Using Spraying as an Alternative Method for Transferring Capsules Containing Shea Butter to Denim and Non-Denim Fabrics
Using Spraying as an Alternative Method for Transferring Capsules Containing Shea Butter to Denim and Non-Denim Fabrics
Preparation of microcapsules for delivery of active ingredients
The aim of this study was to prepare microcapsules and transfer them to denim and non-denim trousers using different application methods. For this purpose, shea butter as active agent was encapsulated in an ethyl cellulose shell using the spray dryer method, and capsule optimisation was studied. A morphological assessment showed that the capsules had a smooth surface and were spherical in shape. The homogenous size distribution of the capsules was supported by laser diffraction analysis. The capsules showed a narrow size distribution, and the mean particle size of optimum formulations of shea butter was 390 nm. Denim fabrics were treated with shea butter capsules using the methods of exhaustion and spraying in order to compare these application methods. The presence of capsules on the fabrics was tested after five wash cycles. The comparison of application methods found similar preferred characteristics for both the exhaustion and spraying methods. However, the spraying method was found to be more sustainable, because it allows working with low liquor ratios in less water, with lower chemical consumption and less waste than the exhaustion method, which requires working with a high liquor ratio. This study showed that the spraying method can be used as an alternative to other application methods in the market for reducing energy consumption, and shea butter capsules can provide moisturising properties to the fabrics.
The concept of wellness has been talked about in recent times in relation to health and a healthy lifestyle. Similarly the wellness or health-improving finishing processes of textiles have gained importance. Cosmetic textiles, also known as wellness textiles, are considered examples of these clothing products (1, 2). Cosmetic textiles are textile products that release a specific substance or solution to the human body, usually to the skin, at certain time intervals; they are claimed to have properties such as cleaning, perfuming, change in appearance, protection and improvement of body odour (1). Such garments, which are mainly designed to transfer certain active substances for cosmetic purposes through contact with the skin, are in increasing demand today, especially in developed nations, where the desire of people to live a longer and higher quality life and to look younger has created a demand for beautifying and anti-ageing products (3).
Advances in cosmetic textiles have been achieved by physically or chemically bonding microcapsules containing cosmetics to the fibre surface. Microencapsulation, which plays an important role in the development of cosmetic textiles, is a technique of packaging active substances in solid, liquid or gas form into a second substance to protect the active substance from the environment (4, 5).
The encapsulation process produces small spheres covered with a thin shell or film to protect the active substance. Using this technology, it is possible to protect easily perishable substances such as insecticides, antibacterials and antioxidants from environmental factors like heat, light and oxygen. In addition, the wearer is exposed to much lower doses of these substances. Using microcapsules in textile finishing, it is possible to produce resistant-to-wash textile products that are effective even when less active substance is used (6–15).
Recent studies have shown microencapsulation for cosmetics to be a logical and effective solution in terms of protection and as a carrier for active ingredients. Microencapsulation has the potential to deliver active ingredients in certain difficult situations, such as when these substances contain glycolic acid, alpha hydroxy acids or salicylic acid or when they have high alcohol content or critical water-in-oil or silicone emulsions. They can be used to deliver active ingredients to the skin in a safe, targeted, effective and painless manner, protecting compounds such as antioxidants from oxidation and from degradation by heat, light and moisture or controlling the release rate (16, 17). Microencapsulation can be used in cosmetic applications such as the production of shower and bath gels, lotions and creams, hair products, sunscreens and tanning creams, makeup, perfumes, soaps and toothpastes, among others. Microencapsulation can help improve the cosmetic and personal care industries through innovation, allowing the production of high-added-value products in response to human needs and desires (18–21). In other studies, biopolymers (natural polymers) and biodegradable polymers such as chitosan were used as encapsulating materials, with greater interest for applications in the field of skin delivery systems (22–24).
In general, the transfer of microcapsules is done using the impregnation and exhaustion method in the textile industry. The spraying method, however, is becoming more commonly used in the textile industry in order to reduce the amount of water, chemicals and energy. This is more sustainable because it works with low liquor ratios and less water, chemical consumption and waste in comparison with traditional methods. Therefore this method was chosen as an alternative to the exhaustion method (25, 26).
