Encapsulation of Rosemary Oil in Ethylcellulose Microcapsules

B.Voncina1, O.Kreft2, V.Kokol1, W.T.Chen3 Dept. of Textile Materials and Design, University of Maribor, Maribor, Slovenia1, Max-Planck-Institute of Colloids and Interfaces, Potsdam-Golm, Germany2 Dept. of Raw Material and Yarn Formations, Taipei, Taiwan, R.O.C.3
Abstract : In textiles, the major interest in microencapsulation is currently in the application of durable fragrances, skin softener, phase-change materials, antimicrobial agents and drugs delivery systems onto textile materials. In our research Rosemary oil was encapsulated in ethylcellulose (EC) microcapsules using a phase separation method; the prepared capsules were analyzed by Scanning Electron Microscopy (SEM) and Confocal Laser Scanning Microscopy (CLSM). The Rosemary oil content in the microcapsules was determined by using CLSM. Capsules were grafted onto cotton textile substrate; the presence of microencapsulated Rosemary oil attached to textile materials was tested by CLSM.

Key words : Microencapsulation, ethylcellulose, confocal laser scanning microscopy, cellulose bers.

1. Introduction
Microencapsulation is one of the latest technologies used for imparting an array of unique characteristics to a garment. Particles filled with active ingredients are applied to the fabric or garments for long lasting effects. Microencapsulated particles can be coated on a textiles' surface or anchored (Chemically or physically) onto the ber. As the wearer moves, the capsules are activated and they release the active ingredient in a controlled manner. The active ingredients in the garment can be moisturizers, vitamins, therapeutic smells, essential oils, drugs and others [1,2,3,4,5,6,7,8,9,10]. The properties of microcapsules (Figure 1), size, shape, wall material, active substance release mechanism, have had to be adapted to the

requirements of textile processing methods and use of nal products. In our current research Rosemary oil was encapsulated in ethylcellulose (EC) microcapsules using the phase separation method [11,12] ; the prepared capsules were analyzed by Scanning Electron Microscopy (SEM) and Confocal Laser Fluorescence Microscopy (CLSM). Prepared capsules were grafted onto cotton textile substrate as mentioned in literature[11]; prepared textile materials were analyzed by Confocal Laser Fluorescence Microscopy.

2. Experimental
2-1 Materials Ethylcellulose (EC) was purchased from

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Aldrich, Austria (Viscosity 4 cP, 5% in toluene/ ethanol 80:20, extent of labeling: 48% ethoxyl). Rosemary oil was provided by Etol, Celje, Slovenia. 1,2,3,4-Butane tetracarboxylic acid (BTCA) by Merck, cyanamide (CA) and fluorescence dye: fluorescein (FITC) from Aldrich and sodium dodecylsulphate by Fluka were used. All other chemicals were of analytical reagent grade. Pure cotton (Mass = 140 g/m2) was used after it was rst desized, scoured, bleached and mercerized on continuous production equipment. It was supplied by MTT, Maribor, Slovenia. 2-2 Test methods and analytical techniques The microcapsule yield was determined as a weight percent of the recovered microcapsules after drying, divided by the initial amount of ethylcellulose and oil employed. Diameters and surface morphology of microcapsules were examined by scanning electron microscopy (SEM). The samples were coated with gold for 3.5 min using an Emscope SC 500 and examined using a Philips XL30 ESEM operating in the secondary electron mode at 10 KV accelerating voltage. The Quanta has a tungsten based electron optical column with a resolution of 3.5 nm and an ion resolution of 10 nm. Measurements were taken in vacuum at different magnifications. Diameters of capsules are presented as the mean value standard

deviation (SD) of fty measurements. For Rosemary oil content in capsules two methods were used; in first one the oil in capsules was removed by extraction and from the differences in capsules mass before and after extraction the amount of oil was determine; in the second method the proportion of empty capsule space was determine by using CLSM. Confocal images were taken with a Leica confocal scanning system mounted to a Leica Aristoplan and equipped with a 100x oil immersion objective with a numerical aperture (NA) of 1.4. For visualization, FITC was used to stain the capsules. 2-3 P  reparation of EC microcapsules and Rosemary essential oil content determination EC microcapsules were prepared as reported in the literature
[11]

