Textile Research Journal

http://trj.sagepub.com Cotton Cellulose 1, 2, 3, 4 Buthanetetracarboxylic Acid (BTCA) Crosslinking Monitored by some Physicalchemical Methods
Olivera Sauperl, Karin Stana-Kleinschek and Volker Ribitsch Textile Research Journal 2009; 79; 780 DOI: 10.1177/0040517508096222 The online version of this article can be found at: http://trj.sagepub.com/cgi/content/abstract/79/9/780

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Textile Research Journal

Article

Cotton Cellulose 1, 2, 3, 4 Buthanetetracarboxylic Acid (BTCA) Crosslinking Monitored by some Physicalchemical Methods
Abstract

Olivera auperl1 and Karin Stana-Kleinschek

University of Maribor, Faculty of Mechanical Engineering, Laboratory for Characterization and Processing of Polymers, Smetanova 17, 2000 Maribor, Slovenia

In this research, the influence of the alkaline modification of cotton cellulose on the crosslinking with 1, 2, 3, 4 buthanetetracarboxylic acid (BTCA) is investigated. In order to anticipate changes after alkaline modification the crystallinity change was evaluated using wide angle Xray diffraction (WAXD), iodine adsorption measurements, and the Knecht method. Tensiometry, the methylene blue method, and the streaming potential method enable hydrophilic/hydrophobic character estimation, carboxyl group content determination, evaluation of dissociation/sorption fiber characteristics, as well as electrokinetic properties characterization. All these parameters define the changes at the accessible polymer surfaces and therefore reflect the relationship between the changed crystallinity and the incorporation of the BTCA molecules into accessible regions of cotton cellulose. It has been concluded that the crystallinity degree characterizes crosslinking effectiveness of cotton cellulose crosslinked with BTCA. Mercerized materials show after crosslinking higher contact angles and retain a higher number of carboxyl groups. Electrokinetic properties are in correlation with carboxyl group amount. It has been confirmed that the physicalchemical methods which were used in this research are suitable methods for the crosslinking efficiency evaluation.

Volker Ribitsch
University of Graz, Institute of Chemistry, Rheology & Colloid Science, Heinrichstrae 28, 8010 Graz, Austria

Key words crystallinity, cotton cellulose, mercerization, Knecht method, iodine adsorption, BTCA, crosslinking, tensiometry, methylene blue method, zeta potential

In general, fibers are formed of microfibrils which consist of an assembly succession of crystallites and intermediate disordered amorphous regions [13]. The amorphous regions and inner surface area of voids significantly influence reactivity and sorption properties of fibers.1 The natural crystal is made up from metastable cellulose I with all the cellulose strands parallel and no inter-sheet

hydrogen bonding. This cellulose I (that is, natural cellulose) contains two coexisting crystal phases, cellulose I (triclinic) and cellulose I (monoclinic), in varying proportions depend-

1 Corresponding author: tel +386 2 220-7889; fax.:+386 2 2207990; e-mail: olivera.sauperl@uni-mb.si

Textile Research Journal Vol 79(9): 780791 DOI: 10.1177/0040517508096222

www.trj.sagepub.com 2009 SAGE Publications Los Angeles, London, New Delhi and Singapore

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Figure 1 Supermolecular structure of cellulose fibres schematically [1].

