In this section, various properties of the yarns produced by the alternative method based on the application of a conductive nanosuspension to the open fibre bundle with an apparatus mounted on the conventional ring spinning system consisting of a feeding pump, syringe and needle were examined. Additionally, some of the fabric properties knitted from these yarns are studied. The results were given below and ring spun yarn without rGO nanoparticles was named as a reference and undoped ring spun yarn while the yarn comprising rGO nanoparticles was called as a conductive and doped yarn.
3.1. Yarn Morphology
rGO nanosuspension was applied on to the viscose fibres at the 70 mL/h feeding rate and SEM images of Ne 16/1 undoped viscose ring spun yarns for different magnifications were analysed (Figure 4a). The images of rGO doped viscose yarns were compared with rGO undoped reference viscose ring spun yarns (Figure 4b).
As seen in Figure 4a, a clean structure could be seen between the fibres and also on the surface of undoped reference viscose ring spun yarn. Comparing with the images of untreated ring spun yarns, rGO nanoparticles were observed on the fibre surface (shown by red circles in Figure 4b). As observed in literature for fabric application (Molina et al. 2013, Shateri-Khalibad and Yazdanshenas, 2013a, 2013b; Karimi et al. 2014), rGO sheets wrinkled, folded and deposited on a fiber surface. According to yarn appearances given in Figure 5, white colour of viscose fibres were getting darker after the rGO nanosuspension application, and this case indicated the presence of rGO nanoparticles in yarn structure. In order to confirm this case, changes in the weight of reference (undoped) and rGO doped yarns were compared. It was found that the weight is 0.036016 g/m for undoped ring spun yarn while 0.038108 g/m for rGO doped yarn (at 70 mL/h). With the application of rGO nanoparticles, the weight of the rGO doped yarns increased. On the other hand, it was observed that reference and rGO applied yarns had similar yarn structure due to the real-twist given by ring-traveller during the classical ring spinning process. Both yarn types still carried the ring spun yarn character. However, it was determined that rGO applied ring spun yarns have lower number of protruding fibres and therefore compact yarn structure was observed on rGO doped yarns in comparison to undoped reference yarns.
Yarn Conductivity
In order to impart the electrical conductivity to viscose fibre bundle, different feeding rate values of reduced graphene oxide (rGO) nanosuspension were researched, and proper feeding rate value was determined. Feeding rates were increased from 30 mL/h to 80 mL/h and rGO nanosuspension was applied to viscose fibre bundle with the needle and syringe in a determined amount provided by the feeding pump. Electrical conductivity of the produced Ne 16/1 viscose ring spun yarns were measured by two-probe measurement method. During the experiments, no resistance value was determined at 30, 40 and 45 mL/h feeding rates, and therefore these feeding rates were concluded as insufficient. In addition, yarn colour was expected to change from white to black after the rGO nanosuspension application. However, it was observed the white or gray places on the yarn surface (shown by red circles in Figure 6) or yarn colour was not completely black. Thus, irregular colour distribution was determined through the yarn length due to insufficient rGO feeding. Following these feeding rates, yarn production was realized at feeding rates of 50 mL/h and above, and electrical resistance value was detected in rGO doped viscose ring spun yarns. This case meant that produced yarns become conductive and show conductivity property after rGO nanosuspension application with the alternative application method. Electrical resistance results are given in Figure 7 for 50-80 mL/h. As seen, electrical resistance values decreased when the feeding rate was increased from 50 mL/h to 80 mL/h. At a feeding rate of 80 mL/h, it was determined that resistance values tend to increase. This finding indicated that rGO nanosuspension application with the alternative method improves the electrical conductivity up to a certain conductive solution feeding value. However, conductivity tended to increase above the limit rGO application value.
This case was similar to the results of the graphene application to textile fabrics in the literature. In the studies, woven and knitted fabrics were impregnated with GO and subsequently reduced by chemical or thermal reduction. In order to improve the electrical conductivity, application cycle comprising rGO nanosuspension padding and drying process was increased, and it was determined that the resistance values decreased up to a certain application cycles. In insufficient rGO nanosuspension application cycles, rGO layers may not be in contact so that electrical conduction is more difficult and higher resistance values were determined. When the rGO application was increased, resistance of the fabric samples tended to decrease due to the improved contact between the rGO sheets. Beyond certain application cycles, electrical resistance values started to increase slightly, and conductivity was getting lower. After a certain rGO deposition, the limit of conductivity was reached and more rGO did not produce an increase in the conductivity due to saturation of textile materials with rGO nanoparticles (Molina et al. 2013; Sahito et al. 2015).