. In order to determine the

Rosemary essential oil content in capsules two methods were used. The Rosemary oil content in EC microcapsules has been determined by pouring them into cyclohexane and ultrasonicating for 1 min to extract Rosemary oil from the capsules. The oil content (ROC) expressed in percent was determined from the mass differences of microcapsules containing Rosemary oil (mECRO) and capsules after oil extraction (MEC). Five repeated measurements were

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carried out. The following equation was used: mECRO-mEC ROC= 100% mECRO EC microcapsules contain around 30% of Rosemary oil. In the second method, where Confocal Laser Scanning Microscopy was used, we placed one drop of an aqueous capsule suspension containing essential oil onto a microscope glass slide and mixed it with a fluorescein solution (0.1 mg/ml H2O). Capsules without Rosemary oil were treated likewise and acted as a negative control. Within a few seconds, the fluorescein penetrated the capsules wall and the overall fluorescence intensity within the boundary of one capsule was determined by CLSM (Figure 2). The ourescence intensity of an identical region outside the capsule was used for calibration and set to 100 percent (Figure 2). Ten repeated measurements were carried out. By comparison of the uorescence intensity of the capsule area with fluorescence intensity of the same blank area it is possible to estimate the proportion of empty capsule space. The average empty space in prepared capsules was 40%. 2-4 G  rafting of EC microcapsules on textile substrate using BTCA EC microcapsules were linked onto cotton via grafting with 1,2,3,4-butanetetracarboxylic acid (BTCA) as described in literature
[6,11]

and with Rosemary oil loaded microcapsules grafted on textile materials were analysed by using CLSM.

3. Results and discussions

3-1 Analysis of ethylcellulose microcapsules From the SEM shown in Figure 1 it was observed that EC microcapsules had a regular spherical shape. Microcapsules in the 10-90 m size range were obtained.

Figure.1. SEM image of EC microcapsules containing rosemary oil (1000 magnication).

The size and degree of sphericity of the microcapsules depend on the stirring speed employed in the encapsulation. Table 1 presents the influence of the stirring speed on microcapsule diameter and on microencapsulation yield. Reducing the stirring speed increases the size of microcapsules. The yield of microencapsulation was measured by comparing the total weight of the microcapsules with the combined weight of the polymer and oil. Good results in terms of recovery, shape and size distribution were obtained in the case of blank microcapsules (Table 1). The presence

. Empty

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of oil causes deficiencies of the microcapsule recovery. In order to facilitate the encapsulation of oil, this should have a density comparable to that of the aqueous external phase and complete

immiscibility with the external phase. The density of Rosemary oil is 0.91 g/ml which could explain the slight decrease in yield of Rosemary oil microencapsulation.

Table1. Inuence of the stirring speed on yield of microencapsulation and diameter of microcapsule. Oil Stirrer speed, rpm 350 Rosemary oil 500 750 1000 Blank microcapsules
a

Yield, % 68 58 67 50 75

Diameter SDa, m 728 4313 425.6 205.1 7815

350

each value represents the mean standard deviation (SD) of fty measurements

3-2 Rosemary oil content determination The Rosemary oil content (ROC) of 30% was determined from the mass differences of microcapsules containing Rosemary oil and capsules after oil extraction by using ultrasound. By using CLSM (The second method mentioned in paragraph 2.3), the representative CLSM images of empty EC microcapsules and EC microcapsules containing Rosemary oil were studied. Figure 2 presents microcapsules without Rosemary oil "embedded" in fluorescent dye. By comparison of the fluorescence intensity of the capsule area with fluorescence intensity of the same blank area it is possible to estimate the proportion of empty capsule space. The

average empty space in prepared capsules was determined to be 40%. Figure 3 a presents CLSM images of microcapsules containing essential oil "embedded" in uorescence dye and empty microcapsule "embedded" in fluorescence dye as Figure 3. In the case when microcapsules contain hydrophobic Rosemary essential oil (Figure 3a) the penetration of the hydrophilic uorescence dye into capsule's porous systems is hindered, while in the case of empty capsules the hydrophilic fluorescent dye can penetrate into capsules easily.

