**Machinery**

The suggested dyeing processes have to be compared with the conventional one. The price of Jet machine is considered as one million Egyptian pounds. For suggestion of dyeing methods, a stainless steel tank of 4m3 is required for preparation and storing the pretreatment solutions of either acetaldehyde or glyoxal. A stainless steel pump (5 Hp) is also required. The total cost of the pump and the storage tank is assumed to be about 10.000 LE, supposing the use of two Jet machines in this study.

**Depreciation** for 10 years as: <sup>1</sup> 10 <sup>X</sup>cost of machine production rate (kg/year)

**Interest** =10 % of the capital cost.

**Repairs** = 5 % of the capital cost.

**Labour** /kg fabric = (Man hour x no. of hours/shift x no. of shifts/day x no. of labours/shift) ÷ (no. of batches/day x Production rate/ batch)

Table 2.7 represents the total fixed operating costs/kg fabric for all dyeing processes in this study. It can be noticed that the investigated pretreatments led to decreasing the operating costs as well as increasing the production rate.

Table 2.8 illustrates the total production cost/kg fabric. Glyoxal/H2O2 pretreated fabric attained a lower production cost than both conventional dyeing method and that pretreated fabric with acetaldehyde. It can be noticed that pretreatment of PA-6 fabric with redox system (glyoxal/H2O2) led to a decrease in the total production cost/kg fabric in the range of 7-11% as well as increasing the production rate/year and decreasing the pollution impacts without impairing the tensile properties of the fibre.

Pretreatment of Proteinic and Synthetic Fibres Prior to Dyeing 321

Increasing the temperature accelerated the migration, giving higher values for the desorption constants than for the absorption constants. Increasing the liquor ratio was more favorable for the dyes having a higher solubility in water. Use of carriers promoted the migration because of the increase in dye solubility. When the acetyl value decreased, the rate of migration was found to increase (2, 8). Acetate fibers were dyed with disperse dyes in tetrachloroethylene in presence of water at a temperature above that of the tetrachloroethylene-water azeotropic mixture under pressure for 30 min. to give fast deep shade. The presence of tetrachloroethylene as a carrier gave fast shade at higher yields than in the presence of aromatic chlorinated hydrocarbons (9-12). Cellulose triacetate was exhaust dyed at 50°-75° in an aqueous bath containing disperse dye, 10-50% methylene chloride or methylene bromide, and a dispersing agent. The result was a level dyeing with good penetration and excellent fastness (13-15). Dyeing acetate yarns with dyeing liquor exposed to ultrasonic waves increased the dye absorption. The dyeing liquor was exposed to ultrasonic waves by passing the liquor through an ultrasonic generator. Acetate yarns were immersed in the resulting liquor for 20 min. at 85 °C to give dyed yarns with the amount of the dye absorbed 50% greater than that obtained without passing the liquor through the ultrasonic generator. In the dyeing of triacetate fibers with disperse dyes in organic solvents; the affinity and the heat of dyeing were much smaller than those in an aqueous system. The

diffusion coefficients varied with different fiber solvent combinations (13- 17).

and dried to give dyed fabric with wash fastness rating (2, 18).

groups to hydroxyl groups (1).

**Acid dyes:** Acid dyes are used for dyeing acetate, nylon, and acrylic fibers. These dyes were originated from basic dye acidification and have a complete color range. The light fastness ratings were generally very good and not affected by gas fading (5). The impregnation of acetate fabrics with liquors containing an acid dye and storing the fabric in ammonia vapor to give dyed fabrics with improved wash fastness was studied. An acetate taffeta fabric was immersed in a bath containing 20% g/l acid dye and 50 g/l thiourea to 50% pick up, dried, and stored in water vapor containing 28% ammonia for 4 h at room temperature, washed,

**Direct dye:** Acetate samples treated with methylamine, dimethylamine and trimethylamine and dyed with direct dye gave satisfactory results. The maximum color intensity was obtained in case of the treatment with diethylamine as compared with the relatively lower color intensities for ethylamine and triethylamine. This can be explained on the basis of higher basicity of diethylamine which led to a higher hydrolyzing effect changing the acetyl