ent on its origin, I being found more in algae and bacteria whilst I is the major form in higher plants [4]. Crystalline structure of native cotton cellulose is classified as cellulose I; it can in addition adopt other polymorphic crystal structures. When native cellulose is treated with relatively strongly alkaline solutions (e.g. NaOH), cellulose adopts a modified crystal structure called hydrate cellulose, mercerized cellulose, regenerated cellulose or, more generally, cellulose II [1,5,6]. Besides cellulose I and cellulose II other polymorphic lattice structures (e.g. cellulose III and IV) are known [1,6]. Cellulose II can be obtained in the mercerization process of cotton, which proceeds via the formation of sodium cellulose by interaction of the polymer with aqueous sodium hydroxide and subsequent decomposition of this intermediate by neutralization or washing out of the sodium hydroxide. In general, the process of transformation of cellulose I to cellulose II is considered an irreversible reaction [7]. The modification of cotton cellulose with sodium hydroxide (1624%) causes significant changes of supermolecular structure determinable by X-ray diffraction. Alkaline modification (mercerization) changes the cellulose at the molecular and macromolecular level [8]. Because of the changes in the fine structure of the fibers (cellulose I changes to cellulose II) the sorption properties of the mercerized fibers are altered [9,10]. The decrease in crystallinity and the increase of amorphous fraction caused by alkaline treatment (mercerization) lead to an increased accessibility of the reactive hydroxyl groups of cellulose fibers which act as active sites where different reactions (e.g. etherification, esterification) occur. The differences between the lattice structures of cellulose I and cellulose II are shown in Figure 2. Accessible hydroxyl groups of cotton cellulose take an active part in crosslinking reactions which can be used to gain/introduce mechanical properties modification [11]. Some reagents used for crosslinking of cotton cellulose react with hydroxyl groups of cellulose fibers in such a way that a crosslinked structure is formed. Applying this treat-

Figure 2 Comparison of crystallographic unit cell of (a) cellulose I and (b) cellulose II [1].

ment, certain exploitable and preservative properties of these materials are obtained [11,12]. Polycarboxylic acids appear as very promising non-formaldehyde crosslinking agents to replace the traditional, mostly formaldehydebased, compounds [1317]. Among these acids 1, 2, 3, 4, buthanetetracarboxylic acid (BTCA) has shown the best results. Crosslinking results from the esterification of the hydroxyl groups of cellulose fibers with carboxyl groups of BTCA. The following mechanisms are proposed: according to Yang et al. a cyclic anhydride is formed first which in the next phase forms an ester with the hydroxyl group of cellulose fibers (Figure 3) [13,14,18,19]. According to the second mechanism (Figure 4) [15] a mixed linear anhydride is formed in the presence of the catalyst (NaH2PO2.H2O). In this study the influence of the changed crystallinity and subsequently changed sorption properties on the cotton cellulose crosslinking is investigated. Crystallinity change was monitored using different techniques: wide angle X-ray diffraction (WAXD), the Knecht method, and the iodine adsorption measurements [2022]. The hydrophilic/hydrophobic properties (hydrophilicity/hydrophobicity) of cotton cellulose were determined using the Powder Contact Angle Method, which is based on measuring the changed samples mass during adsorption of liquids. The contact angle between the solid phase (fibers) and the liquid phase (water) was calculated using the modified Washburn equation on the basis of measured capillary velocity [2327].

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Figure 3 The mechanism of crosslinking of hydroxyl groups of cellulose with BTCA as a result of the formation of cyclic anhydride [18].

Figure 4 The mechanism of crosslinking of hydroxyl groups of cellulose with BTCA as a result of the formation of linear mixed anhydride [15].

Considering the crosslinking mechanism we can suppose that the additional free BTCA carboxyl group which is accessible in the cellulose polymer reflects the effectiveness of cotton cellulose crosslinking. A comparison of accessible carboxyl group amount into crosslinked mercerized and alkaline unmodified (raw) cotton cellulose can be made using the methylene blue method, where the adsorption of methylene blue dye on the cellulose material is monitored spectroscopically. The methylene blue method is based on the ion-exchange capacity of the cellulose polymers. The dye methylene blue binds to acid carboxylic groups of fibers by the principle of ion exchange. Since the treatment is carried out in an alkaline medium (pH = 8.5), the carboxyl groups of the bound BTCA are present in the carboxylate form. Another explanation is that the dye methylene blue can be also adsorbed non-specifically on the fiber surface [28]. Based on the methylene blue method one can also predict how the structural changes of sodium hydroxide treated cotton cellulose influence the accessible carboxyl group amount of the crosslinked cellulose fibers [7,29]. The effectiveness of crosslinking was also studied on the basis of the electrokinetic properties of cotton cellulose crosslinked with different mass fractions of BTCA (w(BTCA) = 1%, 3%, 5%, 7%) in the reaction solution. Electrokinetic properties describe the electrical potential of a solid surface, if this is moved in respect to the surrounding liquid phase. It is described by the zeta potential (), the surface potential at the border line between the stationary and mobile liquid phase. It can be assumed that the surface

potential influences strongly different kinds of solidliquid interactions. Free carboxylic groups of BTCA which are present in the crosslinked material have an influence on the electrokinetic character of the materials. The streaming potential of mercerized and afterwards crosslinked cotton cellulose was measured as a function of the pH and the zeta potential was determined [30,31].

