**3. Results and discussion**

## **3.1. Extraction parameters**

Extraction was carried out by water, water-acetone, and water-ethanol mixtures at 25-60 ◦C for 30-120 min. The ultrasonic efficiency had been determined simultaneously with extrac‐ tion parameters, and compared with the conventional heating method. The yield coefficients of co-solvents were definitively greater than water, with much higher values in case of ultra‐ sonic. Water-acetone mixture was found to be the most selective co- solvent followed by wa‐ ter-ethanol. As shown in Figures [4, 5] water-acetone mixture released over 32% of the total dye absorbency, exhibiting 21% of the total color strength when dyeing the woolen sample. Water-ethanol extracted 27% dye and exhibited 19% color strength, while water extracted less than 21% dye, and exhibited 16% color strength. This was relative to [10, 6, and 4] % of absorbance and [18, 15, and 11] % color strength respectively with the co-ordinate solvents when using the conventional heating method.

**Figure 5.** Effect of solvents on the color strength of Osage orange dyed wool using the conventional [CH] and ultra‐

abs K/S

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213

0 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25 27.5 **acetone conc. (%) V/V**

**Figure 6.** Effect of acetone concentration on the absorbency and color strength of Osage orange dyed wool using

The solvent polarity can change the position of the absorption or emission band of mole‐ cules by solvating a solute molecule or any other molecular species introduced into the sol‐ vent matrix [33]. By the way, dye molecules are complex organic molecules which might carry charge centers and are thus prone to absorption changes in various media [33, 34]

Acetone acts as the non hydrogen-bond donating solvents (also called as non-HBD type of solvents), while water and ethanol are the hydrogen-bond donating solvents (also called as

sonic [US] assisted extraction

ultrasonic assisted extraction

0

0.5

1

1.5

**abs & K/S**

2

2.5

**Figure 4.** Effect of solvents on the absorbency of Osage orange powder using the conventional [CH] and ultrasonic [US] assisted extraction

Figures 6, 7 and 8 showed the absorption, and color strength values of Osage orange pow‐ der extracted by acetone at different concentrations of (2.5 – 25) % v/v at temperatures from 25-60o C, for time intervals varied between 30-120 min.

The maximum values were achieved with 20 % v/v acetone at 60o C, for 60 min. The extrac‐ tion parameters affected the color strength and are influenced by the properties of solvents such as, the dipole moment, dielectric constant, and refractive index values.

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics http://dx.doi.org/10.5772/54410 213

nates, L\* corresponding to brightness, a\* to red–green coordinate (positive sign = red, nega‐ tive sign = green) and b\* to yellow–blue coordinate (positive sign = yellow, negative sign =

Extraction was carried out by water, water-acetone, and water-ethanol mixtures at 25-60 ◦C for 30-120 min. The ultrasonic efficiency had been determined simultaneously with extrac‐ tion parameters, and compared with the conventional heating method. The yield coefficients of co-solvents were definitively greater than water, with much higher values in case of ultra‐ sonic. Water-acetone mixture was found to be the most selective co- solvent followed by wa‐ ter-ethanol. As shown in Figures [4, 5] water-acetone mixture released over 32% of the total dye absorbency, exhibiting 21% of the total color strength when dyeing the woolen sample. Water-ethanol extracted 27% dye and exhibited 19% color strength, while water extracted less than 21% dye, and exhibited 16% color strength. This was relative to [10, 6, and 4] % of absorbance and [18, 15, and 11] % color strength respectively with the co-ordinate solvents

**Figure 4.** Effect of solvents on the absorbency of Osage orange powder using the conventional [CH] and ultrasonic

Figures 6, 7 and 8 showed the absorption, and color strength values of Osage orange pow‐ der extracted by acetone at different concentrations of (2.5 – 25) % v/v at temperatures from

tion parameters affected the color strength and are influenced by the properties of solvents

C, for 60 min. The extrac‐

C, for time intervals varied between 30-120 min.

The maximum values were achieved with 20 % v/v acetone at 60o

such as, the dipole moment, dielectric constant, and refractive index values.

blue). [30-32].

*<sup>Δ</sup>E*\**ab* = {(*Δ<sup>L</sup>* \* )<sup>2</sup> + (*Δ<sup>a</sup>* \* )<sup>2</sup> + (*Δ<sup>b</sup>* \* )2}1/2

when using the conventional heating method.

**3. Results and discussion**

**3.1. Extraction parameters**

212 Eco-Friendly Textile Dyeing and Finishing

[US] assisted extraction

25-60o

**Figure 5.** Effect of solvents on the color strength of Osage orange dyed wool using the conventional [CH] and ultra‐ sonic [US] assisted extraction

**Figure 6.** Effect of acetone concentration on the absorbency and color strength of Osage orange dyed wool using ultrasonic assisted extraction

The solvent polarity can change the position of the absorption or emission band of mole‐ cules by solvating a solute molecule or any other molecular species introduced into the sol‐ vent matrix [33]. By the way, dye molecules are complex organic molecules which might carry charge centers and are thus prone to absorption changes in various media [33, 34]

Acetone acts as the non hydrogen-bond donating solvents (also called as non-HBD type of solvents), while water and ethanol are the hydrogen-bond donating solvents (also called as HBD type solvents) [33]. The absorbency values of Osage orange in these solvents are given in Figure 4, 5. It can noted from this figure that the absorption maximum of the extract is affected by the solvent type, thus the change in values can be noted as a probe for various types of interactions between the solute and the solvent.