In dyeing processes, the use of cyclodextrin (CD) can improve the dye uptake of CA because CD increases the tendency of disperse dye solubilization in aqueous solutions. CD is characterized by a hydrophobic internal cavity and by a hydrophilic exterior. This can give different inclusions of dye molecules depending on the size of the cavity. The formation of complexes between the dye molecules and CD has been thoroughly described and can be used as an alternative to dyebath additives. The structure of CD shows an ability of inclusion of complexes with compounds having a molecular size complementary to the cavity dimensions. No covalent bond is established between the dye molecules as a guest in the CD host molecules. Consequently, the dissociation–association equilibrium in solution becomes one of the characteristic features of the guest/host association. One of the modification possibilities of the fiber surface to alter its properties is attained by a successful binding of CD to the fibers (19). CA samples of known weight were treated with both CD and MCT-CD by a padding technique. The samples were then subjected to the dyeing process. A systematic study on the influence of CD treatments on the dyeing of CA fabric with disperse


Table 2.7. Fixed operating costs in LE/kg fabric


Table 2.8. Production costs in LE/kg fabric

#### **2.3 Cellulose acetate**

Dyeing acetate fibers is reviewed thoroughly to show some new possibilities of improving its dyeability with disperse, azoic, acid and cationic dyes. The fastness, techniques and conditions of dyeing, dye-absorption, fixation, leveling and vapor phase dyeing of acetate fibers are also reported (1-3).

#### **Dyeing characteristics**

Acetate fiber was the first man-made fiber which could not be dyed with conventional dyes used for cotton, wool and silk (4). Dyeing of acetate fibers by the method used for cellulosic fiber was found to be difficult because of the saponification possibility of acetate groups in alkalies. When dyeing was carried out at room temperature, no swelling of acetate fibers took place; consequently the diffusion of the dye component into the fiber was hindered. Dyeing behavior of acetate fiber was found to be very similar to that of synthetic fibers, particularly the affinity for water-insoluble dyes. Acetate fiber was dyed with selected types of cationic and acid dyes. The former produced a brilliant shade, while the latter produced a medium shade. Disperse dyes are generally suitable. Developing dyes of deep, wet-fast shades can be applied to acetate fibers. Pigment dyes were used only in exceptional cases and only for only pale shades. The effect of aromatic amines on dyeing intensity of triacetate fibers was related to change in the fibers' structure, determined by the interaction of amines with cellulose triacetate fiber (2, 5).

**Disperse dyes:** The migration of disperse dyes in the dyeing of triacetate fibers was determined by dissolving the fibers in either chloroform or an acetone-water mixture (4:1) (6, 7). The influences of temperature, liquor ratio, carrier, and acetyl value were determined.

Dyeing process Depreciation Interest Repairs Labour Total

0.278 0.255 0.139 0.127 0.048 0.044 0.743 0.681

0.681 0.625 0.534

3.65 4.35

3.4 3.35 3.26

0.044 0.04 0.034

0.127 0.117 0.1

Chemicals Energy LE/kg LE/kg

0.743 0.681

0.681 0.625 0.534

0.0995 0.0746

0.031 0.0325 0.034

0.255 0.234 0.2

0.278 0.255

0.255 0.234 0.2

Dyeing process Variable cost LE/kg Fixed cost Total

2.805 3.594

2.692 2.692 2.692

Dyeing acetate fibers is reviewed thoroughly to show some new possibilities of improving its dyeability with disperse, azoic, acid and cationic dyes. The fastness, techniques and conditions of dyeing, dye-absorption, fixation, leveling and vapor phase dyeing of acetate

Acetate fiber was the first man-made fiber which could not be dyed with conventional dyes used for cotton, wool and silk (4). Dyeing of acetate fibers by the method used for cellulosic fiber was found to be difficult because of the saponification possibility of acetate groups in alkalies. When dyeing was carried out at room temperature, no swelling of acetate fibers took place; consequently the diffusion of the dye component into the fiber was hindered. Dyeing behavior of acetate fiber was found to be very similar to that of synthetic fibers, particularly the affinity for water-insoluble dyes. Acetate fiber was dyed with selected types of cationic and acid dyes. The former produced a brilliant shade, while the latter produced a medium shade. Disperse dyes are generally suitable. Developing dyes of deep, wet-fast shades can be applied to acetate fibers. Pigment dyes were used only in exceptional cases and only for only pale shades. The effect of aromatic amines on dyeing intensity of triacetate fibers was related to change in the fibers' structure, determined by the interaction of amines

**Disperse dyes:** The migration of disperse dyes in the dyeing of triacetate fibers was determined by dissolving the fibers in either chloroform or an acetone-water mixture (4:1) (6, 7). The influences of temperature, liquor ratio, carrier, and acetyl value were determined.

Conventional dyeing Method Pretreated with acetaldehyde Pretreated with glyoxal/H2O2 and

Conventional dyeing Method Pretreated with acetaldhyde

**2.3 Cellulose acetate** 

fibers are also reported (1-3). **Dyeing characteristics** 

with cellulose triacetate fiber (2, 5).