Ethyl cellulose, which was chosen as shell material, is a rigid, thermoplastic and hydrophobic material. This polymer is resistant to water, alkali and salt. It is compatible with the spray dryer technique and can be applied to a textile surface. The spray drying method is very popular among users in the pharmaceutical and food industries because of its characteristics of fast heat-transfer, rapid water evaporation and short drying time. It can improve the dissolution rate of certain formulations. In this method, materials can be directly dried into powder. It is easy to change the drying conditions and adjust product quality standards, it has high production efficiency and large production capacity (27, 28). Shea butter is a fat extracted from the nut of the African shea tree (Vitellaria paradoxa). In addition to many nonsaponifiable components, shea butter usually contains the following fatty acids: oleic acid (40–60%), stearic acid (20–50%), linoleic acid (3–11%), palmitic acid (2–9%), linolenic acid (<1%) and arachidic acid (<1%). Shea butter melts at body temperature. Proponents of its use for skin care maintain that it absorbs rapidly into the skin, acts as a ‘refatting’ agent and has good water-binding properties (29–32).
In this study, it was aimed to evaluate the behaviour of microcapsules that contain shea butter transferred with the spraying method to become an alternative to conventional methods. Firstly, shea butter carrying ethyl cellulose microcapsules were produced with spray dryer method. As part of characterisation studies of microcapsules, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and gas chromatography–mass spectrometry (GC-MS) analyses were performed. The optimum formula was applied to denim and non-denim fabrics by the exhaustion and spraying methods in order to investigate whether the spraying method can be an alternative to the conventional exhaustion method. After application of microcapsules containing shea butter to textile materials, the existence of capsules on the fabrics were examined after five wash cycles. Some physical tests (air permeability, tensile strength and stretching) were performed on the fabrics after treatment with capsules to evaluate the effect of the encapsulation process on denim and non-denim fabric properties. It was also examined whether there is a difference between denim and non-denim fabrics in the presence of microcapsules.
2. Materials and Methods
In this research, desized, 3/1 twill weave, 98% cotton and 2% elastane denim and non-denim fabrics (specific weight 340–370 g m−2) were used. The shell material ethyl cellulose was donated from Acros, Belgium. Shea butter (Tabia, Aydın) were employed as core materials. Tween® 20 was used as a surfactant. The surface active agent, ethanol and ethyl acetate were supplied from Merck, Darmstadt, Germany. Nano polyurethane crosslinker (Tanatex, Switzerland) was used to bond the microcapsules to the fabric surface. All other auxiliary chemicals used in the study were of laboratory-reagent grade.
The fabric properties used in the study are shown in Table I.
2.2 Preparation of the Microcapsules
In order to obtain the microcapsules, the capsules were prepared with the spray dryer method. In this process the interactions of water-insoluble polymers with water are utilised to form the microcapsules. Firstly, shea butter, which is solid at room temperature, was melted at 50°C. Ethyl cellulose and shea butter were dissolved homogenously in organic solvent in a specific ratio. Polymer-rich organic phase was added to polymer-free aqueous phase. Active ingredients were mixed with a Silverson high shear mixer. Afterwards, a spray dryer (SD-Basic LabPlant, Huddersfield, UK) was used to collect the microcapsules. The compositions were fed to the spray dryer at the following conditions for each batch size: feed flow rate of microencapsulating composition 10 ml min−1; inlet air temperature 125°C and outlet air temperature 85°C. Microcapsules were collected from the product vessel using a soft brush in the fume hood and transferred to glass containers for storage. Chemical quantities and test conditions for spray dryer are given in Table II. Three different core:shell ratios were tested to obtain the optimal conditions for microencapsulation of shea butter. The most homogeneously distributed and high yield capsule production was optimised. For this purpose, the ratio of shea butter was varied to examine the encapsulation state of the active substances as shown in Table II.
2.3 Particle Morphology of Microcapsules
The morphologic properties of the capsules were evaluated using SEM (QuantaTM 250 FEG, FEI Co, USA). Samples were gold-coated (15 mA, 2 min) to assure electrical conductivity. The measurements were taken at 2 kV accelerating voltage. The images were taken at 5000× magnifcation.
2.4 Particle Size of Microcapsules
To determine the size of the resulting optimum capsule, a Zetasizer Nano S (Malvern Panalytical, UK) particle-size distribution tester was used. Before measurement, an aqueous solution of capsules in a certain ratio was prepared and sonicated in an ultrasonic bath until a good mixture was formed. After that, the capsule dispersion was put in disposable cuvettes. Then, the light emitted by the laser Doppler was passed through the dispersion.
