Polymer International

Polym Int 55:236242 (2006) DOI: 10.1002/pi.1958

Carrier-free dyeing of radiation-grafted polyester fabrics with disperse dyes

EH El-Gendy and NM Ali
National Center for Radiation Research and Technology, Atomic Energy Authority, PO Box 29, Nasr City, Cairo 11731, Egypt

Abstract: Carrier-free dyeing of radiation-grafted polyester fabrics with disperse red dye was studied in the temperature range 283363 K. 1-vinyl 2-pyrrolidone (NVP), acrylic acid (AA) or their mixture was used to graft poly(ethylene terephthalate) (PET) fabric. The effects of pH of the dye solution, graft yield (GY), dyeing time (t), dye concentration (C), and dyeing temperature (T ) on the colour difference (CD) of PET fabric were studied. The best dyeing condition was achieved at pH 5.5. CD increases linearly with the increase in GY, with slopes depending on the type of grafted copolymer. CD increased rapidly as the dyeing time increased; this was followed by a relatively slow dyeing rate within a few minutes. The initial dyeing rate (R) was found to increase with an increase in C and T . The dyeing rates for all grafted samples followed 0.35-order kinetics and are temperature-independent. Average activation energy 9.26 kJ mol1 is calculated for the dyeing process and is independent of the fabric treatment. Pre-exponential rate constants 1976, 1839, and 1579 (CD/GY) s1 were calculated for dyeing PET samples grafted with AA/NVP mixture, NVP and AA, respectively, while 1074 CD s1 was evaluated for carrier dyeing of ungrafted fabric. Analysis of the kinetic parameters and the dyeing mechanism revealed that dyeing PET fabric was diffusion-controlled. Grafting PET fabric improved signicantly the dyeing afnity of the DR dye over ungrafted samples dyed in solutions containing a carrier. 2005 Society of Chemical Industry

Keywords: dyeing; radiation grafting; kinetics; polyester

INTRODUCTION The extremely crystalline nature of PET bers presents problems in obtaining dark shades by conventional dyeing methods, even with the temperature of the dye at boiling point. In order to overcome this problem, polyester bers are dyed using carriers or by using high-temperature high-pressure dyeing techniques. The expensive techniques of dyeing polyester bers at high temperatures and pressures and the poisoning effect of the carrier necessitated the need to nd other cheap and adequate dyeing methods. Radiation grafting with vinyl monomers is usually carried out to modify the properties of polyester bers. Considerable literature on the subject was reviewed by Chapiro1 and Hebeish and Guthrie.2 Increases and decreases in the properties of the bers have been reported for the grafting of natural and synthetic materials with various vinyl monomers.3 11 Modications of the swelling properties and the dyeability of radiationgrafted PET fabric toward reactive and basic dyes were studied in our previous investigations.11,12 Grafting polyester fabrics with dimethylaminoethyl methacrylate increased the color strength of reactive drimalan red dye.11 Grafting nylon-6 with Nvinyl pyrrolidone increased the dyeability of the

fabrics toward solar orange, direct dye.6 Dyeing kinetics of PET-graft-poly(MAA) with Astrazonrot violet and rhodamine red,13 and PET-graft-poly(AA) with sandocryl blue12,14 basic dyes, were studied. The dyeing rate increased with the increase in monomer concentration and dyeing temperature. Activation energies ranging from 6 to 13 kJ mol1 were found, depending on the grafted monomer and type of dye used. Electron beam radiation grafting of PET, cotton, and PETcotton blends, with special monomers, was also studied by several authors.15 23 This article presents studies on carrier-free dyeing kinetics of PET fabrics grafted with NVP, AA or their mixture and dyed with disperse red (DR) dye in the temperature range 283363 K. Ungrafted fabrics dyed in solutions containing a carrier are compared. The effects of pH of the dye solution, graft yield, dyeing time, dye concentration, and dyeing temperature (T ) on the color difference of the fabrics were investigated. The kinetic parameters (reaction order (n), dyeing rate (R), rate constant (k), pre-exponential rate constant (A), and the activation energy of the dyeing process (Q)) were determined.