Table 2.7. Fixed operating costs in LE/kg fabric

Pretreated with glyoxal/ H2O2 and dyed at

Table 2.8. Production costs in LE/kg fabric

dyed at 60oC 70oC 80oC

60oC 70oC 80oC Increasing the temperature accelerated the migration, giving higher values for the desorption constants than for the absorption constants. Increasing the liquor ratio was more favorable for the dyes having a higher solubility in water. Use of carriers promoted the migration because of the increase in dye solubility. When the acetyl value decreased, the rate of migration was found to increase (2, 8). Acetate fibers were dyed with disperse dyes in tetrachloroethylene in presence of water at a temperature above that of the tetrachloroethylene-water azeotropic mixture under pressure for 30 min. to give fast deep shade. The presence of tetrachloroethylene as a carrier gave fast shade at higher yields than in the presence of aromatic chlorinated hydrocarbons (9-12). Cellulose triacetate was exhaust dyed at 50°-75° in an aqueous bath containing disperse dye, 10-50% methylene chloride or methylene bromide, and a dispersing agent. The result was a level dyeing with good penetration and excellent fastness (13-15). Dyeing acetate yarns with dyeing liquor exposed to ultrasonic waves increased the dye absorption. The dyeing liquor was exposed to ultrasonic waves by passing the liquor through an ultrasonic generator. Acetate yarns were immersed in the resulting liquor for 20 min. at 85 °C to give dyed yarns with the amount of the dye absorbed 50% greater than that obtained without passing the liquor through the ultrasonic generator. In the dyeing of triacetate fibers with disperse dyes in organic solvents; the affinity and the heat of dyeing were much smaller than those in an aqueous system. The diffusion coefficients varied with different fiber solvent combinations (13- 17).

**Acid dyes:** Acid dyes are used for dyeing acetate, nylon, and acrylic fibers. These dyes were originated from basic dye acidification and have a complete color range. The light fastness ratings were generally very good and not affected by gas fading (5). The impregnation of acetate fabrics with liquors containing an acid dye and storing the fabric in ammonia vapor to give dyed fabrics with improved wash fastness was studied. An acetate taffeta fabric was immersed in a bath containing 20% g/l acid dye and 50 g/l thiourea to 50% pick up, dried, and stored in water vapor containing 28% ammonia for 4 h at room temperature, washed, and dried to give dyed fabric with wash fastness rating (2, 18).

**Direct dye:** Acetate samples treated with methylamine, dimethylamine and trimethylamine and dyed with direct dye gave satisfactory results. The maximum color intensity was obtained in case of the treatment with diethylamine as compared with the relatively lower color intensities for ethylamine and triethylamine. This can be explained on the basis of higher basicity of diethylamine which led to a higher hydrolyzing effect changing the acetyl groups to hydroxyl groups (1).

In dyeing processes, the use of cyclodextrin (CD) can improve the dye uptake of CA because CD increases the tendency of disperse dye solubilization in aqueous solutions. CD is characterized by a hydrophobic internal cavity and by a hydrophilic exterior. This can give different inclusions of dye molecules depending on the size of the cavity. The formation of complexes between the dye molecules and CD has been thoroughly described and can be used as an alternative to dyebath additives. The structure of CD shows an ability of inclusion of complexes with compounds having a molecular size complementary to the cavity dimensions. No covalent bond is established between the dye molecules as a guest in the CD host molecules. Consequently, the dissociation–association equilibrium in solution becomes one of the characteristic features of the guest/host association. One of the modification possibilities of the fiber surface to alter its properties is attained by a successful binding of CD to the fibers (19). CA samples of known weight were treated with both CD and MCT-CD by a padding technique. The samples were then subjected to the dyeing process. A systematic study on the influence of CD treatments on the dyeing of CA fabric with disperse

Pretreatment of Proteinic and Synthetic Fibres Prior to Dyeing 323

[1] Bendak, A.; Raslan, W.M. and Salama, M., 33rd Aachen Textile Conference, 29-30 Nov,

[4] Arai, T.; Freddi, G.; Colona, G. M.; Scotti, E.; Boschi, A.; Murakami, R. and Tsukada, M., J.