2.5 Mass Yield of Microcapsule
The total powder obtained after spray drying was weighed, and the process yield was calculated as a percentage of the amount of solids added during the preparation process according to Equation (i):
where R% is the yield of the process, Qi is the amount of solids initially added for the preparation of capsules and Qf is the quantity of microcapsules obtained at the end of the process.
2.6 Fourier Transform Infrared Analysis
FTIR spectroscopy analysis was performed to determine encapsulation performance with the changes in the infrared (IR) spectrum for optimum capsule formulation. Measurements were taken at a wavelength range of 4000–400 cm−1 using a PerkinElmer® FrontierTM FTIR device. The obtained spectra were smoothed to remove noise with the official software of the device.
2.7 Differential Scanning Calorimetry Analysis
Differential scanning calorimetry (DSC) was performed using a PerkinElmer® PYRISTM Diamond differential scanning calorimeter for the purpose of distinguishing complex formation from simple physical mixing with the help of characteristic endothermic or exothermic peaks. The analyses were conducted in nitrogen medium between 0°C and 300°C. The scanning rate was stated as 5°C min−1.
2.8 Application of the Microcapsules to the Denim and Non-Denim Trousers
Denim and non-denim trousers to be used for capsule transfer were first subjected to the denim washing procedure. This procedure covers ageing processes that are made to give denim fabrics an aged appearance and can vary from very light tones to dark tones in line with customer demands. In this study, after rinse washing, stone washing and softening the trousers were turned over and the capsules were transferred.
The application of the selected optimum formulations to the fabrics was carried out with exhaustion and spraying methods. Capsule transfer was carried out according to Table III in the same ratio to compare the application processes. Nano-polyurethane was selected as binder and each experiment was repeated three times. The optimum capsule sample (6 g l−1) and the binding agent (1.2 g l−1) were dissolved in water and then transferred to the trousers with spraying and exhaustion methods.
|Capsule, g l−1||Binder, g l−1||Drying||Fixing|
|Temperature, °C||Time, min||Temperature, °C||Time, min|
The spraying and exhaustion operations were carried out in the Magic Box model Metaflow MET‐FLW drum machine shown in Figure 1. This system is used to coat denim jeans or any other textile garments with chemicals applied into the drum during tumbling. In the exhaustion method, the fabrics were treated with a bath containing a concentration of 5 g m−2 microcapsules in the presence of binder at 40°C for 20 min in the drum machine. In the spraying method, 5 g m−2 capsules and binder were sprayed at spraying speed of 100 g min−1 with a spray system attached to the same machine. To achieve long lasting effect, fabrics were dried in a circulating air oven at 40°C for 20 min and just after drying, the fabric was mounted on pin frames and exposed for 5 min to 120°C in a laboratory stenter.
After microcapsule application, the fabrics were washed according to ISO 3758:2012 (33) standard to determine the resistance to domestic repetitive washing and durability of capsules. In addition, rubbing tests were carried out according to ISO 105-X12:2016 (34) standard, because of the importance of the rubbing test for denim and non-denim trousers.
2.9 Evaluation of Treated Fabrics
SEM images were taken to determine the existence of capsules on the textile surface from washed, unwashed and rubbed samples. Samples were gold-coated (15 mA, 2 min) to assure electrical conductivity. The measurements were taken at 2 V accelerating voltage. The images were taken at 5000× magnifcation.
DSC was performed using a PerkinElmer® Diamond differential scanning calorimeter for the purpose of distinguishing the capsules on the denim and non-denim fabric with the help of characteristic endothermic or exothermic peaks. The analyses were conducted in nitrogen medium between 0°C and 300°C. The scanning rate was stated as 5°C min−1.
Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analysing compounds that can be vaporised without decomposition. The fabrics were extracted to analyse the contents of the capsules containing shea butter transferred to the fabrics. For GC analysis, an Agilent 7820a model GC‐MS + Headspace Sampler device (Agilent, USA) was used. GC device oven temperature was raised to 40°C and left for 3 min. Later, it was brought to 180°C by increasing at a rate of 7°C min−1. After that, it was brought to 240°C by increasing at a rate of 30°C min−1. It was left for 5 min at 240°C. An injector with a volume of 3 μl was used for sampling. Helium gas was used in the analysis. It was run in the ‘split’ mode at a flow rate of 1:200 at 1.5 ml min−1. The injector temperature was set to 250°C and the column pressure to 37.1 kPa.