Water and ethanol are considered as polar protic solvents, their polarity stems from the bond dipole of the O-H bond, whereas the large difference in the electro- negativities of the oxygen and hydrogen atom, combined with the small size of the hydrogen atom, warrant separating the Osage orange molecules that contain the OH groups from those polar com‐ pounds that do not. On the other hand acetone considered as dipolar aprotic solvent, con‐ taining a large multiple bond between carbon and either oxygen or nitrogen e.g. C-O double bond. [33-35].

Although water has the highest dielectric constant among ethanol and acetone solvents, its extraction demonstrated the lowest value of absorbency. This might due to the formation of strong hydrogen bond between the dyes extract and water molecules [33-35].

2.3 2.35 2.4 2.45 2.5 2.55 2.6 2.65 2.7

**K/S**

ter through hydrogen bonding [33-35]

temperatures

30 40 50 60 70 80 90 100 110 120 130 **time (min)**

**Figure 8.** Effect of ultrasonic assisted extraction time on the color strength of Osage orange dyed wool at different

The dye absorbance is also influenced by the presence of co-solvents. Water-acetone mixture exhibited the highest value of absorbance, followed by the second water-ethanol mixture. In case water-acetone, the salvation of extract is non-HBD type of solvent mainly occurs through charge-dipole type of interaction, whereas in HBD type of solvent, the interaction also occurs by hydrogen bonding besides the usual ion-dipole interaction. In this situation, the methyl groups of acetone are responsible for the solvation of the dye extract. Thus, decreasing the amount of non-HBD acetone solvent "concentration" increasing the amount of HBD solvent (water) shall break these interactions with the dye molecule, thereby decreasing the value of absorbance. Water-ethanol mixtures belong to HBD type of solvents, whereas the dye cation is preferential‐ ly solvated by the alcoholic component in all mole fractions in aqueous mixtures with ethanol. It is well known that water makes strong hydrogen-bonded nets in the water-rich region, which are not easily disrupted by the co-solvent [33, 34]. This can explain the strong preferential salva‐ tion by the alcoholic component in this region since water preferentially interacts with itself rather than with the dye. In the alcohol-rich region, the alcohol molecules are freer to interact with the water and with the dye, since their nets formed by hydrogen bonds are weaker than in water. In this situation, the alcohol molecules can, to a greater or lesser extent, interact with wa‐

Wool fiber is considered as relatively easy fiber to dye, the ease with which the polymer sys‐ tem of wool will take in dye molecules is due to polarity of its polymer and its amorphous nature. The polarity will readily attract any polar Osage orange molecules and draw them into the polymer system. The studies of wool dyeing process have been in two distinct theo‐ ries (The Gilbert- Rideal's and Donnan theories). The Gilbert and Rideal theory based on

at room temp 40 50 60

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**Figure 7.** Effect of ultrasonic assisted extraction time on the absorbency of Osage orange at different temperatures

HBD type solvents) [33]. The absorbency values of Osage orange in these solvents are given in Figure 4, 5. It can noted from this figure that the absorption maximum of the extract is affected by the solvent type, thus the change in values can be noted as a probe for various

Water and ethanol are considered as polar protic solvents, their polarity stems from the bond dipole of the O-H bond, whereas the large difference in the electro- negativities of the oxygen and hydrogen atom, combined with the small size of the hydrogen atom, warrant separating the Osage orange molecules that contain the OH groups from those polar com‐ pounds that do not. On the other hand acetone considered as dipolar aprotic solvent, con‐ taining a large multiple bond between carbon and either oxygen or nitrogen e.g. C-O double

Although water has the highest dielectric constant among ethanol and acetone solvents, its extraction demonstrated the lowest value of absorbency. This might due to the formation of

**room temp 40 50 60**

30 60 90 120 **Time "min"**

**Figure 7.** Effect of ultrasonic assisted extraction time on the absorbency of Osage orange at different temperatures

strong hydrogen bond between the dyes extract and water molecules [33-35].

types of interactions between the solute and the solvent.

0

0.1

0.2

0.3

**abs.**

0.4

0.5

0.6

0.7

bond. [33-35].