Experimental
Materials
The investigations were carried out on raw (unmercerized) and alkaline treated (mercerized) 100% cotton fabric. The surface mass (167 g/m2), warp density (47 threads/cm), filling density (24 threads/cm) and the weave (3-way basic twill) were the same in both types of fabric. Pre-treatment including alkaline modification (mercerization) was carried out in the firm MTT Tekstil d.o.o. Maribor according to its technological procedure. For the alkaline modification (NaOH, w(NaOH) = 24%) a classical technological procedure was used [12].

Crosslinking Procedure
Samples were crosslinked following the procedure of dry crosslinking. This included impregnation with BTCA (Fluka), drying at T = 100C, and crosslinking at 170C. BTCA was

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Table 1 The content of the BTCA in the reaction bath and the conditions of crosslinking.
Mass fraction of BTCA w(BTCA) (%) Mass fraction of catalyst w (NaH2PO2.H2O*) (%) pH Liquor pick up (%) Drying temperature Tdrying (C) Drying time tdrying (min) Crosslinking temperature Tcrossl. (C) Crosslinking time tcrossl. (min) 1, 3, 5, 7 1, 3, 5, 7 2,2 100 100 10 170 3

tion. After standing for 1 hour with frequent shaking, the supernatant solution can be analyzed for the iodine content. The quantity of iodine taken up by the cotton cellulose is calculated as milligrams of iodine per gram of absolutely dry cotton cellulose from the difference in titer of the supernatant solution and of a blank solution [32,33]. For titration 0.01 N sodium disulfate (IV) and a starch solution as an indicator was used: ( a b .1,33 ) . f .2,5384 - (mg/g) ISV = -------------------------------------------------m (1)

used in different mass fractions with NaH2PO2.H2O as catalysts. The amount of applied BTCA is expressed as a weight percentage based on the original weight, so called wet pickup. The conditions of crosslinking are shown in Table 1. After crosslinking the samples were rinsed at room temperature until the conductivity of distilled water (0.4 (s/cm)) was reached.

where ISV is the iodine sorption value (mg/g), a is ml of sodium disulfate (IV) solution equivalent to initial iodine in the aliquot of the sample solution, b is ml of sodium disulfate (IV) solution for the aliquot of supernatant filtered from the sample, f is the aliquot factor, and m is the mass of the absolutely dry cotton cellulose sample.

The Knecht Method

The adsorption of the substantive dye on the fiber was followed using the Knecht method [11]. The raw and mercerized samples were dyed using the substantive dye Tobazol Scharlach 4BS (Cinkarna Celje). The conditions for dyeing are shown in Figure 5. The remission values of the dyed samples were measured using a spectrophotometer, type Datacolor Spectraflash SF600. A numerical assessment of the dye difference between raw and mercerized samples was carried out in accordance with the system CIELAB (Eab* = 6.04), where color difference was calculated according to [34] E* =
2 2 2 ( L ) + ( a ) + ( b )

Methods
Wide Angle X-ray Diffraction
With WAXD the influence of the alkaline modification on cotton cellulose crystallinity change was estimated. The crystallinity of raw and mercerized cotton cellulose was calculated using Hermans/Weidinger and Ruland/Vonk equations. WAXD analyses were performed in the Chemical Institute Karl Franzens, University of Graz. Two circle goniometer (A. Paar), positional sensitive detectors and spherical stops were used. Measurements were carried out with X-ray generator Philips PW 2253/11 under accelerating voltage 50 kV and electric current 45 mA. As X-ray source Cu-anode was used (CuK: = 1.542 ). Experimental curves were corrected for: absorption, incoherent diffraction, and polarization. In such a way, the mathematical correction of experimental curves was processed.

(2)

where L* represents the difference in lightness (L* reference sample L* sample), a* the difference on the axis red/green (a* reference sample a* sample) and b* the difference on the axis yellow/blue (b* reference sample b* sample) and E* the color difference.