Correspondence to: EH El-Gendy, National Center for Radiation Research and Technology, Atomic Energy Authority, PO Box 29, Nasr City, Cairo 11731, Egypt E-mail: eglal elgendy@hotmail.com (Received 15 June 2005; revised version received 27 September 2005; accepted 29 September 2005) Published online 19 December 2005

2005 Society of Chemical Industry. Polym Int 09598103/2005/$30.00

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EXPERIMENTAL Materials Mill-scoured, thermally stabilized (heat-treated at 493 K for 1.5 min) low-density polyester fabric, a product of Hankook Synthetic Inc. (Korea), was used. Scouring was carried out in a solution containing 0.001 g L1 Data scour WS-100 and sodium carbonate (0.5 g L1 ) at boiling point for 1 h. The fabric was thoroughly washed with hot water, dried at ambient temperature and then used for grafting. The monomers and other chemical reagents were used as received. A disperse dye (C.I. 11115) produced by Sandoz (Basle, Switzerland) was used. Methods Radiation grafting Grafting was carried out by the direct irradiation method in a 60 Co source at a dose rate of 1.45 Gy s1 . Different doses and monomer concentrations were used to achieve a wide range of graft yields. Dry and weighed polyester samples (ca 0.7 g) were swollen in chloroform12 overnight before being put in widemouth tubes with ground-glass stoppers. Also put into each tube were methanol and the monomer, so that the fabric-to-liquor ratio (FLR) was 1:40. The solution containing the fabric was de-aerated with bubbling nitrogen for 5 min. The grafted fabrics were removed from the reaction tube after irradiation to the desired dose. The occluded homopolymer was extracted from the grafted fabric with boiling water. The samples were then dried at 313 K in a vacuum oven to a constant weight. The degree of grafting (GY) was determined as the percentage increase in weight.12 14 Dyeing procedure and CD measurements A stock dye solution was prepared by pasting the dye in acetic acid before addition of the required distilled water. Aqueous dye solutions containing 2 % by weight of fabric (owf) dye were prepared from the dyestuffs at a fabric-to-liquor ratio 1:50. The pH of the dye bath was adjusted and the dyeing process was carried out in the presence of 0.1 g L1 Sandozin NIT liquid wetting agent. The ungrafted fabric was dyed in solutions containing 2 g L1 dispersol T, a surface active agent, a benzyl alcohol carrier and Sandozin NIT, while the grafted ones were dyed in carrierfree solutions. After dyeing, a reduction and clearing bath containing 2 g L1 sodium sulfate and 3 g L1 sodium hydroxide was used. The temperature of the dye bath was then raised to 363 K and kept constant for 45 min. After the dyeing, the samples were rinsed in hot water containing non-ionic detergent and in tap water, and allowed to dry. This dyeing procedure was applied to samples dyed at different pHs and GYs. The samples dyed in different concentrations and different temperatures were washed in water containing nonionic detergent at 343 K for 15 min followed by tap water rinse and allowed to dry. A computerized micro-colorimeter unit made by Dr Lange (Germany) was used for the color
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measurements.21 The L , a and b system used was based on the Commission International de lEclairage (CIE) color triangle (CIE units X, Y and Z). In this system, the L value represents the darkwhite axis, a represents the greenred axis and b represents the blueyellow axis. The L , a and b values of ungrafted and grafted fabrics before dye sorption were measured and taken as references. The CD intensity of the grafted samples after dyeing was determined as follows: E = [( L )2 + ( a )2 + ( b )2 ] (1)

RESULTS AND DISCUSSION Effect of pH The effect of the pH of DR dye solutions on CD of grafted and ungrafted fabrics is shown in Fig. 1. The dyeing process was carried out at 361 K for 45 min. The dye solutions contained 2 % of weight of fabric (owf) dye and the dispersing agent. The results indicate that the dye yielded high color strength in acidic solutions. At a constant GY of around 5 %, the afnity of the fabrics toward the dye solutions increased with the increase in pH, reaching maximum values at pH 5.5. A further increase in the pH decreased rapidly the CD of all dyes. The maximum CDs for the grafted fabrics were 59.3, 53.9, and 44.2 for PET-graft-poly(AA/NVP), PET-graft-poly(NVP) and PET-graft-poly(AA), respectively. The CD of ungrafted PET fabrics dyed in the disperse dye solutions with a carrier is 43.9. These results showed that the relative dye afnity toward the grafted fabrics with respect to ungrafted fabrics dyed in solutions with a carrier followed the ratio 1.339:1.217:1.01:1.000 (2)