214 Eco-Friendly Textile Dyeing and Finishing

**Figure 8.** Effect of ultrasonic assisted extraction time on the color strength of Osage orange dyed wool at different temperatures

The dye absorbance is also influenced by the presence of co-solvents. Water-acetone mixture exhibited the highest value of absorbance, followed by the second water-ethanol mixture. In case water-acetone, the salvation of extract is non-HBD type of solvent mainly occurs through charge-dipole type of interaction, whereas in HBD type of solvent, the interaction also occurs by hydrogen bonding besides the usual ion-dipole interaction. In this situation, the methyl groups of acetone are responsible for the solvation of the dye extract. Thus, decreasing the amount of non-HBD acetone solvent "concentration" increasing the amount of HBD solvent (water) shall break these interactions with the dye molecule, thereby decreasing the value of absorbance. Water-ethanol mixtures belong to HBD type of solvents, whereas the dye cation is preferential‐ ly solvated by the alcoholic component in all mole fractions in aqueous mixtures with ethanol. It is well known that water makes strong hydrogen-bonded nets in the water-rich region, which are not easily disrupted by the co-solvent [33, 34]. This can explain the strong preferential salva‐ tion by the alcoholic component in this region since water preferentially interacts with itself rather than with the dye. In the alcohol-rich region, the alcohol molecules are freer to interact with the water and with the dye, since their nets formed by hydrogen bonds are weaker than in water. In this situation, the alcohol molecules can, to a greater or lesser extent, interact with wa‐ ter through hydrogen bonding [33-35]

Wool fiber is considered as relatively easy fiber to dye, the ease with which the polymer sys‐ tem of wool will take in dye molecules is due to polarity of its polymer and its amorphous nature. The polarity will readily attract any polar Osage orange molecules and draw them into the polymer system. The studies of wool dyeing process have been in two distinct theo‐ ries (The Gilbert- Rideal's and Donnan theories). The Gilbert and Rideal theory based on Langmuir's theories of surface adsorption [36], in which the activity coefficient of Osage or‐ ange extract ions adsorbed into the wool phase are reduced due to specific binding with sites on wool, which is the formation of ion pairs. This theory proposed that dyeing process is an anion exchange process, in which the Osage orange extract molecules displace smaller anions, depending on four steps: a) diffusion to fiber surface, b) transfer across that surface, c) diffusion within to appropriate "sites" and d) binding at those sites. On the other hand, according to the Donnan equilibrium theory, the Osage orange extract was considered to partition between the external solution and internal solution phase in the wool. The later phase is believed to contain a high concentration of fixed ionic groups, and hence solute molecules have reduced activity co-efficient in that phase due to coulombic interaction be‐ tween the anionic groups (OH) in fact: O- of Osage orange extract and the protonated amino groups of wool. [36]

an increase in color depth; whereas the maximum color depth was achieved with 8% w/v powder on both fabrics as shown in Figure 9. The relative high K/S values for dyeings can be explained with the high amount of bark extracted for this series of dyeing experiments.

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics

Dyeing temperature and time are important parameters influencing the quality of the dyed silk and wool samples. It is well known that dyeing at high temperature for a long time tends to decrease the fabric strength. [36-38] Therefore, it was proffered to dye the samples ultrasonically at temperatures ranging from 30 to 60 °C, relative to the dyeing time that was

As shown in Figures 10 and 11, it is clear that the standard parameters of dyeing temperature

Generally, the increase in dye-uptake can be explained by the fiber swelling which enhanced the dye diffusion. [37] The effect of dyeing time was conducted to reveal the effect of power ultrasonic on the de-aggregation of dye molecules in the dye bath. It was denoted that the color strength obtained increased as the time increased. The decline in the dye-ability may be attributed to the hydrolytic decomposition of the extract molecules under the influence of

> 30 60 90 120 **Time (min)**

**Figure 10.** Effect of dye bath temperature at different time intervals on the color strength of silk samples dyed ultra‐

30-40

**40-50**

50-60

tively, where the color strength increases with the increase in dyeing temperature.

C, and 50-60 o

C in case of silk and wool respec‐

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217

**3.2. Dyeing parameters**

studied from 30 to 120 mins.

and time were achieved after 90 mins, at 40 – 50 o

sonic energy during prolonged dyeing. [38]

1.5

sonically with 1% (w/v) Osage orange extract.

1.7

1.9

2.1

2.3

**K/S**

2.5

2.7

2.9

**Figure 9.** Effect of Osage orange concentration (w/v)%, extracted ultrasonically in 20 % water/ acetone co-solvent at 60 oC for 90 min, on the color strength of silk and wool samples.

Higher color depth was expected from an increase in the extract concentration and the use of high concentrations of mordant [37]

To study the possibility of forming concentrated extracts, different amounts of Osage orange bark powder (1-10) g were extracted per the optimized 20 % water/ acetone co-solvent. The dyeing process was carried out on silk and wool samples at a liquor ratio of L: R 1:20, for 60 min. at 60 o C. It was noted that, the use of more concentrated extracts resulted in somewhat an increase in color depth; whereas the maximum color depth was achieved with 8% w/v powder on both fabrics as shown in Figure 9. The relative high K/S values for dyeings can be explained with the high amount of bark extracted for this series of dyeing experiments.