Tensiometry
The hydrophilic/hydrophobic character of the fibrous materials can be measured using tensiometry. The Powder Contact Angle Method was used for the contact angle determination. This method is based on measuring the samples mass changes during adsorption of liquids. The contact angle between the fibers and water was calculated using modified Washburn equation (equation (3)) on the basis of measured capillary velocity (mass2/t): mass - -----------------cos = ------------2 t c
2

Iodine Sorption Measurement

As proposed by Schwertassek the iodine sorption method is an empirical method to detect the extent of alkaline modification on the basis of the amount of adsorbed iodine. Using iodine sorption value (ISV) (equation (1)) the crystallinity change can be calculated by comparing the amount of adsorbed iodine. The method procedure is to apply 1.2 ml of a concentrated potassium iodide solution (5 g I2, 40 g KI, 50 ml water) to 0.2 g of cotton cellulose, mix well, let it stand for 3 min and transfer it into 100 ml saturated sodium sulfate decahydrate (Na2SO4x10H2O) solu-

(3)

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Figure 5 Dyeing conditions according to the Knecht method.

where mass2 is the sample mass/g, t is the time (s), is the liquid viscosity (m Pa s), is the liquids density (g/cm3), is the surface tension of the liquid (N/m), is the contact angle between the solid and liquid phases (), and c is the material constant or c factor mass2 sample mass (g). The constant c was determined according to equation (4), where r is average radius for the pores/mm and nk number of capillaries: 1 - . 2 . r2 . n2 c = -k 2 (4)

cally, employing a calibration plot. The total amount of free, i.e. non-adsorbed, methylene blue was calculated. The dye methylene blue binds to acid carboxylic groups of fibers by the principle of ion exchange. Because the treatment is carried out in an alkaline medium (pH = 8.5), the carboxyl groups of bound BTCA are found in carboxylate form: B+A + CelCOO CelCOO B+ + A

The constant c depends on the type of measured sample and the measuring cylinder and is determined measuring the wetting behaviour of the solid sample (fibers) using liquids providing complete wetting, such as hexane and heptane where the contact angle equals zero and cos is 1. When the material has the ability to be wetted with liquid, then the values of the contact angle are between 0 and 90 [2427]. For each individual sample three parallel measurements were performed under identical experimental conditions. The results were statistically evaluated with a standard deviation.

where B+A dye is in the form of salt. The dye methylene blue can be also adsorbed non-specifically on the fiber surface [28]. The number of carboxyl groups relative to the mass of the absolutely dry cellulose sample is calculated from the amount of unbound methylene blue dye as follows: (COOH amount) = (7.5 A) x 0.00313 m (5)

Spectrophotometric Methylene Blue Method

A weighted oven-dry cellulose sample (approximately 0.5 g) of known water content up to 0.5 g was suspended in 25 ml of aqueous methylene blue chloride solution (300 mg/l) and 25 ml of borate buffer of pH = 8.5 for 1 h at 20C in a 100 ml Erlenmeyer flask and then filtered through a sintered-glass disk. Five or 10 ml of the filtrate were transferred to a 100 ml calibrated flask. Then 10 ml of 0.1 N HCl and subsequently water, up to 100 ml, were added and the methylene blue content of the liquid was determined spectrophotometri-

where is COOH groups amount (mmol/g), A is the part of unbound dye methylene blue (g), and m is the mass of the absolutely dry sample of cellulose (g) [7,29,35]. The concentration of the dye solution was determined using the Perkin Elmer Lambda 2 UV/VIS spectrophotometer. For each individual sample three parallel measurements were performed under identical experimental conditions. The results were statistically evaluated with a standard deviation.

The Streaming Potential Method

The streaming potential method is one of the possible ways to obtain information about the nature of charges of solide (fiber) surfaces. This technique enables the determination of electrokinetic properties, i.e. the zeta potential (), of fiber systems, which is calculated from the streaming potential (US) data using the Smoluchowski equation:

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(6)

Table 2 Degree of crystallinity of raw and mercerized cotton cellulose.