The CD of the dyed PET-graft-poly(AA/NVP) and PET-graft-poly(NVP) exceeds that of ungrafted

70
5.2%AA

60 50 40
CD

5.0%NVP 5.2%(AA/NVP) without carrier with carrier

30 20 10 0 2 3 4 5 6 7 pH value 8 9 10

Figure 1. Effect of pH on the CD of grafted and ungrafted PET fabric dyed with DR dye. 2 % owf, dye; 1:50, FLR; 45 min at 361 K.

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and carrier-dyed fabric by about 34 % and 22 %, respectively. However, the CD of dyed PET-graftpoly(AA) fabric is almost the same as that of ungrafted and dyed in solutions containing a carrier. The higher the GY is for all dyed fabrics the higher the CD (Fig. 2). Consequently, the carrier-free dyeing of grafted PET with the DR disperse dye at the proper GY considerably improved their dyeability over that dyed by the well-known convention method using disperse dyes in solutions containing carriers. Thus all the dyeing kinetics experiments were carried out at a pH of 5.5. Effect of the degree of grafting The effect of degree of grafting (GY) on the CD of PET fabrics dyed with DR dye is shown in Fig. 2. The dyeing conditions are similar to those of Fig. 1 at pH 5.5. The increase in CD over that of ungrafted fabric is plotted as a function of GY. The results show linear dependence of the increase in CD with an increase in GY up to about 25 %. The slope of the linear relationship gives the rate of increase in CD per increase in GY. Values of 1.617, 1.563 and 1.120 CD/GY are obtained for fabrics grafted in

solutions containing 80 %AA/20 %NVP comonomer, 100 %NVP and 100 %AA, respectively. The value of the slope of the CDGY dependence for the differently treated fabrics supports the results presented in Fig. 1 and emphasizes the high afnity of AA/NVP mixture grafts toward the DR dye, followed by NVP and AA-grafted fabrics. The parameters affecting these preliminary results have to be veried kinetically. Consequently, dyeing kinetics experiments were carried out at pH 5.5 and suitable GYs for samples dyed in solutions with and without a carrier. The CD of the grafts was divided by the GYs to eliminate the effect of GY on the CD, as shown in Fig. 2. The effect of dye concentration and dyeing temperature on the CD was also investigated. Dyeing kinetics In the kinetic study, the CDs of the grafted and dyed polyester fabrics were measured by the CD value per unit of graft yield (CD/GY) to avoid the contribution of the degree of grafting in the CD measurements, as seen in Fig. 2. In previous investigations6,12,13 we have shown that the dyeing intervals are in the order of seconds. In each experiment, grafted and ungrafted samples were dyed together in the same dye bath, and the increase in CD per graft yield was calculated. In all dyeing experiments the concentration of the dye solutions was given in mol L1 . The dependence of CD/GY of grafted PET fabrics on the dyeing time for C values ranging from 4.6 105 to 4.6 104 mol L1 is shown in Figs 3(ac), 4(ac) and 5(ac) for samples grafted with NVP, AA and 80 %AA/20 %NVP mixture, respectively. Results of ungrafted fabrics, dyed in solutions containing the carrier, are shown in Fig. 6(ac). The dye solutions were adjusted to pH 5.5 and the fabrics were dyed in the temperature range 283361 K. The general features of the curves are nearly the same, except that the color strength increases with the increase in C and T . The color strength increased linearly as the dyeing time increased up to about 5 s; this is followed by a slower increase with a tendency to level off close to 300 s. The initial R value was calculated from the linear part of the CDt relationship. Table 1 shows the values of R at the corresponding C and

50 45 40 35
Increase in CD

AA grafts NVP grafts (y)AA/NVP=1.6166x AA/NVP

30 25 20 15 10 5 0 0

(y)NVP=1.5627x

(y)AA = 1.1203x

10 15 20 Graft yield, %

25

30

Figure 2. Effect of degree of grafting on the increase in the CD of PET fabric dyed in DR dye solutions adjusted to pH 5.5. Conditions are as in Fig. 1.