Air permeability analysis was performed on both denim and non-denim products according to TS 391 EN ISO 9237:1995 (ASTM D737-18) (35) standard in order to examine the effect of microcapsule application on the comfort properties of the products.
Tear strength of the fabrics were measured according to TS EN ISO 13937–2:2000 (36), using an Instron® 4411 tensile strength tester. Elasticity and elastic recovery analyses were made according to ASTM D3107-072019 (37) standard.
An experimental framework in schematic form is provided in Figure 2.
3. Results and Discussion
In this study, capsules containing shea butter were prepared by the spray dryer method. This method is a simple, viable method to obtain microcapsules, suitable to prevent biological activity loss, avoiding exposure to elevated heating and to organic solvents.
3.1 Particle Morphology of Microcapsules
Spray dried microcapsules are usually characterised by spherical shape and narrow particle size distribution. Typical photomicrographs were obtained by SEM of the microcapsules and show that the spray-dried product is composed mainly of spherical shaped particles (Figure 3).
According to SEM analysis, microcapsules filled with active substance (shea butter) were obtained. However, when the micrographs of S1 and S2 coded microcapsule were examined, it was observed that not all particles appeared morphologically spherical. Some of the microcapsules’ centres were collapsed and agglomerated due to sudden solvent evaporation when the polymer solution was introduced into the hot air chamber and also capsule distribution was not homogeneous (38). The biggest cause of shea butter-induced collapse in capsules is thought to be failure of the active ingredient to be encapsulated, resulting in its accumulation on the shell material. When SEM images of S2 coded microcapsules were examined it was seen that the size distribution and capsule shapes were not homogeneous. Therefore, according to SEM images of the microcapsules, the optimum shea butter content to get homogenous spherical microspheres was seen in S3 coded microcapsules. So, other characterisation and capsule transfer studies were carried out with the S3 coded capsule.
3.2 Particle Size of Microcapsules
The particle size of the three formulated capsules (S1, S2 and S3) loaded with shea butter ranged between 369 μm and 420 μm. The particle size results of the microcapsules are presented in Table IV.
When the particle size analysis of the capsules produced at different ratios was evaluated, the S1 coded capsules had a particle size of 400 nm and a high homogeneity. The particle size was 397 nm for S2 coded capsules. According to the data obtained as a result of the analysis, it was determined that 97.9% of the capsules were around 390 nm for S3 coded capsules. It was determined that the particle size analysis graph area showed a uniform distribution. When particle analysis results are evaluated, it was determined that shea butter based capsules with different ratios were homogeneously distributed and had a close value to each other.
3.3 Mass Yield of Microcapsules
The yield of microcapsules produced by a laboratory-scale spray dryer may not be high due to loss of lightweight particles by vacuum suction and adherence to the inside wall of the spray dryer apparatus. The mass yields ranged between 50.9% and 79.4% (w/w) as shown in Table V. A reduction in the amount of active substance in the formulation affected the production efficiency positively. In connection with SEM and particle size analysis, it has been determined that the failure of active substance to be encapsulated caused agglomeration in S1 (3:1 shea:ethyl cellulose) and S2 (2:1 shea:ethyl cellulose) coded capsule formulations.
|Formulation||Mass yield, ethyl cellulose: Econea®, % w/w|
|S1||50.9 ± 1.5|
|S2||55.1 ± 1.7|
|S3||79.4 ± 2.5|
The yield values of the capsule experiments with shea butter and three different molar ratios were calculated and it was concluded that the S3 coded capsules had the highest yield.
After SEM, particle size and mass yield of microcapsules analyses, S3 coded capsules were selected as the optimum ratio. For this reason, FTIR and DSC analyses were carried out over the determined S3 optimum capsules.
3.4 Fourier Transform Infrared Analysis
The FTIR spectra of shea butter capsules and the materials forming them are given in Figure 7.