Sample Raw cotton cellulose Mercerized cotton cellulose wc,x (HW) 0.567 0.029 0.503 0.033 wc,x (RV) 0.569 0.034 0.469 0.052

where is the zeta potential, Us the streaming potential, p the hydrodynamic pressure difference across the plug, the liquid viscosity, the liquid permittivity, 0 the permittivity of free space, L the length of the plug, Q the crosssectional area of the plug, and R the electrical resistance across the plug. Equation (6) is adequate for most practical systems. The term (L/Q) consists of two parameters neither of which can be easily measured. In the Fairbrother and Mastin approach the term (L/Q) is replaced by (Rs s), where Rs is the electrical resistance of the plug when the measurement cell is filled with an electrolyte whose specific conductance, S, is accurately known. Thus, equation (6) becomes: Us Rs . s - ----------- ----------- = ----p 0 R (7)

For most practical systems equation (7) is perfectly adequate and was used in this study. If the surface conductance has to be taken into account a 0.1 n KCl is used instead of the standard electrolyte. Electrokinetic properties of uncrosslinked samples and crosslinked samples with different mass fractions of BTCA in the reaction bath (w(BTCA) = 1%, 3%, 5%, and 7%) were monitored with the streaming potential measurements. The swelling of fibers strongly influences zeta potential values, therefore before the zeta potential was determined the samples were pre-treated for 2 hours in the electrolyte solution. The streaming potential measurements were performed using 0.001 n KCl as an electrolyte solution. The pH of the electrolyte solution was first adjusted to pH 10 using 0.1 n NaOH and afterwards decreased step-wise with 0.1 n HCl. The zeta potential/pH function was determined in this way; each value presented is the mean of five measurements at opposite flow directions calculated according to the FairbrotherMastin equation (equation (7)). Measurements were performed using the Electrokinetic Analyzer, EKA, A. Paar KG, Austria.

Results and Discussion

Crystallinity Changes of Mercerized Cotton Cellulose
Table 2 shows the degree of crystallinity of raw and mercerized cotton cellulose following the methods of Hermans/ Weidinger (wc,x (HW)) and Ruland/Wonk (wc,x (RV)). It is well known that crystallinity of mercerized cotton cellulose is reduced compared with raw cotton cellulose (without alkaline modification). WAXD confirms that the

lower degree in mercerized cotton cellulose is caused due to changes in morphology. During alkaline modification, the cellulose fibers swell. In the swelling action interfibrillary and intrafibrillary processes occur. In more concentrated alkali solutions, the swelling becomes intrafibrillary with the participation of higher lateral order parts of the fiber. This is consistent with the decreased size of alkali hydroxide hydrates when the concentration increases; thus the hydrate NaOH.nH2O appears in a noticeable proportion. In contrast to hydrated ion parts, solvated dipole hydrate is able to enter the crystalline parts of cellulose fiber [20]. This causes the changes of the crystallinity. As shown in Table 2 the degree of crystallinity of raw cotton cellulose calculated with Hermans/Weidinger method amounts to 0.567 0.029 and for mercerized cotton cellulose to 0.503 0.033. Following the methods of Ruland/Vonk one obtains the same decreasing trend of crystallinity degree by alkaline modification of raw cotton cellulose. In the case of mercerized cotton cellulose the degree of crystallinity is lower (0.469 0.052) in comparison with the Hermans/Weidinger approximation. This difference is caused by the fact that the Ruland/Vonk method includes a so-called disorder factor which leads to the differences in calculated values. However, both methods show identical influence of alkaline modification on the degree of cotton cellulose crystallinity. The ISV displays the ability of cotton cellulose to adsorb iodine and it deceases after alkaline modification, indicating also the reduced degree of crystallinity [1]. The fiber modification leads to an increased amount of accessible hydroxyl groups. Iodine is incorporated into the cotton cellulose fibers by interaction with the cellulose hydroxyl groups. It is arranged in a monomolecular layer in comparison with water, which is bound in multimolecular layers. Therefore the amount of adsorbed iodine is first of all influenced by the amount of accessible hydroxyl groups located in the amorphous phase. Figure 6 shows the degree of crystallinity (xC (%)) determined using WAXD and iodine adsorption (xISV (%)). The iodine sorption method correlates with the degree of crystallinity. Both methods show the decrease of the cotton cellulose crystalline phase causing higher accessibility for iodine as a consequence of changed supermolecular structure (cellulose I transformation to cellulose II). With the Knecht method the increased reactivity of the mercerized cotton cellulose was also confirmed. From the remissive value of raw and mercerized samples and the cal-

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Figure 6 Crystallinity degree defined using WAXD and iodine accessibility defined using iodine sorption measurements.