On the other hand, as similar to our study, Karim et al. (2017) obtained GO with a modified Hummer’s method and reduced GO chemically using a reducing agent (Na2S2O4) to enable one-step graphene application process. rGO dispersion applied to the textile fabric using a simple pad-dry technique without the requirement of a reduction process. It was indicated that electrical resistance values reduce about ∼90% after five application cycles. The authors explained the significant improvement in electrical conductivity of the fabrics by an absorption and adsorption phenomenon. In first few application cycles, absorption of rGO dispersion into the fibres was pre-dominant. The nanoplates could disperse on the fibre surface uniformly as the rGO application cycles were increased. When the saturation point was reached, rGO was then mainly adsorbed on the fibre surface and continuous conductive film was formed by creating better connections between flakes. Thus, the resistance of the fabric decreased by presenting more flakes on the fibre surface and by the restacking of the flakes through the Van der Waals forces applied by the squeeze rollers (Karim et al. 2017). As a result, electrical conductivity improved up to a certain rGO nanosuspension feeding rate as reported in rGO fabric application studies.
One the other hand, in the study, the lowest resistance value was determined as 1.008 MΩ/cm in rGO/viscose ring spun yarns at a feed rate of 70 mL/h produced with alternative method. The lowest variation in the resistance values and better stability of the rGO nanoparticles in the yarn structure was obtained at 70 mL/h and therefore 70 mL/h was decided as an optimum feeding rate (Figure 7).
Tensile Properties
In order to analyze the effect of rGO nanosuspension application on tensile properties of the yarns, tenacity and breaking elongation of rGO doped Ne 16/1 viscose ring spun yarns were analyzed. The results of the yarns were compared with undoped reference viscose ring spun yarns. As seen in Figure 8, tenacity of rGO doped yarns changed depending on rGO nanosuspension feeding rates. As the rGO feeding was increased, tenacity of rGO doped yarns was getting higher, and the highest yarn tenacity values were obtained at the highest rGO nanosuspension feeding rate values (75 mL/h and 80 mL/h). rGO doped viscose yarns had slightly higher yarn tenacity values at 75 mL/h and 80 mL/h feeding rates. The differences in tenacity values of doped (75 mL/h and 80 mL/h) and undoped yarns were about 2-3%. It was determined that optimum feeding rate of 70 mL/h ensure stronger and also conductive yarn production.
The increase in rGO doped yarn tenacity might result from reinforcing characteristic of graphene. Graphene has extraordinary mechanical properties, including a record tensile strength (130 GPa) (Xu and Gao 2015). In literature, it was reported that the addition of a low fraction of graphene nanosheets into polymer composites as a filler results in a significant improvement in the mechanical strength of the composites. It was stated that the carboxyl and hydroxyl functional groups on the basal planes and edges of the starting GO nanosheets may act as linkers between the graphene and the polymer (Cheng et al. 2014). Regarding graphene application to textile fabrics, it was indicated that the breaking and tearing strength of graphene (rGO) applied fabrics is increased (Yaghoubidoust et al. 2014; Gan et al. 2015; Karim et al. 2017). The presence of graphene particles had positive effect of mechanical properties and graphene was shown as the reason of this case (Gu and Zhao 2011; Abbas et al., 2013; Yaghoubidoust et al. 2014).
Breaking elongation of the yarns obtained with alternative and classical ring spinning methods was compared and the results are shown in Figure 9. As similar to yarn tenacity results, breaking elongation values of rGO nanosuspension doped yarns changed depending on nanosuspension feeding rates. According to the values, breaking elongation values of viscose ring spun yarns were about 15% while they were about 11.8-15% for doped yarns depending on feeding rates. rGO doped yarns produced at 70 mL/h feeding rate had similar yarn breaking elongation values with undoped reference viscose ring spun yarns. However, rGO doped yarns produced at lower and higher feeding rates than 70 mL/h had mostly lower elongation values than that of the undoped ring spun yarns. In literature, Kaynak et al. (1996) stated similar findings for carbon black (CB) containing composites and indicated that elongation at break values decreased sharply with the filler content for all types due to the stress–concentration effect. Therefore, breaking elongation values of rGO doped yarns might be decreased to some extent due to the incorporation of the rigid filler into yarn structure.
As a conclusion, yarn tenacity and breaking elongation results indicated that rGO nanosuspension applied yarns with the developed alternative method have comparable tensile properties with undoped reference viscose ring spun yarns. However, optimum feeding rate of nanosuspension was effective on tenacity and breaking elongation values of the doped yarns. Particularly, insufficient nanosuspension feeding caused a loss of yarn tenacity and breaking elongation values of the yarns besides low electrical conductivity values.