18 16 14 12 10 8 6 4 2 0 0

25 20 CD/GY CD/GY 15 10 5 0 100 200 t, s 300 400 (b) 0 100 200 t, s 300 400 (c) 303 K
4.60 E*-5 1.75 E*-4 4.60 E*-4

283 K

4.60 E*-5 1.75 E*-4 4.60 E*-4

40 35 30 25 20 15 10 5 0 0

CD/GY

361 K 100 200 t, s

4.60 E*-5 1.75 E*-4 4.60 E*-4

300

400

(a)

Figure 3. Dependence of the CD/GY of NVP-grafted PET fabric on the dyeing time for various DR dye concentrations (mol L1 ) at (a) 283, (b) 303, and (c) 361 K.

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12.0 10.0 8.0 CD/GY CD/GY 6.0 4.0 2.0 0.0 0 (a) 50 100 t, s 150 200 (b) 283 K 4.60*E-5 1.75*E-4 4.60*E-4 35 30 25 CD/GY 20 15 10 5 0 0 50 100 t, s 150 200 (c) 0 50 100 t, s 150 200 363 K 4.60*E-5 1.75*E-4 4.60*E-4

18 16 14 12 10 8 6 4 2 0

303 K

4.60*E-5 1.75*E-4 4.60*E-4

Figure 4. Dependence of the CD/GY of AA-grafted PET fabric on the dyeing time for various DR dye concentrations at (a) 283, (b) 303, and (c) 363 K.

25 18 16 14 12 10 8 6 4 2 0 0 (a) 20 15 CD/GY 10 5 0 100 200 t, s 300 400 (b) 0 100 200 t, s 300 400 (c) 303 K
4.60 E*-5 1.75 E*-4 4.60 E*-4

383 K

4.60 E*-5 1.75 E*-4 4.60 E*-4

40 35 30 25 20 15 10 5 0 0

CD/GY

CD/GY

361 K 100 200 t, s

4.60 E*-5 1.75 E*-4 4.60 E*-4

300

400

Figure 5. Dependence of the CD/GY of 80 %AA/20 %NVP-grafted PET fabric on the dyeing time at various DR dye concentrations at (a) 283, (b)303, and (c) 361 K.

20 16 12 CD CD 8 4 0 0 (a) 100 200 t, s 300 400 (b)

283 K 4.60*E-5 1.75*E-4 4.60*E-4

16 12 8 4 0 0 100 200 t, s 300 400 (c)

303 K
4.60*E-5 1.75*E-4 4.60*E-4

50 40 CD 30 20 10 0 0 100 200 t, s 300 400

358 K 4.60*E-5 1.75*E-4 4.60*E-4

Figure 6. Dependence of the CD of ungrafted PET fabric on the dyeing time for various DR dye concentrations containing the carrier at (a) 283, (b) 303, and (c) 358 K. Table 1. Dependence of R [(CD/GY)s1 ] on C and T for fabrics grafted with NVP, AA, AA/NVP mixture and dyed in a carrier-free solutions together with ungrafted fabrics dyed in solutions containing a carrier

C (mol L1 ) 4.60 105 RNVP at 283 K RNVP at 303 K RNVP at 361 K RAA at 283 K RAA at 303 K RAA at 363 K R(AA/NVP) at 283 K R(AA/NVP) at 303 K R(AA/NVP) at 361 K RUngrafted at 283 K RUngrafted at 303 K RUngrafted at 358 K 0.77 1.175 2.427 0.76 1.02 1.66 0.8 1.203 2.46 0.72 0.00 1.62 1.75 104 1.28 1.98 3.631 1.023 1.48 2.29 1.32 2.00 3.68 1.16 1.40 2.10 4.60 104 1.86 2.877 5.546 1.78 2.345 3.98 1.90 2.951 5.56 1.58 2.38 3.784