Figure 7 Remissive curves of raw and mercerized cotton cellulose stained with the substantive dye Tobazol Scharlach 4BS.

culation of dye difference Eab*, which amounts to 6.04, a considerably larger absorption of mercerized cotton cellulose was noted (Figure 7). The Knecht method confirms also the foreseen higher accessibility of mercerized cotton cellulose for the substantive dye. Results are in good accordance with structural changes determined by WAXD analysis and ISV.

Changed Sorption Character of Mercerized and Subsequently Crosslinked Cotton Cellulose

It is obvious that the contact angle of crosslinked cotton cellulose increases with increasing BTCA mass fraction in the reaction solution (Figure 8). In the raw sample group the highest contact angle (43) is observed with the uncrosslinked cotton cellulose sample.

A relatively high contact angle (33) is also observed with uncrosslinked mercerized sample. The difference of 10 is due to the more hydrophobic character of raw uncrosslinked cotton cellulose compared with the uncrosslinked mercerized one. The latter has a higher number of reactive hydroxyl groups and therefore a more hydrophilic character. In the case of raw cotton it is remarkable that the contact angle of the non-crosslinked fiber exceeds that of the crosslinked fibers independently of the applied BTCA concentration. It can be assumed that due to the raw cotton celluloses relative high crystallinity only a relatively small amount of hydroxyl groups is able to react with the BTCA carboxyl groups. A considerable part of these carboxyl groups remains therefore uncrosslinked. These hydrophilic polar groups increase the hydrophilic character (hydrophilicity) of the crosslinked material and therefore the contact angles of crosslinked raw samples are lower in comparison with

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Figure 8 Contact angle as a function of the BTCA content in the reaction solution for raw and mercerized cotton cellulose.

Figure 9 The content of the carboxyl groups with dependence on the concentration of the BTCA for raw and mercerized cotton cellulose. The mass fractions of BTCA in the reaction solution were 1%, 3%, 5%, and 7%.

the raw uncrosslinked one. The treatment of raw cotton cellulose with different mass fractions of BTCA in the reaction solution (1%, 3%, 5%, and 7%) gradually increases the contact angles. Nevertheless they are anyway lower in comparison with the raw uncrosslinked cotton cellulose. In the case of mercerized cotton cellulose where the extent of less ordered regions is higher than that of raw cotton cellulose, the influence of the accessible hydrophilic polar groups is clearly seen. In the case of crosslinking with 1% and 3% BTCA mass fraction the contact angles are lower in comparison with uncrosslinked cotton cellulose. It can be estimated from the contact angle results that a satisfactory ratio between hydroxyl cotton cellulose groups and BTCA carboxyl groups, and therefore a satisfactory reaction of esterification, is reached using mass fractions of BTCA in the reaction bath of 5% and more. It can be concluded from the contact angle results that mercerized cotton cellulose crosslinked with the same mass fraction of BTCA in the reaction bath shows a better

crosslinking effect than raw cotton cellulose. Mercerized cotton cellulose treatment with 5% and 7% BTCA mass fraction of BTCA in the reaction bath causes considerably higher contact angles. It is evident that in this example more carboxyl groups are included in the esterification process. Tensiometry as a method suitable for the determination of the degree of crosslinking confirms that the alkaline modification gaining more reactive cotton cellulose noticeably improves the crosslinking effect. Based on the results of the methylene blue method it is proven that the content of the carboxyl groups increases in all cases with the increased mass fraction of BTCA (Figure 9). The diagram (Figure 9) illustrates the situation that the mercerized samples have on average a 2.2 mmol/kg or 5% higher carboxyl group content than the raw cotton cellulose, regardless of the degree of crosslinking (amount of BTCA in the reaction bath). Figure 9 shows that the treatment with 1% mass fraction of BTCA does not affect the contents of the carboxyl