The characteristic peaks of shea butter were obtained in the FTIR spectra. In the hydrogen stretching region, the following peaks were seen: 2920 cm−1, 2852 cm−1, 2917 cm−1, 2851 cm−1. These bonds signal the presence of symmetric and asymmetric stretching vibration of the aliphatic CH2 group. In the second spectral region of double bond stretching, frequency of 1741 cm−1 occurred, which indicates that the ester carbonyl functional group of the triglycerides is present. The third region of deformation and bending in the functional group showed bonds at 1460 cm−1 as well as 1370 cm−1 and 1475 cm−1 for shea butter. The peaks at 1460 cm−1 indicate bending vibrations of the CH2 and CH3 aliphatic groups while 1370 cm−1 and 1475 cm−1 peaks showed bending vibration of the CH2. In the fingerprint region, the bonds at 1243 cm−1, 1165 cm−1 and 1250 cm−1, 1170 cm−1 indicate the presence of shea butter. These bonds signal the stretching vibration of the C–O ester groups (39, 40).
When the IR spectrum of ethyl cellulose was examined, the stretching vibrations of characteristic –C–O–C– band and –C–H band were observed at 1054 cm−1 and at 2870 cm−1 and 2972 cm−1, respectively. The C–C stretching vibration was located at 1640 cm−1. When the spectra of the capsules were examined, both ethyl cellulose and shea butter peaks were identifed. The strong peak of ethyl cellulose at 1053 cm−1 due to the –C–O–C– band was observed in the capsules. The C–H bands obtained at 2973 cm−1 and 2870 cm−1 were found to be deeper than ethyl cellulose peaks and close to the peak intensity of shea butter. This may indicate successful encapsulation.
3.5 Evaluation of Treated Fabrics
After characterisation using SEM, particle size and mass yield of microcapsules, the S3 coded capsules were determined as the optimum formulation. The capsules were transferred to denim and non-denim fabrics by exhaustion and spraying methods and compared.
SEM images of denim and non-denim fabrics are indicated in Figure 8. These images show that capsule application succeeded for both exhaustion and spraying methods. It was observed that capsules were covered with the binder and fixed onto the textile surface for denim and non-denim fabrics. Also, the effect of repeated washings on capsules was evaluated. Capsules on the textile surface and embedded in the binder were observed even after five washes and rubbing test for both methods and fabrics.
As a result of the SEM analysis, it was observed that the transfers made by the spraying method have similar results to the transfers made by the exhaustion method. It was concluded that capsules can also be transferred by the spraying method which can be used as an alternative to the conventional exhaustion method. Therefore, in order to determine the efficiency of the spraying method, analyses were carried out on the fabrics with capsules transferred by the spraying method.
3.6 Differential Scanning Calorimeter Analysis
The DSC diagrams of ethyl cellulose are given in Figure 9. When the DSC spectrum of shea butter is examined, based on data from Sigma Aldrich, the glass transition temperature (Tg) of ethyl cellulose is about 155°C. The melting temperature of shea butter is about 35–37°C in accordance with the literature (41). The endothermic movement observed at 169.64°C in the DSC analysis of ethyl cellulose is thought to be related to the glass transition temperature. When the microcapsules obtained with shea butter were examined, peaks corresponding to the melting point of the active substance are seen. It was concluded that these small peaks were due to the non-encapsulated active substance. When the DSC spectrum of microcapsules developed with shea butter and ethyl cellulose were examined, low intensity exothermic peaks were observed at 37°C. The reason for the low intensity of these peaks due to shea butter was attributed to being confined by ethyl cellulose.
DSC diagrams of shea butter capsule transferred denim and non-denim fabrics are shown in Figure 10. When the DSC graphs of shea butter transferred fabrics were examined, similar graphs were seen in both denim and non-denim fabrics. This is thought to be due to the use of the same material (containing cellulose) as the raw material. As a result of SEM and DSC analysis, no difference could be detected between denim and non-denim fabrics (42, 43).
The GC analysis results of fabrics transferred to microcapsules containing shea butter and the same samples after five washes are shown in Figure 11. As a result of GC analysis, shea butter peaks can be clearly seen in the GC diagrams. It was found that some of these peaks decreased after five washes, but significant peaks remained for shea butter. Oils transferred to the fabric in capsule form were protected.