#### **3.2. Dyeing parameters**

Langmuir's theories of surface adsorption [36], in which the activity coefficient of Osage or‐ ange extract ions adsorbed into the wool phase are reduced due to specific binding with sites on wool, which is the formation of ion pairs. This theory proposed that dyeing process is an anion exchange process, in which the Osage orange extract molecules displace smaller anions, depending on four steps: a) diffusion to fiber surface, b) transfer across that surface, c) diffusion within to appropriate "sites" and d) binding at those sites. On the other hand, according to the Donnan equilibrium theory, the Osage orange extract was considered to partition between the external solution and internal solution phase in the wool. The later phase is believed to contain a high concentration of fixed ionic groups, and hence solute molecules have reduced activity co-efficient in that phase due to coulombic interaction be‐ tween the anionic groups (OH) in fact: O- of Osage orange extract and the protonated amino

14.09

18.73

**silk wool**

1% 2% 3% 4% 5% 6% 7% 8% 9% 10%

**Figure 9.** Effect of Osage orange concentration (w/v)%, extracted ultrasonically in 20 % water/ acetone co-solvent at

Higher color depth was expected from an increase in the extract concentration and the use

To study the possibility of forming concentrated extracts, different amounts of Osage orange bark powder (1-10) g were extracted per the optimized 20 % water/ acetone co-solvent. The dyeing process was carried out on silk and wool samples at a liquor ratio of L: R 1:20, for 60

C. It was noted that, the use of more concentrated extracts resulted in somewhat

**dye conc. (w/v) %**

groups of wool. [36]

216 Eco-Friendly Textile Dyeing and Finishing

0

60 oC for 90 min, on the color strength of silk and wool samples.

of high concentrations of mordant [37]

min. at 60 o

5

10

**k/S**

15

20

Dyeing temperature and time are important parameters influencing the quality of the dyed silk and wool samples. It is well known that dyeing at high temperature for a long time tends to decrease the fabric strength. [36-38] Therefore, it was proffered to dye the samples ultrasonically at temperatures ranging from 30 to 60 °C, relative to the dyeing time that was studied from 30 to 120 mins.

As shown in Figures 10 and 11, it is clear that the standard parameters of dyeing temperature and time were achieved after 90 mins, at 40 – 50 o C, and 50-60 o C in case of silk and wool respec‐ tively, where the color strength increases with the increase in dyeing temperature.

Generally, the increase in dye-uptake can be explained by the fiber swelling which enhanced the dye diffusion. [37] The effect of dyeing time was conducted to reveal the effect of power ultrasonic on the de-aggregation of dye molecules in the dye bath. It was denoted that the color strength obtained increased as the time increased. The decline in the dye-ability may be attributed to the hydrolytic decomposition of the extract molecules under the influence of sonic energy during prolonged dyeing. [38]

**Figure 10.** Effect of dye bath temperature at different time intervals on the color strength of silk samples dyed ultra‐ sonically with 1% (w/v) Osage orange extract.

349.999115 349.999115 349.999115 349.999115

**wave length K/S**

**pH 3.5 pH 5 pH 6.5 pH 8**

**Figure 12.** Effect of the dye bath pH on the color strength and wave length of silk samples dyed ultrasonically with

**wave length pH values**

2.35

339.9990845

1.75 1.755 1.76 1.765 1.77 1.775 1.78 1.785 1.79 1.795

**K/S**

334.9990845

336.665741

**pH 3.5 pH 5 pH 6.5 pH 8**

**Figure 13.** Effect of the dye bath pH on the color strength and wave length of woolen samples dyed ultrasonically

As shown in Figures 14 and 15, ultrasonic [US] assisted mordanting method possesses a re‐ markable improvement in the color strength, in comparison with the classical thermal meth‐

339.9990845

**3.3. Mordanting methods & colour properties**

**wave length (nm)**

with 1% Osage orange at 50-60 oC for 90 min.

2.4 2.45

2.5

2.55

**K/S**

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219

2.6 2.65

2.7

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics

**wave length (nm)**

1% Osage orange at 40-50oC for 90 min.

**Figure 11.** Effect of dye bath temperature at different time intervals on the color strength of wool samples dyed ultra‐ sonically with 1% (w/v) Osage orange extract

As shown in Figures 12 and 13 the pH values of the dye bath, have a considerable effect on the dyeability of silk and wool fabrics with Osage orange extract under ultrasonic. As the pH increases the dyeability, decreases. The effect of dye bath pH can be attributed to the correlation between dye structure and the protein based materials.

Since the used dye is a water-soluble dye containing hydroxyl groups, it would interact ion‐ ic-ally with the protonated terminal amino groups of silk and wool fibers at acidic pH via ion exchange reaction.

The anion of the dye has a complex character, and when it is bound on fiber, further kinds of interactions take place together with ionic forces. This ionic attraction would increase the dye-ability of the fiber as clearly observed in Figures 12 and 13. At pH greater than 5, the ionic interaction between the hydroxyl anion of the dye and the protein fibers decreases due to the decreasing number of protonated terminal amino groups of silk and wool and thus lowering their dye-ability. It is to be mentioned that the lower dye-ability may be attributed to the enhanced desorption of the dye as its ionic bond is getting decreased [36].

**Figure 12.** Effect of the dye bath pH on the color strength and wave length of silk samples dyed ultrasonically with 1% Osage orange at 40-50oC for 90 min.

**Figure 13.** Effect of the dye bath pH on the color strength and wave length of woolen samples dyed ultrasonically with 1% Osage orange at 50-60 oC for 90 min.