T for PET-graft-poly(AA), PET-graft-poly(NVP) and PET-graft-poly(AA/NVP), together with ungrafted samples dyed in DR solutions containing the carrier. The results show that as C and T increased, R increased. It is known6,12,13 that the initial R value is related to C according to the following equation: R = kCn (3)

By taking the logarithm of both sides of Eqn (3) the relationship becomes log R = log k + n log C (4)

The plot of log R versus log C produces a straight line, the slope of which is the order n and the intercept of which yields the logarithm of the rate constant (log k)
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0.8 283 K 303 K 361 K y = 0.3559x + 1.9102 0.6 log R, CD/s 0.4 0.2 0.0 -3.0 -0.2 log C, mol/L
Figure 7. Logarithmic plots of R versus C at various T values for NVP-grafted fabrics dyed in solutions without the carrier.

0.8 283 K 0.6 0.4 y = 0.335x + 1.4398 0.2 0.0 -4.5 -0.2 303 K 358 K y = 0.3508x + 1.7076

log R, (CD\GY)/S

y = 0.3891x + 1.7579 y = 0.3876x + 1.5331 -4.5 -4.3 -4.0 -3.8 -3.5 -3.3

y = 0.3424x + 1.3448 -4.0 -3.5 log C, mol/L

-3.0

Figure 10. Logarithmic plots of R versus C at various T values for ungrafted fabrics dyed in solutions containing the carrier.

0.8 0.6 log R, (CD/GY)/S 0.4 0.2 y = 0.3602x + 1.4194 0.0 -4.5 -0.2 log C, mol/L
Figure 8. Logarithmic plots of R versus C at various T values for AA-grafted fabrics dyed in solutions without the carrier.

283 K 303 K 363 K y = 0.3715x + 1.8088 y = 0.3653x + 1.5718

Table 2. Values of k of the DR dye at different values of T (K) for PET-graft-NVP, PET-graft-AA, PET-graft-80 %AA/20 %NVP (CM) and ungrafted fabrics dyed in solutions containing the carrier

T 283 303 57.27 46.08 58.56 27.50 361 81.32 84.35 85.21 51.00

-4.0

-3.5

-3.0

(k)(NVP) , (CD/GY) s1 (k)(AA) , (CD/GY) s1 (k)(CM) , (CD/GY) s1 (k)DRwithacarrier , CD s1

34.13 26.16 36.58 22.13

4.7
(y)CM = -1.1165x + 7.5886

0.8 In k, (CD/GY)/s 283 K 0.6 log R, (CD/GY)/s 0.4 0.2 y = 0.3756x + 1.5632 0.0 -4.5 -0.2 log C, mol/L
Figure 9. Logarithmic plots of R versus C at various T values for AA/NVP-grafted fabrics dyed in solutions without the carrier.

4.5 303 K 363 K y = 0.3894x + 1.7676 y = 0.3581x + 1.9305 4.3 4.1 3.9 3.7 3.5 2.5 -4.3 -4.0 -3.8 -3.5 -3.3 -3.0 3.0 3.5 4.0 1000/T, K-1
Figure 11. Arrhenius-type plot of the natural logarithm of the dyeing rate constant (k) versus the inverse of the absolute temperature for NVP-grafted and comonomer-grafted PET fabrics.
(y)NVP = -1.1059x + 7.5168 NVP comonomer

at a C of 1 mol L1 . Figures 710 show logarithmic plots of R versus C at different values of T , as given in Table 1 for grafted and ungrafted fabrics. The relationship is linear, and the equations relating the different parameters are displayed on the gures. The equations show that the values of n are almost constant and independent of T , with an average value of 0.35 for dyed grafted and ungrafted PET fabrics. The values of the intercepts yield log k for the different dyeing temperatures. Consequently, the general equation for the dependence of R on C can be written as follows: (R)DRdye = kC0.35 (5)