Effect Of Fiber Type
In this part of the study, it was aimed to evaluate the performance of alternative production method using different fibre types. Therefore, in addition to viscose fibres, rGO nanosuspension was applied to cotton and polyester fibres. rGO nanosuspension was doped to hydrophilic (bleached) cotton and polyester fibre bundle with alternative method on conventional ring spinning machine at 70 mL/h feeding rate. Electrical resistance values of the ring spun yarns are given in Table 2.
As seen in Table 2, cotton and polyester fibres had a certain degree of electrical resistance and hence conductivity values. Therefore, developed alternative method allows the conductive yarn production with various fibre types. However, rGO doped cotton and polyester yarns had higher resistance than viscose ones. Hydrophobic structure of the cotton and polyester fibres was thought a possible for their lower conductivity values.
Table 2
Electrical resistance values of rGO doped ring spun yarns for different fibre types
Fibre type
|
Mean resistance (MΩ/cm)
|
Viscose
|
1.008
|
Cotton
|
21.780
|
Polyester
|
43.411
|
Effect Of Yarn Winding Process
In order to convert the rGO doped ring spun yarns into fabric form with industrial weaving and knitting processes, the yarns must be transferred from cops to bobbin in order to be used in post-spinning processes. For this reason, reference undoped and rGO applied viscose ring spun yarns were wound on to the bobbin by winding machine. As known, the yarn during the winding process passes from various parts of winding machine such as yarn guide, tension regulator, quality control units, and hence subjects to friction intensely. In order to evaluate the effect of friction on electrical conductivity of yarns, rGO doped ring spun viscose yarns were wound from cops to bobbin on the Schlafhorst winding machine at high production speeds of 1000 m/min (Figure 10). Three undoped and rGO doped yarn cops (produced at 70 mL/h feeding rate) were wound on the bobbin and ten electrical resistance measurements were done on the bobbin by two-probe measurement method. Electrical resistance values of the rGO yarn bobbins given in Table 3 indicated that the yarns still maintain their conductivity property after winding process. However, the resistance values of the yarns increased approximately 2 times after the winding process. An expected increase might be resulted from friction occurred during the winding. In addition to the analysis of resistance results, the ratio of change in resistance values to initial resistance values was calculated (ΔR/R0). When the results were examined, it was determined that ΔR/R0 was very small (≈1).
Table 3
Electrical resistance results after winding process
Before winding (MΩ/cm)
|
After winding (MΩ/cm)
|
ΔR/R0
|
1.008
|
2.197
|
1.179
|
Conductivity Of Knitted Fabrics
In the study, rGO doped yarns were used in a flat knitting machine to investigate the usability of the yarns in the knitting process. In this part, it was also aimed to evaluate the changes in conductivity property of the rGO doped yarns against intense friction occurred in fabric knitting. The yarns rub against various metal parts such as thread guide, needle, and platinum during the knitting process. For the knitted fabric production, conductive viscose ring spun yarns wound on to the bobbin were used and electrical resistance values of the fabrics (Figure 11) were measured by two-probe method.
When the electrical resistance results were examined (Table 4), it was determined that the resistance values increase after fabric production, as expected. However, the ratio of change in resistance values to initial resistance value (from yarn cops to fabric) (ΔR/R0) was very small (<1) and the resistance values increased slightly. This result shows that electrical resistance values almost does not change during the processes from yarn to fabric production. Additionally, knitted fabrics obtained from rGO doped yarns had still electrical conductivity feature even after high friction effect in knitting process.
Table 4
Electrical conductivity results of fabric samples knitted from rGO doped viscose ring spun yarns
Resistance of yarn cops (MΩ/cm)
|
Resistance of yarn bobbin (MΩ/cm)
|
Resistance of knitted fabric (MΩ/cm)
|
Resistance change from cops to fabric form (ΔR/R0)
|
1.008
|
2.197
|
1.803
|
0.788
|
Comparison With Impregnation Method
To evaluate the performance of the alternative method, rGO nanosuspension was applied to the fabrics knitted from undoped reference viscose ring spun yarns. rGO nanosuspension was applied to 10 × 10 cm2 knitted fabrics by immersion&drying method due to its low cost, easy application and does not require complex equipment on the ATAÇ-FY350 laboratory type foulard device. After application, rGO doped fabrics were dried at room temperature. Immersion&drying process was repeated 5 times due to better conductivity values determined in literature (Javed et al. 2014; Sahito et al. 2015; Zhou et al. 2015) and also our previous study (Özen 2020; Özen et al. 2021). Resistance values of the fabrics were measured by the two-probe method. The results were compared with that of the knitted fabrics obtained from developed alternative application method. When the results were examined (Table 5), it was determined that knitted fabrics obtained from alternative application method have higher resistance and hence lower electrical conductivity values compared to the impregnation&drying method. However, the difference between resistance values of both application methods was about 4 times. Nevertheless, both fabrics had a resistance value of MΩ level and hence it is thought that the results of the fabrics are comparable. Higher resistance values obtained from alternative method indicated that amount of rGO nanoparticle applied with alternative method might be lower than that of the impregnation&drying method. Therefore, comparing with alternative application method, more connections between flakes realized by impregnation&drying method might lead to more reduction in resistance of the fabric.
