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Abrasion Resistance of Durable Press Finished Cotton


Investigators: Gary C. Lickfield ( Clemson University)
Charles Q. Yang ( University of Georgia) Michael J. Drews ( Clemson University) J. Richard Aspland ( Clemson University)

Participants:

Wei Chen (graduate student, Clemson University) Ning Feng (graduate student, Clemson University) Cheng Hu ( Visiting Scholar, University of Georgia)

Goal
The combination of inadequate abrasion resistance and relatively severe tensile strength loss has been the major disadvantage for durable press finished 100% cotton fabrics. The overall objectives of this work are to: characterize the surface nature of the wear of durable press (DP) finished cotton fabrics; investigate the cause and mechanism for loss in abrasion resistance of crosslinked cotton fabrics; further develop relationships between the molecular structure of crosslinking agents and their affect on the mechanical properties of crosslinked textile structures; and develop a technology for improving the abrasion resistance of DP finished cotton fabrics by preventing and/or removing the crosslinks on the fabric surface.

Introduction
Durable press finishing is widely used in the textile industry to impart wrinkle-resistance to cotton fabrics and garments. Significant loss in mechanical strength and abrasion resistance of the durable press finished fabrics has been a major concern for the industry. The increase in dimensional stability and wrinkle resistance with resin finishing of cotton has always been correlated with the lower abrasion resistance and tensile strength (1-4). In previous research, we investigated the strength loss for the cotton fabric treated with multifunctional carboxylic acids and found that the strength loss can be attributed to two factors: acid-catalyzed depolymerization of cellulose molecules and crosslinking of cellulose molecules (5). The strength of the fiber depends on how much the crosslinked chains can still be mutually displaced under tension in order to adequately resist the applied load. The rigid crosslinks that are formed with the standard formaldehyde based resins and with polycarboxylic acids, such as BTCA, obviously prevent the redistribution of stresses by preventing movement within the fiber microstructure. The crosslinking of cellulose molecules with these relatively rigid crosslinks causes stiffening of the cellulosic macromolecular network and fiber embrittlement thus reducing the mechanical strength of the treated cotton fabrics. These same mechanisms are responsible for the reduced mechanical properties of the fiber surface thus leading to poorer abrasion resistance. Cuff edge abrasion or frosting is also a source of much consumer dissatisfaction, especially with continuous dyed cotton fabrics due to inadequate dye penetration into the yarn bundle(6). Fiber surface property modification, such as through the use of softeners, has been shown to play an important role in minimizing abrasion and frosting(6,7). This report is a summary of the work conducted this past year in three of the project areas and examines the effects on fabric properties such as wrinkle recovery and abrasion resistance

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C00-C01 2 due to 1) commercial softeners and 2) cellulase enzymes; including 3) the results of molecular modeling studies on the rigidity and deformation recovery of several crosslink systems. I. Effect of Commercial Softeners on the Mechanical Properties of Durable Press Finished Cotton Fabric The abrasion resistance, tearing strength and tensile strength are known to have a close relation to the wear life of garments. In order to maintain the desired physical properties of finished fabrics and garments, fabric softeners are frequently used in durable press treatment. Polyethylene and the more recently developed aminofunctional silicon softeners are the most commonly used additives in durable press finish formulations. In this portion research, we examined the effects of polyethylene and aminosilicone softeners on the mechanical properties of the cotton fabric crosslinked by BTCA. Experimental Materials: The cotton fabric used is a warp-faced twill weave 100% cotton fabric (8 oz/yd2). 1,2,3,4-butanetetracarboxylic acid (BTCA) and sodium hypophosphite are reagent grade chemicals supplied by Aldrich. Polyethylene and aminosilicone softeners are commercial products Mykon HD and Viscosil VP345 supplied by Sequa Chemicals and Boehme Filatex, respectively. Fabric treatment: The cotton fabric is immersed in a solution containing the BTCA, sodium hypophosphite (NaH2PO2) 8.75% (w/w) and a softener. The wet pick-up was in the range of 6872%. The impregnated fabric is dried at 85oC for 3 min, then cured in Mathis curing oven for 2 min. The cured fabric was evaluated after one washing cycle to remove the catalyst and the acid not bound to cotton cellulose. Fabric Performance Evaluation: The conditioned flex abrasion resistance, tear strength and tensile strength were measured according to ASTM Test Method D3885-92, D1424-83 and D503590. The repeatedly home laundry testing was carried out according to AATCC standard method 124-1992. Results and Discussion In general, while there was no significant influence on the fabric tensile properties due to the presence of either softener, on either the BTCA treated or untreated control fabrics, significant improvements were observed in both tear strength (250%) and flex abrasion resistance (2000%) for the untreated control fabric. However, the effects on the DP finished fabric properties, while significant, were much less dramatic. As similar results were observed for both types of softeners, only the results for the aminosilicone are presented here. Figure 1 shows the effect of the softener on the tear strength and Figure 2 the effect on the flex abrasion resistance of the BTCA finished fabric. While the softener does improve the fabric tear strength, its presence does not fully counteract the negative effect of the BTCA crosslinks on the fabric. In addition, while the softener can provide for full recovery of the flex abrasion resistance lost, at least in the warp direction, due to crosslinking with such rigid crosslinks it is impossible to obtain the level of increased flex abrasion observed in the untreated control fabric with these same softeners.

