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Textile Research Journal OnlineFirst, published on August 14, 2009 as doi:10.

1177/0040517509105074

Textile Research Journal

Article

Water Shedding Angle: A New Technique to Evaluate the Water-Repellent Properties of Superhydrophobic Surfaces
A new technique is introduced to evaluate the wetting properties of superhydrophobic textiles which are not accessible by classical contact angle measurement techniques. The principle behind the new water shedding angle technique is the ability of a superhydrophobic surface to repel drops of water upon impact. In this sense it shows a strong reference to application and its results are easily understood in terms of water protection. The procedure is simple and straightforward and the experimental setup can be easily built or adapted to most available contact angle measurement systems. In view of the significant potential of superhydrophobic coatings for textile applications, the water shedding angle provides a reliable and comparable measure to judge the quality of a superhydrophobic textile in terms of water repellency. It constitutes a useful addition to existing techniques and has proven to be better suited to evaluate the wetting properties of superhydrophobic textiles than the contemporary methods presently in use.

Abstract

Jan Zimmermann and Stefan Seeger1


Physikalisch-chemisches Institut, Universitt Zrich Irchel, Winterthurerstr. 190, CH-8057 Zrich, Switzerland

Felix A. Reifler
Advanced Fibers, Empa Swiss Federal Laboratories for Materials Testing and Research, Lerchenfeldstrasse 5, CH-9014 St. Gallen, Switzerland

Key words

superhydrophobic, water repellence, contact angle measurement, nanofilaments

Inspired by natural surfaces like the lotus leaf [1], surfaces with extreme water-repellent properties have received considerable interest in the last decade [29]. Drops of water deposited on such so-called superhydrophobic surfaces exhibit extremely high contact angles (>150) and roll off at slight inclination. Potential applications range from nonwettable, quick-drying surfaces to anti-fouling or selfcleaning surfaces. In order to meaningfully characterize a superhydrophobic surface it has long been established that both the static and dynamic wetting properties must be evaluated [10]. While the static wetting properties determine the equilibrium shape of a drop of water deposited on a solid surface and are therefore a measure of the contact area between a drop of water and the surface, the dynamic wetting properties are a measure of the water adhesive properties of a surface. Typically the wetting

properties of superhydrophobic surfaces are evaluated by measuring the static water contact angle as well as the contact angle hysteresis. Modern contact angle measurement systems allow for a recording of the drop image with a charge-coupled device camera and also provide software for an automatic determination of contact angle. In order to achieve reproducible results with these techniques, a good optical representation of the drop is crucial. Both the drop profile as well as the three-phase contact line (substrate baseline) must be well resolved, especially when extremely high contact angles (>160) are evaluated. Here, for instance, a shift of the substrate baseline by only a sin-

Corresponding author: e-mail: s.seeger@pci.uzh.ch

Textile Research Journal Vol 0(0): 16 DOI: 10.1177/0040517509105074

The Author(s), 2009. Reprints and permissions: http://www.sagepub.co.uk/journalsPermissions.nav

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Textile Research Journal 0(0) from left to right. The bottom three images show the drop profile at slightly different foci. The average contact angle determined from these nine images is 171 4. So although technically the automated fitting routine is considered to be able to reproduce a contact angle measurement with an accuracy of 0.2 (as opposed to 2 for manual determination) [11], the systematic error caused by the operator can be considerably higher. It is therefore clear that despite recent advances in goniometry, there is still a significant bias inherent in the measuring technique when high contact angles are evaluated. In the worst case, inexperienced performance of an automated contact angle routine and blind trust can produce completely misleading results [12]. The situation becomes even more complicated if the substrate that is to be evaluated is non-reflective or even macroscopically rough. In these cases, a reliable determination of the substrate baseline is often impossible. A substrate type that is greatly affected by this problem is woven textiles. In most cases, the macroscopic weave of the textile fibers and the flexibility of the fabric will hinder a discerning of the substrate baseline (Figure 3). In view of the significant potential of superhydrophobic textiles, for instance as water resistant apparel, or any other kind of application where textile surfaces are exposed to the environment, it is important to develop an alternative method to judge the water repellent properties of these substrates. Several reports of superhydrophobic textiles