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Figure 10 Zeta potential as a function of electrolyte pH of raw cotton cellulose crosslinked with 1%, 3%, 5%, and 7% of BTCA in the reaction bath.

group. The biggest increase in the carboxyl groups appears when the mass fraction of BTCA is increased from 1% to 3%. This amounts to 4 mmol/kg or 16% in mercerized samples and to 5 mmol/kg or 13% in raw samples. The maximum increase of carboxyl groups is gained if crosslinked with 7% BTCA; an increase of 16% in the case of raw and 24% in the case of mercerized cotton cellulose is obtained. Again it was noted that the more reactive mercerized samples contain larger amounts of carboxyl groups than raw samples if identical BTCA mass fractions are used in the reaction solution. The results of the methylene blue method also confirm that the changes in crystallinity of cotton cellulose induced by alkaline modification increases the effect of crosslinking, caused by the increased amount of the carboxyl group content [20]. Polymer surfaces in aqueous (polar) solutions of electrolytes create charged groups on the surface. The phenomenon of the surface charge is connected with the polymers functional group dissociation as well as adsorption of ions (preferably -OH) onto the polymer surface. The representative quantity depends on ionic strength, and the electrolyte pH and type. Since the process of crosslinking is performed in an aqueous medium, knowledge of the polymers electrokinetic properties give us information about their accessibility as well as their interaction ability. Therefore these properties should also offer the possibility to monitor the crosslinking efficiency and were applied to obtain additional information about the extent of crosslinking dependent on the BTCA mass fraction in reaction solutions. Zeta potential measurements in 0.001 n KCl solutions were performed as a function of the electrolyte pH. The increase in negative with increasing pH is due to the increased dissociation of acidic surface groups. In the case

of basic groups, the number of positively charged groups increases with decreasing pH [36]. Complete dissociation of acidic or basic functional groups is related to the plateau in the pH curve. The zeta potential ()pH functions of raw and mercerized cotton cellulose crosslinked with 1%, 3%, 5%, and 7% of BTCA in the reaction solution are shown in Figures 10 and 11. at the plateau of the totally dissociated surface groups above pH = 5 correlates with the amount of accessible carboxyl groups and with the crosslinking efficiency. It is clearly displayed (Figures 10 and 11) that the zeta potential decreases with an increasing degree of crosslinking. This is more pronounced in the case of mercerized than in the case of raw samples. The isoelectric point (IEP) is a direct measure of the acidity or basiticity of a solid surface if the dissociation of surface groups is the predominant mechanism of the formation of the electric double layer [37]. It describes the pH value, where a balance between negative and positive surface charge is reached. The isoelectric point of anionic surface groups can frequently not be obtained experimentally because the low pH value would chemically change the sample. Therefore a positive is never reached. The IEP is usually obtained by extrapolation. In the case of amphoteric materials both the negative and positive plateau (where total dissociation is obtained) are experimentally accessible. IEPs ( = 0) are shifted slightly to lower pH values. In the case of raw uncrosslinked cotton cellulose samples the IEP is shifted from pH 3.4 with 1% mass fraction of BTCA to 2.8 with 7% BTCA in the reaction solution. In the case of mercerized cotton cellulose a similar trend is observed. The plateau is shifted to even more negative values, from 12.8 mV for uncrosslinked to 46 mV of 7% BTCA.

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Figure 11 Zeta potential as a function of electrolyte pH of mercerized cotton cellulose crosslinked with 1%, 3%, 5%, and 7% of BTCA in the reaction bath.