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100

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40 warp 20 filling

0 0.00

0.40

0.80

1.20

1.60

2.00

2.40

Concentration of the Aminosilicone Softener ( % )

Figure 1.

Tearing strength retention of the cotton fabric treated with 8.57% BTCA and cured at 180 C for 2 min as a function of the concentration of the aminosilicone softener applied to the fabric.

140 120 100 80 60 40 20 0 0.00 warp filling

0.40

0.80

1.20

1.60

2.00

2.40

Concentration of the Aminosilicone Softener ( % )

Figure 2.

Flex abrasion resistance of the cotton fabric treated with 8.57% BTCA and cured at 180 C for 2 min as a function of the concentration of the aminosilicone softener applied to the fabric.

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C00-C01 4 II. Effect Of Cellulase on Properties of Durable Press Finished Cotton Fabrics As part of the baseline work in enzyme treatment of DP finished fabrics, this part of the work was concerned with developing protocol and characterizing fabrics treated using a standard enzyme system. As we are still identifying potential enzymatic systems to remove crosslinks from fibers, this initial enzyme work was focused on the application of cellulase enzymes and their effect on BTCA finished fabrics. Experimental Materials: The cotton fabric used was a desized, scoured and bleached cotton print cloth (Testfabrics Style 400). Cellulase enzyme (ROCKSOFT BioACE, activity >820 DTU/g) was kindly provided by Dyadic International Inc. 1,2,3,4-butanetetracarboxylic acid (BTCA), hypophosphite (NaH2PO2), and other chemicals were all reagent grade (Aldrich). Fabric treatment: Fabrics were padded twice with an aqueous solution containing 6% BTCA and 3% NaH2PO2 producing wet pickups of 100%. The fabric was dried at 80C for three minutes and then cured at 180C for an additional three minutes. Cured fabric was subjected to one normal washing cycle without detergent to remove any residual acid. Fabrics were then treated with cellulase enzyme (1:30 liquor ratio) at different concentrations for one hour at a temperature of 55C and a pH of 4.8, using an acetate buffer solution. All enzyme treatments were performed using a New Brunswick Scientific C-76 Classic water bath shaker at a 140 RPM shaking speed. Cellulase was deactivated using hot water (80C-90C) for ten minutes. Sets of fabrics were treated with the Cellulase enzyme either prior to ( pre-treatment) or after (posttreatment) the DP finishing procedure. Fabric Performance Evaluation: Tensile strength and flex abrasion resistance were preformed according to ASTM Method D 5035-95 and D3885-92, respectively. For the flex abrasion measurements on the print cloth, the head weight and tension weight used were 1/2 pound and 2 pounds; for the twill fabric, the head weight and tension weight were 1 pound and 4 pounds respectively. Wrinkle recovery angle (WRA) was measured according to AATCC Test Method 66-1996. Results and Discussion Figure 3 shows that, as expected, the breaking strength of cotton fabric decreases with increasing cellulase concentration. However, this decrease in breaking strength (~15% at 5g/L cellulase) is much less than observed due to just DP finishing alone (~55%). A more significant decrease in flex abrasion resistance was observed due to cellulase treatment (Figures 4). Again, this level of decrease in flex abrasion resistance is still less than that observed due to DP finishing. BTCA finishing of fabrics pre-treated with cellulase showed similar trends in both breaking strength and loss in abrasion resistance, as presented in Figures 5 and 6. Treatment of BTCA finished fabric with cellulase also showed a decrease in properties with increasing concentration of enzyme (Figures 7 and 8). Thus, the cellulase enzyme was still able to degrade cellulose even in the presence of the BTCA ester crosslinks. While losses in overall properties are similar for both treatments, the final fabric properties are slightly better for post-treatment as compared with pretreatment with cellulase enzyme. Cellulase enzyme treatment was found to have little effect on the wrinkle recovery angle of BTCA finished fabric.