Figure 1 The drop profile of a drop of water on a superhydrophobic surface analyzed with the Laplace-Young fitting routine. The left and right images show the identical drop image but a shift of the substrate baseline by only a single pixel results in an apparent difference of almost 5 in the determined contact angle.

gle pixel can lead to a high deviation of the determined contact angle (Figure 1). Also, factors such as contrast, lighting and focus can have a significant effect on the contact angle determination (see Figure 2). These issues make contact angle measurements less trivial than often assumed, and even modern equipment requires an experienced operator to achieve reliable and reproducible results. The top three images in Figure 2 show the drop profile at slightly different lighting conditions. In the middle images, the baseline was successively shifted down by a single pixel

Figure 2 Automated contact angle determination performed on the same drop of water under slightly varying settings. Top row: varying lighting conditions. Middle row: varying position of the three-phase contact line. Bottom row: varying focus.

Water Shedding Angle: A New Technique to Evaluate the Water-Repellent Properties J. Zimmermann et al.

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Figure 3 Typical picture of a sessile drop on a superhydrophobic textile surface, indicating the difficulties encountered when trying to detect the full drop profile for contact angle measurement.

Figure 4 Principle setup employed for measuring water shedding angles (WSA, ).

needle type, material and diameter. Details of the specific setup used in the measurements can be found in the Materials and Methods section. exist [7,1321] and an awareness that classical contact angle measurement is not well suited to evaluate the wetting properties of superhydrophobic textile substrates is growing [19,22]. Therefore, to support work on superhydrophobic textile coatings, a new technique was developed that enables a comparison of the water repellent properties of different textile substrates. In essence it is as simple and straightforward as classical contact angle measurement and can be easily adapted for most contact angle measurement systems, or easily built from standard laboratory equipment. Its relation to existing techniques such as sliding angle measurements, critical sliding volume determination [23] or determination of self-cleaning ability [24] should make it easily accessible to most researchers in the field.

Materials and Methods


Sample preparation
Superhydrophobic textile samples were prepared by coating various fabric materials with a layer of silicone nanofilaments in a gas phase coating process at ambient conditions. Details on the coating process can be found elsewhere [7,22]. A total number of eleven different textile materials, comprised of natural and artificial polymers with varying weave, thickness and density, were provided by the EMPA Testmaterials AG (Mvenstrasse 12, 9015 St. Gallen, Switzerland). All were coated in the same manner at 40 50% relative humidity, ambient temperature, with a total amount of 300 L trichloromethylsilane and a coating time of ten hours.

Principle Setup for the Measurement of Water Shedding Angles


Figure 4 illustrates the principle setup for the measurement of water shedding angles (WSA, ). In essence, a water drop of defined volume is released onto the substrate from a defined height and the minimum angle of inclination at which the substrate needs to be tilted for the drop to completely roll or bounce off the substrate is determined. Four parameters need to be controlled: the tilt of the substrate, the needle-to-substrate distance, the relative distance of the impact point to the lower end of the substrate, and the drop volume. Most contemporary contact angle measurement systems provide means to control these parameters, or can be suitably equipped by the manufacturer or by a mechanical workshop. Accurate and reproducible drop volumes can be achieved by selecting a suitable

Contact angle measurement


Contact angle measurements were performed on an OCA 20 contact angle system (Dataphysics, Germany) and included software. A custom-built tilting stage was used for sliding angle measurements. Both contact and sliding angle measurements were typically performed with 10 L drops of water. Textile samples were attached to glass cover slips with double-sided adhesive tape to generate a planar surface.

Water shedding angle measurement


Textile samples were attached to glass cover slips with double-sided adhesive tape and placed on a custom-built tilting table. A syringe holding the desired test fluid was mounted

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Table 1 Textile substrates used for coating with silicone nanofilaments.