Table 5
Electrical resistance results of the knitted fabric samples
Application type
|
Two-probe
|
Four-probe
|
Immersion&drying method (5 repeations)
|
0.456 MΩ/cm
|
-
|
Alternative method
|
1.803 MΩ/cm
|
1.64 kΩ.cm
|
In the study, electrical resistance of the knitted fabric samples was determined by four-probe method in order to compare the resistance values of this study with the findings given in literature. As seen in Table 6, the resistance values of the fabric samples knitted from rGO doped yarns were about 1.64 kΩ.cm and the values were lower than 100 kΩ. In literature, Fugetsu et al. (2010) classified the usage of conductive fabrics according to a resistance value of 100 kΩ.cm and stated that the fabrics with a resistance value of 100 kΩ.cm and lower values can be used in soft and flat electric heaters while the fabrics with a resistance value higher than 100 kΩ.cm can be used in antistatic products. Therefore, rGO applied fabric samples with a resistance value of 100 kΩ.cm could be thought as a considerably conductive material. On the other hand, an accurate and precise measurement of four-probe method led to a considerably difference (103) between the resistance values determined by two and four-point methods. Therefore, the results of both methods were not coincided with each other completely.
The Effect Of Washing On Electrical Conductivity
In order to investigate the washability the conductive rGO viscose knitted fabrics, fabric samples were washed with the detergent at 40°C. Resistance values of washed samples were determined by four-probe method and it was seen that electrical resistance values of rGO-containing fabrics tend to increase after washing process (Table 6). However, the value was lower than 100 kΩ. Therefore, it can be said that laundering did not have considerable effect on the electrical conductivity of these fabric samples, and the samples kept their conductivity property.
Table 6
Electrical resistance results of the unwashed and washed fabric samples
Application method
|
Before washing
(kΩ.cm)
|
After washing
(kΩ.cm)
|
Rate of resistance change (ΔR/R0)
|
Alternative method
(knitted fabric)
|
1.64
|
7.66
|
3.67
|
Air Permeability
Air permeability is an important factor used to provide an indication of the breathability of the fabrics and hence clothing comfort. In some products, high air permeability is desirable. In order to determine the effect of alternative application method on permeability property of the fabric, air permeability of knitted fabrics produced from rGO doped viscose ring spun yarns was compared with that of the reference fabrics obtained from undoped yarns. Test results were analyzed statistically by SPSS 16.0 statistical software to determine any significant differences. ANOVA multiple-range test (LSD method) were used and ANOVA analyses were performed for α = 0.05 significance level (Table 8). According to Figure 12 and Table 8, it was observed that the fabrics produced from alternative application method had significantly higher air permeability values than the fabrics knitted from undoped yarns. In addition, all knitted fabrics produced at three different rGO feeding rates gave better air permeability values than undoped reference fabrics. This result indicated that knitted fabrics obtained from alternative application method have a more permeable structure resulted from compact structure of rGO doped viscose ring spun yarns. As seen in Figure 13, rGO doped yarns had lower protruding hairs and more space between the yarns might enhance the air permeability of the fabrics. In the impregnation method, the pores in the fabric are covered with the applied nanoparticle and thus the gaps are closed. But, in alternative application method, the pores are not closed by rGO nanoparticles and hence, it is possible to obtain higher permeability values.