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35 30 25 20 15 10 0 1 2 3 4

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Filling Warp

Filling Warp

Cellulase Concentration, g/l Figure 3. Breaking strength of cotton fabrics treated with different concentrations of cellulase for 1 hour.

Cellulase Concentration, g/l

Figure 4. Flex abrasion resistance of cotton fabrics treated with different concentration of cellulase

13 12 11 10 9 8 7 6 0 1 2 3 4 5
Cellulase Concentration, g/l

170 Filling Warp 150 130 110 90 0 Filling Warp

1 2 3 4 Cellulase Concentration, g/l

Figure 5. Breaking strength of DP-finished cotton fabric pre-treated with cellulase.

Figure 6. Flex abrasion resistance of DP-finished cotton fabrics pre-treated with cellulase.

15 14 13 12 11 10 9 8 7 6 0

200

Filling Warp

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F W
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1 2 3 4 Cellulase Concentration, g/l

Figure 7 Effect of cellulase concentration on the breaking strength of DP-finished fabric

Cellulase Concentration, g/l

Figure 8 Flex abrasion resistance of DPfinished cotton fabrics treated with cellulase

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C00-C01 6 III. Molecular modeling In previous reports, the results of a series of molecular modeling studies on amorphous cellulose and the effect of crosslinking on the calculated properties was presented. The calculated stress-strain curves for amorphous cellulose showed an apparent yield stress and yield strain. Incorporation of rigid DMDHEU crosslinks between the polymer chains served to increase the predicted initial modulus and to minimize yielding resulting in a more elastic response to the applied strain, in complete agreement with observed increase in wrinkle resistance in durable pressed cotton fabrics. As the number of crosslinks increased, the calculated effects become more pronounced. As part of the initial investigation into potential structures for an elastomeric crosslinking agent, conformationally flexible structures such as decane were examined. It was envisioned that such flexible structures would extend and allow the cellulose chain segments to move and align upon the application of stress, allowing the structure to maintain tensile strength and abrasion resistance, then return to a more random conformation conferring the required dimensional recovery and wrinkle resistance. Crosslinked cellulose models containing decane (24% by wgt.) as the crosslink structure were constructed using the similar techniques as were used for DMDHEU-crosslinked cellulose models. Here the initial backbone conformations for the decane crosslinks were generated and sampled while within the amorphous cellulose environment prior to bonding to the chain segments thus producing a more coiled structure to the decane chain. Stress-strain calculations were performed on these models and the results compared with those of cellulose models crosslinked with 10% DMDHEU, which has the same number of crosslinked sites. The calculated stress-strain curves for selected models are presented in Figure 9. Cellulose models crosslinked with rigid DMDHEU crosslinks had a higher initial modulus and less apparent yielding. The calculated stress-strain curve for decane crosslinked cellulose was very similar to that of non-crosslinked amorphous cellulose having a slightly lower initial modulus along with a lower yielding stress than the DMDHEU crosslinked cell, thus producing a less rigid structure.
1.5

0.5

0 0 5 10 15

Strain (%) 10% DMDHEU 24% decane Amorphous

Figure 9. Stress-Strain curves for the selected models. The strained crosslinked cellulose structures generated during the stress-strain calculations were examined to determine the average extension of the crosslinks at each deformation step. The average extension for each crosslink type as a function of applied strain is presented in Figure 10. As these crosslinked models were strained, even up to 15 % strain, the DMDHEU National Textile Center Annual Report: November 2001 C00-C01 6

C00-C01 7 crosslinks showed little extension. These rigid crosslinks serve to hold in place the cellulose chain segments to which they are attached thus conveying durable press characteristics to the cellulose. This same crosslink rigidity also results in decreased tensile strength and abrasion resistance by not allowing chain segments to move and realign to distribute the applied stress among the chain elements.