#### **3.3. Mordanting methods & colour properties**

1.5

correlation between dye structure and the protein based materials.

30 60 90 120 **Time (min)**

**Figure 11.** Effect of dye bath temperature at different time intervals on the color strength of wool samples dyed ultra‐

As shown in Figures 12 and 13 the pH values of the dye bath, have a considerable effect on the dyeability of silk and wool fabrics with Osage orange extract under ultrasonic. As the pH increases the dyeability, decreases. The effect of dye bath pH can be attributed to the

Since the used dye is a water-soluble dye containing hydroxyl groups, it would interact ion‐ ic-ally with the protonated terminal amino groups of silk and wool fibers at acidic pH via

The anion of the dye has a complex character, and when it is bound on fiber, further kinds of interactions take place together with ionic forces. This ionic attraction would increase the dye-ability of the fiber as clearly observed in Figures 12 and 13. At pH greater than 5, the ionic interaction between the hydroxyl anion of the dye and the protein fibers decreases due to the decreasing number of protonated terminal amino groups of silk and wool and thus lowering their dye-ability. It is to be mentioned that the lower dye-ability may be attributed

to the enhanced desorption of the dye as its ionic bond is getting decreased [36].

30-40

40-50

**50-60**

1.55

1.6

1.65

**K/S**

sonically with 1% (w/v) Osage orange extract

ion exchange reaction.

1.7

1.75

1.8

218 Eco-Friendly Textile Dyeing and Finishing

As shown in Figures 14 and 15, ultrasonic [US] assisted mordanting method possesses a re‐ markable improvement in the color strength, in comparison with the classical thermal meth‐ od [CH]. The obtained dyeings are governed by the descending dyeing sequence, and can be ranked as follows: pre-mordanting with a mixture of alum and cream of tartar followed by dyeing > post mordanting with alum > post mordanting with a mixture of alum and cream of tartar > premordanting with alum > unmordanted samples.

ed to apply cream of tartar with alum as preferable mordant to get good strong colors as discussed previously. It helps to soften fibers when alum is used, and can also help brighten

**CH US**

the yellow color with good levelness. [40]

**K/S**

rate, and penetration through the fibers. [22-24, 41]

**Blank**

**Figure 15.** Effect of mordant and mordanting method on the color strength of wool dyeings

**alum \***

**alum+cream**

**Mordant & mordanting method**

Sonic energy succeeded in accelerating the rate of mordanting at lower temperatures rather than the conventional heating technique. The exhibited improvement was generally attribut‐ ed to the acoustic cavitation, which is the formation of gas-filled micro-bubbles or cavities in a liquid media, producing implosive collapse, which often forming fast-moving liquid jets, where large increases in temperature and pressure are generated. The micro-jets increase the diffusion of solute inside the intermediate spaces of silk and wool fabrics facilitate the deaggregation of Osage orange molecules in the dye bath and thus increase the dye diffusion

A variety of color hues were obtained with respect to the mordant. It was observed from the color fastness data that the extracted dye from *Osage orange* furnished different color hues with very good affinity for silk and wool fabrics in presence of alum and cream of tartar mordant as illustrated in Tables 1 and 2. The color intensity reached its highest value when the fabrics treated with a mixture of alum and cream of tartar. The brightness of the shades on the dyed samples might be due to the better absorption of Osage orange extract and the easy metal complex formation of mordant with the fibers. Data represented good to very good fastness to washing, because the mordant lead to the formation of a complex dye which aggregates the dye molecules into a large particles insoluble in water. Control sam‐ ples exhibited poor fastness to washing due to the weak dye- fiber bond, and the ionization

of the (OH) groups of the dye during washing under the alkaline condition. [42-45]

**of tartar\***

**alum \*\***

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221

**alum+cream**

**of tartar\*\***

Silk and wool fabrics are highly receptive to mordants due to their amphoteric nature; they can absorb acids and bases with equal effectiveness. Mordants during natural dyeing, exhib‐ its fast color due to their complex formation with the dye and fiber [27, 38]

**Figure 14.** Effect of mordant and mordanting method on the color strength of silk dyeings

It is clear that: (i) pre-mordanting with the nominated mordant brings about a significant en‐ hancement in the K/S values of the obtained dyeings. (ii) the extent of improvement is gov‐ erned by the physical and chemical states of the dye and degree of fixation, (iii) premordanting followed by dyeing gives dyeings with better fastness properties than those dyed without mordant and mordanting after dyeing (iv) the improvement in the dyeings color strength and fastness, reflects higher extent of dye adsorption, interaction and bridg‐ ing with the pre-mordanted substrate via different conjugated bonds [27]

The low color strength in post-mordanting condition is due to the accumulation of the metal dye complex in form of clusters. [39]. The high aluminum content might provide useful ecofriendly chelating with Osage orange molecules presented in the extract that might resist their hydrolysis by water. [39]

The commercial cream of tartar (Potassiun Bitartrate) contains a small percentage of calcium tartrate is frequently employed as a mordant for wool. [40]. In this study it was recommend‐ ed to apply cream of tartar with alum as preferable mordant to get good strong colors as discussed previously. It helps to soften fibers when alum is used, and can also help brighten the yellow color with good levelness. [40]

od [CH]. The obtained dyeings are governed by the descending dyeing sequence, and can be ranked as follows: pre-mordanting with a mixture of alum and cream of tartar followed by dyeing > post mordanting with alum > post mordanting with a mixture of alum and cream

Silk and wool fabrics are highly receptive to mordants due to their amphoteric nature; they can absorb acids and bases with equal effectiveness. Mordants during natural dyeing, exhib‐

**CH US**

of tartar > premordanting with alum > unmordanted samples.