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3-3 Microcapsules on textile substrate Prepared microcapsules containing Rosemary oil and microcapsules without Rosemary oil were covalently bound to hydroxyl groups of cellulose by using BTCA. Grafting of microcapsules onto textile materials occurred at 110C for 2 min thus some of the essential oil might evaporated through the microcapsule walls. When textile material grafted with empty microcapsules was embedded in uorescence dye solution, the dye
Figure.2. Microcapsules without Rosemary oil "embedded" in uorescent dye.

penetration into microcapsules was indicated by the capsules colouring green (Figure 4a), on the other hand, fluorescence dye penetration into microcapsules was hindered when textile materials was grafted with microcapsules containing Rosemary oil. This can be indicated by black microcapsules on image b in Figure 4. We can conclude that heating of microcapsules containing Rosemary oil at 110C for 2 min during the grafting process does not have a signicant inuence on the Rosemary oil content of microencapsulated textile material.

a)

b)
Figure.3. Microcapsule containing essential oil "embedded" in uorescence dye (a) and empty microcapsule "embedded" in uorescence dye (b).

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that the empty space in capsule is around 40%. We can conclude that results obtained from both methods are comparable; EC microcapsules have in average 40% of empty space which are is fully occupied by Rosemary oil. Further, microcapsules were grafted onto cotton textile substrate and the presence of Rosemary oil in a) microcapsules bonded onto textile materials was tested by CLSM. We observed that after grafting of microcapsules on textile materials at elevated temperature the Rosemary oil is still present in microcapsules. This indicates that grafting of EC microcapsules containing Rosemary oil onto textile materials at 110C for 2 min by using BTCA is appropriate method to prepare textile b)
Figure.4. Microcapsules without Rosemary oil on textile materials "embedded" in uorescence dye, a) and microcapsules containing Rosemary oil on textile materials "embedded" in uorescence dye, b).

materials for cosmetic application.

Acknowledgement
We are grateful to European project MTKD-

4. Conclusion
This work described the preparation of EC microcapsules containing Rosemary oil by the phase separation method. The size range of EC microcapsules depends on the stirring speed employed during encapsulation. Reducing the stirring speed increased the size of microcapsules. The Rosemary oil content in microcapsules was determined by extraction of oil in cyclohexane by ultrasound and CLSM. We observed that the oil content is about 30% and

CT-2005-029540 POLYSURF, for its financial support.

References
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4. Lou, J., Zhou, X., J. Polymer Sci. A, 42(9), p.2145(2004) 5. Li S., He,Y.,Li, C., Liu, X., Colloid Polym. Sci., 283-480(2005) 6. Voncina B., Majcen Le Marechal A., J. Appl. Polymer Sci.,96(4), 1323-1328(2005) 7. Geiger T., et al, Polymer Bulletin, 52, pp.65(2004) 8. http://www.aapspharmscitech.org/view. asp?art=pt030213, Jan(2008) 9. http://www.imt.ro/cenobite/eng/pp_inst.htm, Avg.(2007) 10. Boh B., Knez E., Indian Journal of Fibre & Textile Research, 31, 72-88(2006) 11. Badulescu, R., Vivod, V., Jauovec, D., Von ina, B., Carbohydr. Polym., Vol. 71, Iss. 1, 85-91(2008) 12. Babtsov, V., Shapiro, Y., & Kvitnitsky, E. (2005). Method of microencapsulation. US Patent Ofce, Pat. No. 6 932 984. (2008.11.10Receive/2008.12.9Emend/2009.1.17 Accept)

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