0.7 Change of crosslink length (A) 0.6 0.5 0.4 0.3 0.2 0.1 0 0 5 Strain (%) c1-c1 in DMDHEU c1-c2 in DMDHEU c2-c2 in DMDHEU decane 10 15

Figure 10. The change of crosslink length as a function of strain. In this figure c2-c2 represents the crosslink with two methylol groups on DMDHEU, c1-c1 represents the crosslink with two ring hydroxyls, and c1-c2 represents the crosslink with one methylol group and one ring hydroxyl. Compared to DMDHEU crosslinks, the decane crosslinks extend to a much larger extent during the straining of the crosslinked cellulose models, indicating that decane crosslinks are much more flexible than DMDHEU. This increased extension for decane is a result of the chain changing conformations in response to the stress generated due to the straining of the model. Thus, crosslinks of this type should allow the cellulose chain segments orient in response to an applied stress and minimize loss in tensile strength and abrasion resistance. Deformation recovery simulations were performed, using both a molecular mechanics technique and a molecular dynamics technique, in order to ascertain the effect of crosslink structure on the ability of amorphous cellulose structure to return to its original dimensions. As similar results were obtained with both types of calculations, only the results from the molecular mechanics calculations will be presented here. The procedure used was to compress the strained models backed to 0% strain from four different initial strain positions: 2%, 4%, 10% and 15%, using a compression step of 0.5% strain. Models were then relaxed after each compression step using molecular mechanics and the stress obtained from the calculated internal stress tensor. The average percent recovery results for the National Textile Center Annual Report: November 2001 C00-C01 7

C00-C01 8 set of DMDHEU crosslinked models, the decane crosslinked model and amorphous cellulose are presented below in Figure 11.
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90

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70 0 5 5 Strain (%) 10 1 15

20% DMDHEU 24% decane

Dry Cellulose

Figure 11. Deformation recovery from different strain positions All molecular models showed essentially a 100% recovery from an applied strain of 2%. With increasing levels of applied strain, the percent recovery decreased for all models. The DMDHEU crosslink models showed significantly better deformation recovery than amorphous cellulose with greater recovery for higher levels of crosslinking, in complete agreement with experimental results on DP finished cotton. In contrast, the "conformationally flexible" decane crosslink showed little improvement in recovery over the non-crosslinked amorphous cellulose. Thus, it appears that the thermodynamic driving force for the decane crosslinks to return to their original coiled conformation is not sufficient enough to provide any recovery to the strained cellulose chains. Flexibility and recoverability are the two basic requirements any new crosslinking system must satisfy in order to be used as a durable press finishing agent; sufficient flexibility to allow the cellulose chain segments to align to minimize loss in tensile strength and abrasion resistance and excellent recoverability to provide the required wrinkle resistance. We are currently examining molecular structures that are extensible yet do not change conformation.

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C00-C01 9 References: 1. Grant, J. N., Andrew, F. R., Weiss, L. C., Hassenboehler, C. B., Abrasion and Tensile Properties of Crosslinked Cotton Fabrics, Textile Res. J., 38, 217 (1968). 2. Meyer, U., Mueller, K., and Zollinger, H., Comparison of Textile Mechanical Properties of Cotton in Crosslinking with Dimethylolethyleneurea and Formaldehyde, Textile Res. J., 45, 813 (1975). 3. Murphy, A. L., Margavio, M. F., and Welch, C. M., All-Cotton Durable Press Fabrics of High Strength from Slack-Mercerize, Partially Restretched Yarn, Textile Res. J., 41, 22-31 (1971). 4. Welch, C.M., Improved strength and flex abrasion resistance in durable press finishing with BTCA, Textile Chemist and Colorist, 29, 21 (1997) . 5. Kang, I., Yang, C. Q., Wei, W., and Lickfield, G. C., The Mechanical Strength of the Cotton Fabrics Crosslinked by Polycarboxylic Acids: Part I. Acid Degradation and Crosslinking of Cellulose, Textile Res. J., 68, 856 (1998). 6. Farias, Leonard T., Aspects of Wet Processing Which Affect Color Retention and Crease Edge Abrasion in Wrinkle Resistant Cotton Slacks, Book of Papers, AATCC 1999 International Conference and Exhibition, Oct. 12 15, Charlotte, NC, pp. 325 327. 12. 7. Turner, John D., Improving the DP Appearance of Cotton Fabrics with Additives and Aminofunctional Silicones, Textile Chemist and Colorist, 20(5), 36 (1988).

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