EMPA Testmaterials Product No. #211 #213 #214 #402 #403 #404 #405 #407 #408 #413 #414 Product name Cotton fabric, percale Polyester/cotton fabric 65/35 Cotton twill fabric Wool muslin Silk Crpe Viscose spun, shiny 2,5 Acetate Polyester Dacron, type 54 spun Polyacrylnitrile Orlon, type 75 spun Cotton for crockmeter Wool tricot JWS SM29 (Hercosett superwash) Type of weave plain weave plain weave twill plain weave crpe plain weave taffeta weave plain weave plain weave plain weave knitted fabric Weight per unit area [g m2] 190 165 210 120 170 120 125 140 150 100 350

above the tilting table with a fixed needle to substrate distance. The syringe was positioned in a way that a drop falling from the needle would contact the substrate 20 1 mm from the bottom end of the sample. Two needles with inner diameters of 130 m (Hamilton #90531) and 250 m (Krss #NE 43) were used to produce water drops with volumes of 5.0 0.3 L and 13.0 0.3 L respectively. To control the volume of the drops released from the needle, a drop of 4.5 or 12.5 L volume was generated at the needle tip using the automated syringe control of an OCA 20 contact angle system (Dataphysics). Then the drop was successively expanded in steps of 0.1 L until it detached from the needle. To determine the WSA, measurements were started at an inclination angle of 85. Drops of water were released onto the samples at a minimum of five different positions, each 20 mm from the bottom end of the sample. If all drops completely bounced or rolled off the sample, the inclination angle was reduced by 5 and the procedure repeated until one or more of the drops would not completely roll off the surface. This could either be evident from the whole of the drop coming to rest on the surface after rolling a short distance or from parts of the drop sticking to the surface at the impact point or on the path down the incline. The lowest inclination angle at which all the drops completely rolled or bounced off the surface was noted as the WSA. The WSA was determined for two different volume drops (5.0 0.3 L and 13.0 0.3 L) and two different needle substrate distances (10.0 0.5 mm and 40.0 0.5 mm) to gauge a possible effect of impact velocity on the WSA. All experiments were performed at 21 1C under ambient conditions.

Results and Discussion


When evaluating the eleven coated textile fabrics in terms of their wetting properties it became immediately clear that the standard techniques of contact and/or sliding angle measurement are not sufficient to distinguish between the individual fabrics. All coated fabrics showed strong waterrepellent properties. On all substrates, drops of water remained almost spherical (Figure 5).

Figure 5 Drops of water on four of the 11 textile fabrics coated with silicone nanofilaments.

Water Shedding Angle: A New Technique to Evaluate the Water-Repellent Properties J. Zimmermann et al.

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Table 2 Water shedding angles at varying drop volumes and needlesubstrate distances of various textile samples coated with silicone nanofilaments (missing values indicate a pinning of all drops even close to 90 inclination).
Needlesubstrate distance 10 mm Polymer* Sample # PET 407 5 2 3 3 silk 403 10 5 15 15 PET/CO 65/35 213 20 10 15 10 PAN 408 20 10 30 35 wool 402 20 15 30 40 viscose 404 25 25 35 40 CO 413 35 25 50 50 CO 214 45 35 50 40 wool 414 65 40 70 45 CO 211 70 35 75 45 acetate 405 55 70