**12.5 13 13.5 14 14.5 15 15.5 16 16.5 17**

**K/S**

220 Eco-Friendly Textile Dyeing and Finishing

their hydrolysis by water. [39]

**Blank**

**Figure 14.** Effect of mordant and mordanting method on the color strength of silk dyeings

ing with the pre-mordanted substrate via different conjugated bonds [27]

**alum\***

**Mordant type and mordanting method**

It is clear that: (i) pre-mordanting with the nominated mordant brings about a significant en‐ hancement in the K/S values of the obtained dyeings. (ii) the extent of improvement is gov‐ erned by the physical and chemical states of the dye and degree of fixation, (iii) premordanting followed by dyeing gives dyeings with better fastness properties than those dyed without mordant and mordanting after dyeing (iv) the improvement in the dyeings color strength and fastness, reflects higher extent of dye adsorption, interaction and bridg‐

The low color strength in post-mordanting condition is due to the accumulation of the metal dye complex in form of clusters. [39]. The high aluminum content might provide useful ecofriendly chelating with Osage orange molecules presented in the extract that might resist

The commercial cream of tartar (Potassiun Bitartrate) contains a small percentage of calcium tartrate is frequently employed as a mordant for wool. [40]. In this study it was recommend‐

**alum+cream**

**of tartar\***

**alum\*\***

**alum+cream**

**of tartar\*\***

its fast color due to their complex formation with the dye and fiber [27, 38]

**Figure 15.** Effect of mordant and mordanting method on the color strength of wool dyeings

Sonic energy succeeded in accelerating the rate of mordanting at lower temperatures rather than the conventional heating technique. The exhibited improvement was generally attribut‐ ed to the acoustic cavitation, which is the formation of gas-filled micro-bubbles or cavities in a liquid media, producing implosive collapse, which often forming fast-moving liquid jets, where large increases in temperature and pressure are generated. The micro-jets increase the diffusion of solute inside the intermediate spaces of silk and wool fabrics facilitate the deaggregation of Osage orange molecules in the dye bath and thus increase the dye diffusion rate, and penetration through the fibers. [22-24, 41]

A variety of color hues were obtained with respect to the mordant. It was observed from the color fastness data that the extracted dye from *Osage orange* furnished different color hues with very good affinity for silk and wool fabrics in presence of alum and cream of tartar mordant as illustrated in Tables 1 and 2. The color intensity reached its highest value when the fabrics treated with a mixture of alum and cream of tartar. The brightness of the shades on the dyed samples might be due to the better absorption of Osage orange extract and the easy metal complex formation of mordant with the fibers. Data represented good to very good fastness to washing, because the mordant lead to the formation of a complex dye which aggregates the dye molecules into a large particles insoluble in water. Control sam‐ ples exhibited poor fastness to washing due to the weak dye- fiber bond, and the ionization of the (OH) groups of the dye during washing under the alkaline condition. [42-45]


In the light fastness test, mordanted colored samples exhibited better light fastness relative to the control ones. This may be due to: i) the aluminum metal in alum mordant protects, both by the steric and electronic effects of the weak point in the dye structure from attack by means of the reactive species during photochemical reaction, in addition ii) the aluminum metal in alum mordant promotes aggregation of the dye. By the way, the poor light fastness is due to the inherent susceptibility of the dye chromophore to the photochemical degrada‐

The colorimetric data indicated the depth and natural tone of the control and mordanted dyed samples. The *L*\* values were found to be lower using alum and cream of tartar as mor‐

mordanted dyed samples corresponding to lighter shades. Similarly, by using alum as

tively. As a result, alum and cream of tartar might be effectively used as mordant for Osage

The light fading of the dyed samples was recorded in terms of the color difference *(ΔE)* as shown in Figures 16-20. It was denoted that sonic energy assisted alum and cream of tartar mordanting method, exhibited a lower degree of fading in comparison with the convention‐ al heating and the application alum mordant in absence of cream of tartar, whereas the premordanting method appears to be preferred having a great efficiency in lowering the degree

The dye physical state is generally important than the chemical structure in determining the color fastness on fibers. (31). It was recognized that the light fastness of many dyed systems has been found to increase with the increase dye concentration applied to the substrate [50].