[5] Freddi, G.; Arai, T.; Colona, G. M.; Boschi, A. and Tsukada, M., J. Appl. Polym. Sci., 82,

[6] Tsukada, M.; Arai, T.; Colonna, G. M.; Boschi, A.; and Freddi, G., J. Appl. Polym. Sci., 89,

[9] Judd, D. and Wyszeeki, G., "Colour in Business, Science and Industry", John Wiley &

[10] Bendak, A.; Allam, E. E. and Allam, O. G., 2nd Inter. Conf. of Text. Res. Div., NRC,

[11] Bendak, A. and Allam, O. G., 6th Int. Conf. Text. Res. Div. NRC, Cairo, Egypt April (2009)

[14] Nakanishi, K. and Philppa, H. S., "Infrared Absorption and Spectroscopy", Holden-

[15] Bendak, A. and Allam, O. G., 3rd Inter. Conf. of Text. Res. Div., NRC, Cairo, Egypt,

[22] Bendak, A. and Allam, O. G, 4th Inter. Conf. of Text. Res. Div., NRC, Cairo, Egypt, (April

[33] Ghalab, S.; Raslan, W. M.; El-Khatib, E. M. and El-Halwagy, A. A., RJTA, 15, 115 (2011).

[2] Bendak, A and El- Marsafi S. M., Bull of the National Research Centre, 21, 63 (1996). [3] Bendak, A and El- Marsafi S. M., J. Islamic Academy of Science, 4, 275 (1991).

**3. References** 

**3.1 References - Proteinic fibres** 

3513 (2001).

638 (2003).

Aachen, Germany (2006).

Sons, New York (1975).

[13] Holme, I., J. Text. Inst., 84, 520 (1993).

Day, USA (1977).

(April 2-4, 2006).

15-17, 2007)

**3.2 References – Polyester** 

Cairo, Egypt, (April 11-13, 2005)

[18] Lewis, D. M., Melliand Textillber, 67, 717 (1986) [19] Lewis, D. M. J. Soc. Dyers Col., 98, 165 (1982).

Appl. Polym. Sci., 80, 297 (2001).

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[20] Cameron, B.A. and Paithorpe, M.T; J. Soc. Dyers Col., 103. 257(1987). [21] Richard, V. F. and Manfred, J. P; Text. Res. Inst., 141, 15 (1983).

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[1] Olson, L. M. and Wentz, M., Text. Chem. Col., 16, 48 (1984).

[27] Yeung, K. W. and Shang; S. M., J. Soc. Dyers Col., 115, 228 (1999).

dye was performed to optimize new possibilities to dye CA fabric at a lower temperature than the conventional dyeing one without using additives as well as enhancing the fastness properties and increasing the dye penetration into the interior of the fiber structure to ensure homogeneity and leveling of the dye. Disperse dyes are hydrophobic compounds, it was anticipated that CD could serve as host sites if incorporated into the molecular structure of a warp size. CD treatment offered a significant dyeability effect on CA than MCT-CD. The color intensity of the dyed CA was found to depend on the CD concentration. The differential thermal analysis data of the untreated CA and that one pretreated with CD is given in Table 2.9. A slight decrease in glass transition temperature (Tg), crystallinity temperature (Tc), and melting temperature (Tm) was observed. CD treatment of CA fabric imparts no effect on the thermal properties of CA.


Treatment: padding, pick up 100%, 0.2 g CD/100 g fiber, pH 8.0, 150ºC, 3 min.

Table 2.9. Differential Thermal Analysis of Untreated and Pretreated CA Fabric With CD

Scanning electron micrographs (SEM) of the untreated and pretreated CA fabric with CD are depicted in Figure 2.5(a, b). Some changes on the surface features of the pretreated CA were observed. The mean depth of the disperse dye inside the pretreated CA fiber was found to be twice more than that of the dyed untreated one. The % mean depth of dye into the dyed fiber is ranged from 60 to74% for CD-treated CA compared to 20–21% for untreated one. A mean dye depth <30% inside the fiber is defined as ring dyeing.

Fig. 2.5. (a) SEM of untreated CA fabric. (b) SEM of treated CA fabric with CD.

**Dyeing behaviour of laser treated fabric:** The excimer UV-laser treatment can improve the dyeability of polyester fibres. The maximum colour intensity of untreated one could be attained at shorter time. Also, the half dyeing time of laser treated sample decreases from about10min for untreated one to 7 min. The main factor which explains the improvement of the dyeability of the irradiated CA fabric is the increase of the overall surface area as a result of the morphological modification induced by excimer laser. The mean depth % of dye into the dyed treated CA sample is that 43.9 % compared to 20.2% for untreated one (20).