The values of k for the different T values were calculated from the intercepts of the equations displayed on the gures. The results are shown in Table 2 and indicate that k increases with the increase in T . The dependence of k on T is presented by Arrhenius-type plot. Figure 11 shows the ln k versus 1000/T for PET-graft-poly(NVP) and PET-graftpoly(AA/NVP), while Fig. 12 shows the same plot for dyed PET-graft-poly(AA) and ungrafted samples. The relationship is linear, and the slope gives the value of Q/R, where R is the universal gas constant. The intercept of the relationship is the natural logarithm of the pre-exponential rate constant (A). The values of Q, ln A and A for grafted and ungrafted samples, calculated from the equations displayed on
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Carrier-free dyeing of radiation-grafted polyester fabrics

4.3 In k,(CD/GY)/s OR CD/s 4.0 3.7 3.4 3.1 2.8 2.5 2.5 3.0 3.5 4.0 1000/T, K-1
Figure 12. Arrhenius-type plot of the natural logarithm of the dyeing rate constant (k) for AA-grafted and ungrafted PET fabrics versus the inverse of the absolute temperature.

yAA = -1.1496x + 7.3643

AA-grafts ungrafted y = -1.1035x + 6.979

Table 3. Values of Q, ln A and A for grafted and ungrafted PET fabrics dyed with DR dye

Q, kJ mol PET-graft-NVP PET-graft-AA PET-graft-CM PET-ungrafted 9.15 9.51 9.24 9.13