The fiber swelling was increased with ultrasonic technique due to the sonic energy which i) improves the diffusion and penetration of the dye and mordant molecules inside the pores of the fabric, and ii) the fast breaking-down of the dye molecules, which became much more smaller in size and thus fully dispersed with much higher amount in the dyed samples rela‐ tive to the samples subjected to the conventional heating method, resulted in, the lower de‐ gree of fading in case of ultrasonic assisted dyeing and mordantinting processes. [22-25, 41]

Mixture of alum and cream of tartar mordant renders the dye more bonded and more aggre‐ gated onto fibers, therefore the surface area of the dye accessible to light is reduced, and

Aluminum ions apparently produce metal chelates with improved the overall fastness prop‐ erties. This either could be evidence of the aggregation of dye molecules within the fiber or perhaps of the formation of dye-metal chelates that forms grater stability of the dye mole‐ cules when co-ordinated with the complex aluminum metal atom that might form quite large aggregates giving the highest light fast with the lowest fading degree. [23, 51], resulted

thereby the dye fades at lower degree with nearly constant rate of fading.

in, the low and nearly constant fading rate in case of the mordanted samples.

values were also higher corresponding to lighter shades. The higher values

indicated the brightness, representing the redness and yellowness hues respec‐

values were found to be higher in case of un‐

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223

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics

tion. [46-51]

mordant the *L*\*

and *b*\*

orange extract.

of *a*\*

dant corresponding to deeper shades. The *L*\*

of fading in comparison with the post mordanting

**Table 1.** The CIELab values and fastness properties of Osage orange dyed silk


**Table 2.** The CIELab values and fastness properties of Osage orange dyed wool

In the light fastness test, mordanted colored samples exhibited better light fastness relative to the control ones. This may be due to: i) the aluminum metal in alum mordant protects, both by the steric and electronic effects of the weak point in the dye structure from attack by means of the reactive species during photochemical reaction, in addition ii) the aluminum metal in alum mordant promotes aggregation of the dye. By the way, the poor light fastness is due to the inherent susceptibility of the dye chromophore to the photochemical degrada‐ tion. [46-51]

**Sampls L\* a\* b\* Wash fastness Light fastness**

CH 50.95 3.57 43.37 3-4 5-6

US 55.05 3.56 51.67 4 6

alum\*\* CH 54.45 4.83 48.08 3-4 6

alum\*\* US 54.99 5.40 52.12 3-4 6

**Sample L\* a\* b\* Wash fastness Light fastness**

CH 65.07 - 0.59 60.08 3-4 5-6

US 67.46 - 2.93 62.40 4 6

alum\*\* CH 64.61 0.68 62.40 3-4 6

alum\*\* US 64.71 1.56 58.98 3-4 6

Alum + cream of tartar \*\* CH 64.54 0.40 60.72 3-4 6

Alum + cream of tartar \*\* US 65.03 1.23 55.29 3-4 6

CH 65.43 - 0.14 56.89 4 6-7

US 64.11 - 1.14 52.60 4 6-7

Blank US 68.97 - 0.02 55.19 3 5

Alum + cream of tartar \*\* CH 53.01 3.96 38.21 3-4 6

Alum + cream of tartar \*\* US 52.75 5.52 47.49 3-4 6

**Table 1.** The CIELab values and fastness properties of Osage orange dyed silk

**Table 2.** The CIELab values and fastness properties of Osage orange dyed wool

CH 50.57 3.81 37.31 4 6-7

US 50.29 6.43 44.8 4 6-7

Blank US 54.12 4.71 49.2 3 5

alum\*

222 Eco-Friendly Textile Dyeing and Finishing

alum\*

Alum + cream of tartar \*

Alum + cream of tartar \*

alum\*

alum\*

Alum + cream of tartar \*

Alum + cream of tartar \*

The colorimetric data indicated the depth and natural tone of the control and mordanted dyed samples. The *L*\* values were found to be lower using alum and cream of tartar as mor‐ dant corresponding to deeper shades. The *L*\* values were found to be higher in case of un‐ mordanted dyed samples corresponding to lighter shades. Similarly, by using alum as mordant the *L*\* values were also higher corresponding to lighter shades. The higher values of *a*\* and *b*\* indicated the brightness, representing the redness and yellowness hues respec‐ tively. As a result, alum and cream of tartar might be effectively used as mordant for Osage orange extract.

The light fading of the dyed samples was recorded in terms of the color difference *(ΔE)* as shown in Figures 16-20. It was denoted that sonic energy assisted alum and cream of tartar mordanting method, exhibited a lower degree of fading in comparison with the convention‐ al heating and the application alum mordant in absence of cream of tartar, whereas the premordanting method appears to be preferred having a great efficiency in lowering the degree of fading in comparison with the post mordanting

The dye physical state is generally important than the chemical structure in determining the color fastness on fibers. (31). It was recognized that the light fastness of many dyed systems has been found to increase with the increase dye concentration applied to the substrate [50].