Table 8
ANOVA LSD test results of air permeability values of the fabrics knitted from undoped and rGO doped yarns
Yarn types
|
Sig.
|
Undoped
|
rGO doped-65 mL/h
|
0.000*
|
rGO doped-70 mL/h
|
0.000*
|
rGO doped-75 mL/h
|
0.000*
|
rGO doped-65 mL/h
|
rGO doped-70 mL/h
|
0.103
|
rGO doped-75 mL/h
|
0.040*
|
rGO doped-70 mL/h
|
rGO doped-75 mL/h
|
0.606
|
*. The mean difference is significant at the 0.05 level. |
In fabric finishing treatments such as impregnation, coating, vapour deposition etc. methods, air permeability of the applied fabrics generally decreases due to coating of the fabric and presence of nanoparticle in the fabric structure. Nanoparticles block the passage of air and the pores in the fabric structure are closed. This results in a decrease in air permeability and hence the properties related with fabric comfort. It is desirable to have a fabric with higher air passage to facilitate heat dissipation and sweat evaporation (Chen et al. 2010). Summing up, alternative application method provided an important advantage in air permeability and hence the properties related with fabric comfort.
Overview Of Ecological Impact
Textile industry has important environmental impacts such as high energy consumption, water and air pollution, waste disposal and odour generation (Butekom 2014). Among the textile processes, in particular, dyeing and finishing processes cause high amount of natural resource consumption and wastewater discharge comprising high amounts of chemical substances. Especially, in recent years, dyeing-finishing processes have become even more important with the increasing expectations of consumers from textile products. This results in the production of wastewater arising not only from the removal of impurities from the raw materials but also from the residual chemical reagents used in processes. Therefore, large amounts of water are generally required for processing (Correia 1994). For example, water consumption reaches to 80–100 m3/ton of finished textile and waste water discharge is about 115–175 kg of COD/ton for a finished textile product. Therefore, biggest impact of finishing processes on the environment is related to primary water consumption and waste water discharge (a large range of organic chemicals, low biodegradability, colour, salinity) (Savin et al. 2008).
Nowadays, the shortage of water resources is severe in the world and clean water has become increasingly scarce as discharges of industrial effluents. Textile wastewater includes a large variety of dyes and chemicals additions (detergents, sulphide compounds, solvents, heavy metals, inorganic salts etc.) and this case makes the textile industry an environmental threat in terms of liquid waste and also its chemical composition (Venceslau et al. 1994). Therefore, negative effects of the textile industry on human health and natural life have reached a nonignorable level. From this point on, in the textile industry, there is a need to use production methods and materials that have lower environmental impacts in terms of chemical, energy and water consumption and waste water generation.
In the study, ecological impact of the developed alternative application method was evaluated in general with the finishing methods widely used in practice. Finishing processes used in practice involve impregnation of the fabric using a padding technique followed by a fixation step by heat. Subsequent washing may be carried out to remove residual chemicals. However, in developed application method, drying/fixation and subsequent washing processes are not required. On account of no need of drying/fixation and additional washing, the method actually provides an advantage. When the water consumption was taken into consideration, water consumption varies between 0.5-10 litres per 1 kg of fabric depending on fabric and machine types in impregnation and exhaustion methods widely used in textile dyeing and finishing operations (Tarakçıoğlu 1979). Güngör et al. (2009) reported that 100 litres of water is averagely consumed per 1 kg of textile product in textile dyeing and finishing processes. Lu et al. (2010) stated that about 150 litres of water are consumed on the average for every kg of cloths processed in a typical dyeing and finishing mill. However, in alternative application method, it is between 0.4-0.5 litres per 1 kg. In addition, in other application methods such as impregnation, exhaustion and coating, substances that cannot be taken by the fabric are thrown away, and hence negative effects such as environmental load caused by wastewater and inefficient use of functional materials arise. In the alternative method, unused solution was not disposed since the sample was not kept in a solution or passed through a solution as in conventional application methods such as impregnation, exhaustion etc. Therefore, the alternative application method may offer significant advantages, especially in terms of clean water usage and wastewater disposal, compared to commonly used application methods such as impregnation, exhaustion and coating.
Table 9
Ecological evaluation of application methods used in textile dyeing & finishing processes
Method
|
Application conditions
|
Ecological situation
|
Impregnation
|
Short flotte
(1/0.5 - 1/1)
|
-Water consumption
(min. 0.5 L for 1 kg fabric)
|
-Dispersion, which is not absorbed by the fabric, turns into waste water together with the chemicals.
|
Exhaustion
|
Long flotte
(1/3 - 1/50)
Generally, 1/8 or 1/10 flotte rate is used.
|
-Water consumption
(min. 3-10 L for 1 kg fabric)
|
-The fabric cannot incorporate the functional material in the bathroom.
-Efficiency is low.
-After application, a significant amount of wastewater occurs.
|
Alternative method
|
-
|
-Dispersion is applied onto the fiber strand in the yarn spinning zone.
-The amount of water used for 1 kg of fabric is approximately 0.4-0.5 L.
|
-Water consumption is lower than current methods.
-There is no apparent wastewater problem.
|