#### **3. References**

322 Textile Dyeing

dye was performed to optimize new possibilities to dye CA fabric at a lower temperature than the conventional dyeing one without using additives as well as enhancing the fastness properties and increasing the dye penetration into the interior of the fiber structure to ensure homogeneity and leveling of the dye. Disperse dyes are hydrophobic compounds, it was anticipated that CD could serve as host sites if incorporated into the molecular structure of a warp size. CD treatment offered a significant dyeability effect on CA than MCT-CD. The color intensity of the dyed CA was found to depend on the CD concentration. The differential thermal analysis data of the untreated CA and that one pretreated with CD is given in Table 2.9. A slight decrease in glass transition temperature (Tg), crystallinity temperature (Tc), and melting temperature (Tm) was observed. CD treatment of CA fabric

> CA Sample Tg (ºC) Tc (ºC) Tm (ºC) Untreated 64.5 168.8 260 Pretreated with CD 62.1 163.0 259

Table 2.9. Differential Thermal Analysis of Untreated and Pretreated CA Fabric With CD

untreated one. A mean dye depth <30% inside the fiber is defined as ring dyeing.

Fig. 2.5. (a) SEM of untreated CA fabric. (b) SEM of treated CA fabric with CD.

for untreated one (20).

**Dyeing behaviour of laser treated fabric:** The excimer UV-laser treatment can improve the dyeability of polyester fibres. The maximum colour intensity of untreated one could be attained at shorter time. Also, the half dyeing time of laser treated sample decreases from about10min for untreated one to 7 min. The main factor which explains the improvement of the dyeability of the irradiated CA fabric is the increase of the overall surface area as a result of the morphological modification induced by excimer laser. The mean depth % of dye into the dyed treated CA sample is that 43.9 % compared to 20.2%

Scanning electron micrographs (SEM) of the untreated and pretreated CA fabric with CD are depicted in Figure 2.5(a, b). Some changes on the surface features of the pretreated CA were observed. The mean depth of the disperse dye inside the pretreated CA fiber was found to be twice more than that of the dyed untreated one. The % mean depth of dye into the dyed fiber is ranged from 60 to74% for CD-treated CA compared to 20–21% for

imparts no effect on the thermal properties of CA.

Treatment: padding, pick up 100%, 0.2 g CD/100 g fiber, pH 8.0, 150ºC, 3 min.

#### **3.1 References - Proteinic fibres**


#### **3.2 References – Polyester**


Pretreatment of Proteinic and Synthetic Fibres Prior to Dyeing 325

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**15** 

*Iran* 

**Effect of Plasma on Dyeability of Fabrics** 

The unique physical and chemical characteristics of the plasma environment make it attractive for textile processing. Plasma is an ionized gas, i.e. it contains electrons, ions and neutral atoms and/or molecules. However, not all of the ionized gases used in textile processing will exhibit the properties associated with plasmas, mainly because of their low charge state densities compared to the neutral gas density or are produced by transient

Plasma activation is being used in several fabric and nonwoven applications in the textile

There are many industrial applications of thin film deposition by plasma sputtering or plasma polymerization in the technical textile and nonwoven industry. Roughly, the coatings deposited in those industries can be categorized under either (permanently) hydrophilic coatings or hydrophobic/oleophilic coatings. In most cases, the deposited coatings give rise to unique products that are difficult or even impossible to produce using

The textile market is trying to make deep, dark colours and this is not easy to achieve.

One way to do this is to reduce the specular component of reflection of the fabric surface after dyeing. A plasma etching leads to a controlled nano or micro-roughness, increasing diffuse reflectance and minimizing the specular component. In consequence, the dyed fabric

In various research programs, it has been shown that pick-up of dyestuff can be strongly

Polypropylene fibers have such excellent properties as low specific weight (0.91 g/cm3 only), high strength (42-53 CN/ Tex) and good resistance to acids and alkalis, and they also possess good thermal resistance and antibacterial properties. The poor wettability (only 0.05 % at 20 oC) and dyeability have, however, limited the application of these fibers in garments and other industries (Huang et al, 2006). It is of importance to improve the wet ability and dyeability of PP fabrics for many applications. Although chemical modification of the fibers has been somewhat successful in improving hydrophilic and antistatic properties, there are environmental concerns related to the disposal of chemical after

improved after plasma pre-treatment of natural and synthetic fibre fabrics.

will have an intense darker colour after plasma etching.

**1. Introduction** 

phenomena.

industry. (Pane *et al.*, 2003)

other technologies.

(Svensson, 2004)

*1Department of Textile, Arak Branch, Islamic Azad University, Arak, 2Plasma Physics Research Center, Science and Research Branch,* 

Sheila Shahidi1 and Mahmood Ghoranneviss2

*Islamic Azad University, Tehran,* 


#### **3.3 References - Polyamide**


#### **3.4 References - Cellulose acetate**