The fiber swelling was increased with ultrasonic technique due to the sonic energy which i) improves the diffusion and penetration of the dye and mordant molecules inside the pores of the fabric, and ii) the fast breaking-down of the dye molecules, which became much more smaller in size and thus fully dispersed with much higher amount in the dyed samples rela‐ tive to the samples subjected to the conventional heating method, resulted in, the lower de‐ gree of fading in case of ultrasonic assisted dyeing and mordantinting processes. [22-25, 41]

Mixture of alum and cream of tartar mordant renders the dye more bonded and more aggre‐ gated onto fibers, therefore the surface area of the dye accessible to light is reduced, and thereby the dye fades at lower degree with nearly constant rate of fading.

Aluminum ions apparently produce metal chelates with improved the overall fastness prop‐ erties. This either could be evidence of the aggregation of dye molecules within the fiber or perhaps of the formation of dye-metal chelates that forms grater stability of the dye mole‐ cules when co-ordinated with the complex aluminum metal atom that might form quite large aggregates giving the highest light fast with the lowest fading degree. [23, 51], resulted in, the low and nearly constant fading rate in case of the mordanted samples.

**Post mordanting dyed silk**

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics

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225

0 2 4 6 8 10 12 14 16 18 20 22 24 **Exposure time (hr)**

**Pre mordanting dyed wool**

0 2 4 6 8 10 12 14 16 18 20 22 24 **Exposure time [hr]** 

**Figure 19.** Effect of Xenon arc lamp exposure time on the color retained of the pre-mordanted dyed wool samples

alum + cream of tartar CH\*\* alum + cream of tartar US\*\*

alum CH\*\* alum US\*\*

**Figure 18.** Effect of Xenon arc lamp exposure time on the color retained of the post mordanted dyed silk samples

alum+cream of tartar CH\*\* alum+ cream of tartar US\*\*

alum CH\*\* alum US\*\*

0

0

20

40

60

80

**color retained**

100

120

140

20

40

60

**color retained %**

80

100

120

**Figure 16.** Effect of Xenon arc lamp exposure time on the color retained of silk and wool blank dyed samples

**Figure 17.** Effect of Xenon arc lamp exposure time on the color retained of the premordanted dyed silk samples

**Blank**

0 2 4 6 8 10 12 14 16 18 20 22 24 **Exposure time (hr)**

**Figure 16.** Effect of Xenon arc lamp exposure time on the color retained of silk and wool blank dyed samples

**pre mordanting dyed silk**

alum CH\* alum US\*

0 2 4 6 8 10 12 14 16 18 20 22 24

alum + cream of tartar CH\* alum + cream of tartar US\*

**Exposure time (hr)**

**Figure 17.** Effect of Xenon arc lamp exposure time on the color retained of the premordanted dyed silk samples

**Silk Wool**

0

20

40

60

**color retained %**

80

100

120

**color retained %**

224 Eco-Friendly Textile Dyeing and Finishing

**Figure 18.** Effect of Xenon arc lamp exposure time on the color retained of the post mordanted dyed silk samples

**Figure 19.** Effect of Xenon arc lamp exposure time on the color retained of the pre-mordanted dyed wool samples

sonic energy during prolonged dyeing. Osage orange is a water-soluble dye containing hy‐ droxyl groups that interacts ionic-ally with the protonated terminal amino groups of silk and wool fibers at acidic pH 5 via ion exchange reaction. The lower dye-ability at pH greater than 5 may be attributed to the enhanced desorption of the dye as its ionic bond is getting decreased. Improvement in the dyeing color strength and fastness properties reflects the higher extent of dye adsorption, interaction and bridging with the pre-mordanted dyed samples via different conjugated bonds with the mixture of alum and cream of tartar mor‐ dant. The low color strength in post-mordanting method is due to the accumulation of the aluminum metal dye complex in form of clusters. Sonic energy succeeded in accelerating the rate of mordanting at lower temperatures rather than the conventional heating technique due to the acoustic cavitation which increases the diffusion of solute inside the intermediate spaces of silk and wool fabrics, facilitating the de-aggregation of Osage orange molecules in the dye bath and thus increases the dye diffusion rate, and its penetration through the fibers. A variety of hues were obtained with respect to the mordant. It was observed from the color fastness data that the extracted dye from *Osage orange* furnished different color hues with very good affinity for silk and wool fabrics in presence of a mixture of alum and cream of tartar mordant. Mordanted dyed samples exhibit better wash and light fastness, with a low‐

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics

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227

Special thanks for the school of chemical and physical science, at Victoria university of Well‐ ington in NZ for their financial support. Also many thanks for King abdul-Aziz University, Faculty of Arts and Designs, Fashion Design department for their kindly scientific support

1 King Abdul- Aziz University, Faculty of Arts and Design, Fashion Design, Saudi Arabia

2 Helwan University, Faculty of Applied Arts, Textile printing dyeing and Finishing Depart‐

[1] Gulrajani M L. Introduction to Natural Dyes, Indian Institute of Technology. New

[2] Gulrajani ML. Natural Dyes- Part 1, Present status of Natural Dyes. Colourage 1999;.

est degree of photo fading relative to the control ones.

**Acknowledgements**

**Author details**

Heba Mansour1,2

ment,

**References**

Delhi: India;.1992

46(7): 25-27.

**Figure 20.** Effect of Xenon arc lamp exposure time on the color retained of the post mordanted dyed wool samples