Isoelectric points of all mercerized samples are near pH region 3.2 with the exception of crosslinking with 7% BTCA mass fraction in the reaction solution, where the isoelectric point could not be detected but is extrapolated to a pH of 3.0. Previous studies have shown [23] that crosslinking with this relatively high BTCA mass fraction in the reaction solution (7%) causes a relatively high extent of crosslinking (i.e. relatively high extent of ester connections between cotton cellulose and BTCA) as well as a relatively high amount of free BTCA carboxyl groups which remain uncrosslinked. Therefore, the plateau is shifted towards very negative values and the isoelectric point ( = 0) towards a lower pH value. Cellulose functional groups (-OH, -COOH) dissociate in alkaline pH environments therefore the cellulose fibers are negatively charged and have negative value. According to Figures 10 and 11 zeta potential plateau values are shifted to the electronegative region in both raw and mercerized cotton cellulose with increasing BTCA mass fraction in the reaction solution. This phenomenon is connected with the cotton cellulose hydrophilicity (with increasing BTCA concentration in the reaction solution the cotton cellulose hydrophobicity gradually increases) and with the accessible carboxyl group dissociation. As shown by other authors, the plateau of differently pre-treated cellulose fibers can be between 4 and 14 mV [30]. Due to carboxyl groups which are present in the cellulose fibers the negative increases if crosslinked. As seen from the crosslinking mechanism [13], an average of two groups of BTCA are not included in crosslinking reaction. The zeta potential plateau difference at constant pH (8.5) is, for mercerized uncrosslinked cotton cellulose, 9%.

In the case of alkaline modification followed by crosslinking the zeta potential plateau increases between 7% and 40% in the BTCA concentration range 17%. The contact angle results coincide with zeta potential results (Figure 12). Increased hydrophobicity and higher amounts of accessible carboxyl groups which are entered into material by the crosslinking (confirmed with tensiometry) decrease the zeta potential plateau values to more negative values (even to -46 mV in the case of 7% BTCA crosslinking). The methylene blue method has proven that crosslinking with a higher BTCA mass fraction in the reaction solution produces an increased amount of accessible carboxyl groups. This trend correlates with calculated differences of the plateau values (Figure 12). Both results indicate that a high BTCA concentration improves the crosslinking efficiency

Conclusion
In this study the influence of mercerization on crosslinking efficiency of cotton cellulose crosslinked with 1, 2, 3, 4 buthanetetracarboxylic acid (BTCA) was evaluated. In order to estimate how the structural changes (cellulose I into cellulose II) influence the crosslinking, several physicalchemical methods were applied. The results were compared to see if there is any correlation between the crystallinity and crosslinking efficiency. The aim of the presented work is also to clarify whether the physical chemical methods used in this research are suitable tools for crosslinking efficiency monitoring.

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Figure 12 Correlation between the number of accessible hydroxyl groups in the example of plateau position and contact angles.

After mercerization the crystallinity changes were evaluated using WAXD, iodine adsorption values and the Knecht method. All methods confirm that cotton cellulose alkaline modification (mercerization) reduces the degree of crystallinity. Using tensiometry, the methylene blue method, and electrokinetic measurements the connection between cotton cellulose structure, hydrophilic/hydrophobic character (hydrophilicity/hydrophobicity), number of carboxyl groups, and dissociationadsorption properties of crosslinked cotton cellulose were investigated. With increasing BTCA mass fraction in the reaction solution the contact angle increases almost linearly in both raw and mercerized cotton cellulose. In comparison with raw crosslinked cotton cellulose crosslinked mercerized cotton cellulose had a much lower sorption ability (higher contact angle), which means a much better esterification effect. The sorption ability increases if BTCA carboxyl groups remain uncrosslinked. This phenomenon is especially perceivable in the group of raw cotton cellulose because of the relatively high crystallinity level. It seems that structural changes in mercerized cotton cellulose improve the effect of crosslinking, particularly when the reaction solution contains a relatively high level of BTCA. Another criterion describing crosslinking efficiency is the number of free accessible carboxyl groups. These groups were estimated using the spectroscopic methylene blue method, which shows that the extent of free carboxyl groups increases with the increasing BTCA mass fraction in the reaction solution. The results of the methylene blue method also confirmed that alkaline modification favorably influences the effect of crosslinking. Changes of the hydrophilic/hydrophobic character (cellulose hydrophilicity/hydrophobicity) and a changed amount of free carboxyl groups caused by the crosslinked process influence the surface dissociation/adsorption characteris-

tics of the accessible surfaces. Streaming potential measurements show that zeta potential of crosslinked cotton cellulose with a higher number of ester connections (mercerized) is shifted towards a more electronegative region in comparison with raw cotton cellulose, where the number of ester connections is smaller. This is indicated by the higher hydrophobicity of the crosslinked material. In this research it was estimated that all physicalchemical methods used in this study are suitable tools to determine the crosslinking efficiency of cellulose hydroxyl groups with BTCA.

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