicrobial activity to washing is one of the major concerns of textile researchers and users because textiles are subjected to frequent laundering. The treated samples with 30% concentration of turmeric were washed under condition of the ISO 105-CO2 Test Method to determine the bacteriostatic effect of fabrics after 1, 5, 10 and 20 cycles of laundering.

Results and discussion

Toxicity assay

The results demonstrate that turmeric at different concentrations caused no inhibition to germination and root growth to the green grams and a growth rate of more than 90% was observed. The untreated and treated green grams were almost equal in their germination and growth rate. Thus, the turmeric was found to be non-toxic.

Color strength of polyamide fabrics

The majority of natural dyes need a mordant in the form of a metal salt to create an affinity between the fiber and the pigment. These metals form a ternary complex on one side with the fiber and on the other side with the dye. Such a strong coordination tendency enhances, the interaction between the fiber and the dye, resulting in high dye uptake.

anti-proliferative, antifungal, and antibacterial activity [27]. Ghoreishian and coworkers dyed silk fabric with turmeric and proved antibacterial properties to silk fabric [28]. Sundrarajan et al. modified cotton fabrics with enzymes and chitosan, and reported the enhancement of dye uptake and washing fastness of cotton fabrics dyed with turmeric [29].

Polyamide has been one of the most widely used polymers in various industries such as fiber, film, and plastic. It has major advantages of high modulus and strength, stiffness, stretch, wrinkle, and abrasion resistances [30]. However, polyamide can be easily attacked by bacteria in vivo. In this study, simultaneous antibacterial and dyed polyamide fabric was prepared by turmeric natural dyeing in the presence of various mordants, and we also focused on the antibacterial activity of treated fabrics against two common pathogenic bacteria: Escherichia coli(E. coli) and Staphylococcus aureus (S. aureus).

Experimental section

Materials

The polyamide (nylon 6.6) fabric was used with warp density 50 ends/cm and weft density 28 ends/cm. The turmeric was purchased from Iranian traditional natural dyers. Mordants such as potassium aluminum sulfate, cupric sulfate, and ferric sulfate were purchased from Merck. Escherichia coli, a Gram-negative bacterium, was selected due to its popularity as a test organism and its resistance to common antimicrobial agents. Staphylococcus aureus, a pathogenic Gram-positive bacterium, was used because it was the major cause of cross-infection in hospitals and it is the most frequently evaluated species. Cultures of the following microorganisms were used in the study: S. aureus ATCC 25922 and E. coli ATCC 25923.

Toxicity assay

Turmeric solution containing 1 g⁄100 ml was prepared and, 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. Then 10 surface-disinfected green grams were placed on the wetted paper. After 14 days of incubation at 27±°C, the total root growth (germination) was measured and compared with the control (untreated sample) and was expressed as root growth inhibition percentage [31].

Dyeing procedure

To study the relationship between dye concentration and antimicrobial activity, 100% polyamide fabrics were dyed with 5, 10, 20, and 30% turmeric on weight of fabric (OWF) with potassium aluminum sulfate, cupric sulfate, and ferric sulfate mordants, and un-mordant. The polyamide fabric was dyed in an AHIBA dyeing system with turmeric dye. The dye bath comprised dye, 1% acetic acid, and 3% mordant. The liquor ratio was kept at 40:1. The temperature was raised to 100°C by a thermal gradient of 2°C/min, and dyeing operation continued for 60 min.

RR

SK

2)1( 2−

=



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Bacteriostatic activity

Table 1 shows the photographs of bacterial growths upon treated polyamide fabrics. Figures 3 and 4 exhibit comparative diagrams of bacteriostatic activity results for the treated sample in the presence of E. coli and S. aureus bacteria. Curcumin

Figure 2 shows the graph of treated samples K/S dyed by turmeric (20%). The result of dyeing samples shows that using mordants considerably increased dye absorption leading to higher K/S values in case of mordanted samples than un-mordanted ones. Ferric sulfate mordant was found to have the most prominent effect on color strength.

Turmeric concentration

(OWF, %)

S. aureus

Cupric sulfate Ferric sulfate Potash alum Un-mordanted Raw sample

10

30

E. coli

10

30

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

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



53

effects. Hence, it is suggest that the turmeric dye can be used for dyeing polyamide as an alternative to the very expensive, synthetic, and toxic antibacterial agents.

Washing fastness properties

Textiles are subjected to frequent washing, rubbing, and sweating during their use and the requirement of durability is a very important parameter. Figures 5 and 6 depict the durability of antibacterial activity after repeated home launderings. As shown, the antibacterial activity reduced with increased number of washing cycles. The inhibition rate of treated sample un-mordant was more reduced than the treated sample with mordant after laundering.

Conclusion

This is the first report where turmeric, used in polyamide dyeing, has been shown as a source of a natural, non-toxic dye. This

found in turmeric affects RNA and DNA of microorganisms and their fights.

The bacteriostatic activity of treated fabrics was ranked as ferric sulfate > cupric sulfate > potassium aluminum sulfate > un-mordant against S. aureus and cupric sulfate > ferric sulfate > potassium aluminum sulfate > un-mordant against E. coli.

Based on the obtained results, specimens showed a better efficiency against E. coli in comparison with S. aureus. This can be explained by the difference between thicknesses of the cell walls. Staphylococcus aureus has a thicker cell wall [32]. They also showed that using mordant had better bacteriostatic activity. It is well known that the metallic salts used as mordants exhibit toxic effects against the pathogens.

Natural dyes are non-toxic, biodegradable, and do not cause pollution and wastewater problems, while synthetic dyes have been known to cause health hazards due to their carcinogenic

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.



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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 to produce an ideal antibacterial polyamide fabric. A common dyeing process provides polyamide with color and antibacterial properties. Since the dyeing process and bacteriostatic finishing have been conducted in one step and do not require an additional step, this method is cost-effective. Natural-dyed

polyamide presented a strong bacteriostatic activity against two well-known pathogenic bacteria S. aureus and E. coli. Turmeric is more effective against E. coli than S. aureus. Moreover, using mordant had better bacteriostatic activity. The bacteriostatic activity of turmeric mordant-finished polyamide is more durable to home laundering than the un-mordanted ones.

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