40 mm

5L 13L 5L 13L

* CO cotton; PET polyester; PAN polyacrylnitrile

By eye, no significant difference in the shape of the drops could be determined. However, subjectively, a clear difference in the water-repellent properties of the individual fabrics was noted. In some cases drops would roll off the surface at slight inclination, in others, a slight agitation of the fabric was required to dislodge the droplets. None of the fabrics could be evaluated by classical contact angle measurements since in all cases the substrate baseline could not be determined from the drop images (compare Figure 3). Also, sliding angle measurements of sessile drops, a method that is often employed as an alternative to dynamic contact angle measurements [7,25], did not produce meaningful results. In some instances, single textile fibers projecting out from the fabric would attach to the drop and prevent it rolling off. In other cases, sliding angles on a single substrate would vary considerably, depending on the positioning of the drop on the macroscopically rough fabric. A drop deposited in a depression in the weave of the fabric would require a considerably higher tilting angle to roll off than a drop deposited on a more planar part of the fabric. Similar difficulties in sliding angle measurements on superhydrophobic textiles were also noted by Hoefnagels et al. [19]. In contrast, the water shedding angle measurements were able to clearly reveal the difference in the waterrepelling qualities of the individual coated textiles. Table 2 summarizes the results of the water shedding angle measurements on the various substrates at two different needleto-substrate distances and for two different drop volumes. In the development of the WSA technique a 5 increment in the WSA measurements proved to be a good compromise between accuracy and expenditure of time. Typically three or more of the five drops applied to a fabric remain pinned to the substrate at an inclination of 5 below the reported WSA and all drops would remain pinned at an inclination of 10 below the WSA. As can be seen in Table 2, the WSA generally increases with the needle-to-substrate distance. A larger impact height increases the kinetic energy of the drops, leading to a deeper penetration into the fabric structure and a higher WSA. For different drop volumes, the interpretation is not as straightforward. Although the kinetic energy of the drop also increases with drop volume, the WSA does not gener-

ally increase for the 13 L drops. At 40 mm the WSA increases (PAN, wool 402, viscose), remains constant (PET, silk, CO 413) or decreases (PET/CO, CO 214, wool 414, CO 211, acetate) with the drop volume. In contrast, at 10 mm needle-to-substrate distance, the WSA generally decreases with drop volume. This varying behavior is due to a delicate balance of the individual parameters expected to influence the WSA. On the one hand, for larger drop sizes, the shape of the drop upon impact becomes less dependent on the surface tension of the liquid, that is, larger drops are able to deform more strongly and some of their kinetic energy is stored in this deformed shape. This reduces the contact pressure of the drop at the dropsubstrate interface and decreases the penetration depth. Also, the elastic deformation provides additional energy to the drop upon relaxation and promotes the release from the substrate [26,27]. On the other hand, textile parameters such as dimension, yarn and weave of the fabric will also affect the behavior of the WSA. More pliable open weave and knitted structures, for instance, will cushion the drop upon impact. The energy loss due to dissipation into the fabric will hinder the release of the drop. Analyzing the individual textile and coating parameters and their influence on the WSA, however, would go beyond the scope of this work. Measurements at varying temperatures showed that small variations ( 5C) did not influence the WSA measurements. Higher temperature deviations, however, significantly alter the physico-chemical properties of the liquid as well as the substrate, and were noted to affect the WSA results.

Conclusions
Overall, the presented data shows that the WSA is a wellsuited measure to judge the water-repellent properties of superhydrophobic textile fabrics (or other non-reflecting, pliable materials). The data shown here provides a general ranking of the coated textiles in terms of their water-shedding abilities, a ranking that is, with few exceptions, independent of the experimental parameters (drop volume, needlesubstrate distance). In this sense the WSA tech-

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nique could be used to optimize the coating procedure and the fabric parameters of a given textile material to yield the best possible water repellency at the desired cost or material specifications. Furthermore, the described procedure provides unambiguous results for a specific set of experimental parameters. Experiments also showed that small temperature fluctuations ( 5C) do not affect the WSA measurements. Unlike contact angle measurements, which may be biased depending on the operator and experimental procedures (Figure 2), this makes the WSA a very reliable and transferable measure of water repellency. In a first application, it was successfully used to detect changes in the water-repellent properties of textile fabrics after mechanical, environmental or chemical stress, i.e. to judge the durability of a superhydrophobic coating on textiles [22]. As a note of caution, it must be said that the water shedding angle alone is not sufficient to judge the wetting properties of a textile. Since in the WSA measurements the exposure time of the drop to the substrate is very short, effects such as wicking can be overlooked [22]. In this sense, WSA experiments should always be supplemented by other wetting experiments in which a prolonged exposure to water is realized.

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Acknowledgements
We thank the EMPA Testmaterials AG for providing the textile samples and Dr. Georg Artus for helpful discussions.
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