When the physical analysis results in Table VI are examined, it can be concluded that microcapsule application on both denim and non-denim products did not significantly affect the tear strength, elasticity and elastic recovery of the fabrics. The breaks in the warp direction were an expected result in denim products. If there is a break in the warp direction in denim fabrics, it means that the strength of the weft direction is above the standards and this situation is within acceptable limits for fabrics. The test results were evaluated by IBM® SPSS® software to examine the difference between the denim and non-denim fabrics. Results showed that the effect of fabric type is statistically significant for all microcapsule procedures and p value is 0.000 (p < 0.05).
In order to examine the effect of microcapsule application on the comfort properties of the products, air permeability analysis was performed on both denim and non-denim fabrics according to the TS 391 EN ISO 9237:1995 (ASTM D737‐18) (35) standard and the results are stated in Table VII. When the air permeability results are examined, it can be observed that microcapsule application on both denim and non-denim products did not significantly affect air permeability.
Within the scope of this study, shea capsules were produced successfully with the spray dryer method. In this method, materials can be directly dried into powder to produce shea microcapsules. It is easy to change the drying conditions and adjust product quality standards. The method has high production efficiency and large production capacity. These advantages will enable this method to be used in capsule production in future studies. Denim and non-denim products were developed by encapsulating shea butter with ethyl cellulose which were then successfully applied on denim and non-denim fabrics. The capsules remained on the fabric at a certain rate after five washes. When physical properties such as air permeability, tear strength and elasticity of the fabrics were examined, it was seen that the capsules did not create any negative effects on the fabrics. Denim and non-denim fabrics were compared with each other. As a result of SEM and DSC analysis, no difference could be detected between denim and non-denim fabrics as they consist of similar (cellulosic) materials.
Transferring microcapsules to denim and non-denim fabrics by spraying method is an innovation for the denim sector. Transfer of microcapsules that give functional properties to textile materials is mostly done by impregnation and exhaustion methods. In this study, the efficiency of the spraying method was compared with the conventional transfer method. As a result of the comparisons, the main objectives of the study have been achieved in both methods. The spraying method provided a more sustainable process as it uses less water, has lower chemical consumption and produces less waste compared to the exhaustion method, which works at higher liquor rates. When transferring with the spray method, the temperature and processing time used during the exhaustion method are eliminated. With this study, we demonstrate that adoption of the spraying technique for microcapsule application could be an efficient way to produce textiles while minimising energy and resource consumption.
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İsmail İvedi graduated from Dokuz Eylül University, Turkey, in 2015 with a Bachelor’s degree in Textile Engineering. He received his Master’s degree from the same department in 2019. He is working in the Research and Development Department at Roteks Tekstil AŞ, Turkey, since 2017.
Bahadır Güneşoğlu graduated from Ege University, Turkey, in 1994 with a Bachelor’s degree in Textile Engineering. He is a General Coordinator at Roteks Tekstil AŞ since 1993.
Sinem Yaprak Karavana received her Master’s degree in Ege University Faculty of Pharmacy, Department of Pharmaceutical Technology. She has been working for Ege University Faculty of Pharmacy Department of Pharmaceutical Technology since 1999. Her research interest is bioadhesive formulations, mucosal delivery and controlled release systems.
Gülşah Ekin Kartal is currently working as a Research Assistant in the Textile Engineering Department, Faculty of Engineering, Dokuz Eylül University, İzmir Turkey. She received her Master’s and PhD degrees in the Textile Engineering Department, Dokuz Eylül University. Her research interests are micro/nano encapsulation technology, functional textile finishing, textile dying, textile printing, layer-by-layer technology in textile treatment, liposomes and fishing nets.
Gökhan Erkan is currently working as an Associate Professor in the Textile Engineering Department, Faculty of Engineering, Dokuz Eylül University, İzmir Turkey. He received his PhD degree in Textile Engineering from Dokuz Eylül University. His area of research is microencapsulation, textile functional finishing and textile printing. His research interests also include natural dyes.
Merih Sariişik is currently working as a Professor in the Textile Engineering Department, Faculty of Engineering, Dokuz Eylül University, İzmir Turkey. She has 34 years’ teaching and research experience. She received her Master’s and PhD degrees from the Department of Textile Technology, Ege University. Her research interests are micro/nano encapsulation technology, enzyme treatment in textiles, medical textiles and layer-by-layer technology in textile treatment.