ln A 7.5168 7.714 7.364 6.979

A, (CD/GY) s1 or CD1 s 1839 1578 1976 1074

the computer chart, are given in Table 3. Table 3 shows that Q of grafted and ungrafted PET fabrics is almost constant (9.26 0.2 kJ mol1 ). The values of A for PET-graft-poly(AA/NVP) and PET-graftpoly(NVP) and PET-graft-poly(AA) are 1976, 1839 and 1578 (CD/GY) s1 , respectively. However, the value of A for the carrier-dyed ungrafted samples (1074 CD s1 ) is much lower than those for grafted PET fabrics. The results show the value Q is constant and is independent of the type of grafted copolymer or the presence of the carrier in the dye liquor. The k of the dyeing process is only dependent on A. It is obvious that A for PET-graft-poly(AA/NVP) has the highest value, followed by PET-graft-poly(NVP) and PET-graft-poly(AA), respectively. Ungrafted and carrier-dyed samples, however, have the lowest value of A. The relative value of A of grafted samples with respect to that of carrier-dyed ungrafted fabric is as follows: 1.84:1:71:1.47:1.00 These results agree with those given by Eqn (2) and indicate that the efciency of dyeing PET-graftpoly(NVP) and PET-graft-poly(AA) increased by 84 %, 71 % and 47 % over that of ungrafted and carrier-dyed polyester fabric. They also emphasize the dependence of the dye shade on the grafting monomer as well as the importance of studying the dyeing kinetics. The results obtained for grafted and ungrafted fabrics dyed in DR dye showed that the kinetic order of the dyeing process n is independent of whether the polyester fabric was grafted or not, the type of grafted
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copolymer and the dyeing temperature. Moreover, the activation energy Q of the dyeing process is also constant and independent of the different treatments carried out on the ungrafted fabric. However, R and k are dependent on the dyeing temperature and the type of grafted copolymer, while A is independent of C and T of the dye bath. Consequently, the values of A were considered to represent adequately the effect of the carrier, the type of monomer, or monomer mixture used in the dyeing or grafting processes. The dependence of R and k on T indicates that the dyeing process is diffusion-controlled and Q is the activation energy for the diffusion of the dye through the ber polymer system.13,23 Heating the dye liquor swells the ber to some extent and assists the dye to penetrate through the fabric, resulting in the dye being located in the amorphous regions of the ber. Once the non-polar disperse dye is within the ber polymer system, the dye molecules are held by hydrogen bonds and van der Walls forces. The use of carriers in the dye liquor assists the DR dye to enter the polyester ber polymer, enabling dark shades to be produced (Fig. 1). It is well known that there is no universally accepted explanation for the way in which carriers assist in dyeing polyester bers using disperse dyes.23 However, the most common explanation is that carriers swell the polyester ber polymer and, in so doing, allow the disperse dye molecules to enter the PET ber more readily. Moreover, swelling of polymers via grafting opens their structure with the result of enhancing the grafting and the subsequent dyeing processes.4,5,7,12,13 The degree of swelling increased with an increase in graft yield (Fig. 2). The increase in R, k and A due to grafting and carrier dyeing and the independence of n and Q on the type of grafted monomer indicate that the process responsible for enhancing the dyeing process is of the same nature, i.e., swelling of the polymer bers. According to the dependence of k and A on the type of grafted monomer, it could be concluded that the degree of ber swelling is highest for the PET-graft-poly(AA/NVP) followed by PET-graft-poly(NVP), PET-graft-poly(AA) and lastly by carrier dyeing. The increase in the swelling ability of the differently grafted monomers can be explained by the structure of the monomer and its molecular weight (MW). AA has an MW of 72 and a simple molecular structure. NVP has a MW of 111 with a structure that contains a cyclic ring attached to the vinyl group. Consequently, the PET-graft-poly(AA) and PET-graft-poly(NVP) chains will have different congurations and molar volumes. The higher the molar volume, the higher the internal stresses and the internal energy, i.e., E = V = Fd. The and V are the internal stress and the volume, respectively. The increase in E causes an increase in the built-in force (F) and hence displaces the PET ber polymer system with a distance d. Therefore, it is expected that PET-graft-poly(NVP) will increase the swelling of the PET fabric at a
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degree higher than that resulting from PET-graftpoly(AA). Hence, dyeing PET-graft-poly(NVP) will result in higher rates if compared with those produced from the use of PET-g-poly(AA). However, the dyeing rates of PET-graft-poly(AA/NVP) are higher than those of PET-graft-poly(NVP) or PET-graftpoly(AA) copolymers. According to the discussion based on the MW and structure of AA and NVP, it is expected that the dyeing rates of PET-graftpoly(AA/NVP) should be between or closer to those of PET-graft-poly(AA) rather than those of PET-graftpoly(NVP). The discrepancy in the expected and the experimental results was attributed to the reaction between AA and NVP during the radiation grafting process. It is noticed that the GY resulting from grafting AA/NVP monomer mixture on to PET was extremely low compared to that obtained from grafting each monomer alone.24 These results were explained by the strong inter-polymer complex formation (Hcomplex). Similar results have been reported by Georgiev et al.25 during their study on the formation and relative reactivity of comonomer H-complexes in the radical copolymerization of acrylic acid with 1-vinyl-2-pyrrolidone. The H-complex formed has a higher molecular weight, higher molar volume and more complex structure compared with those of NVP and AA. Once grafted on to PET, it will cause a high increase in the internal energy of the polymer ber system and consequently a high increase in the degree of swelling. This explains the high dyeing rates of carrier-free dyeing of AA/NVP-grafted fabrics and recommends its commercial use in dyeing polyester bers with disperse dyes.

industry and at an extremely short dyeing time. This considerably reduces the energy consumption and cuts down the dyeing cost to a minimum.

ACKNOWLEDGEMENTS The authors would like to thank Prof. IA ElShanshoury and Prof. MM Marie for their help during the course of this work.

REFERENCES
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CONCLUSION The kinetics of dyeing grafted and ungrafted fabrics in disperse red dye solutions with and without a carrier showed that grafting improves the afnity of the dye toward the polyester fabric. The efciency of the dyeing process is the highest toward samples grafted with AA/NVP mixture and NVP, while AA grafted and carrier-dyed ungrafted polyester fabrics showed the lowest. The mechanism of the dyeing process for grafted and ungrafted fabrics was diffusion-controlled and the dyeing rates were dependent on the type of grafted copolymer, dye concentration, dyeing temperature, additives in the dye liquor and pre-treatment of the fabric. Dyeing grafted PET fabrics with different types of hydrophilic monomers could be carried out at temperatures lower than those usually applied in

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