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Ultrahydrophobic Textiles Using Nanoparticles: Lotus Approach

Karthik Ramaratnam, Ph.D.1, Swaminatha K. Iyer, Ph.D.1, Mark K. Kinnan2, George Chumanov, Ph.D.2, Phillip J. Brown, Ph.D.1, Igor Luzinov, Ph.D.1
1

School of Materials Science and Engineering, Clemson University, Clemson, South Carolina, USA
2

Department of Chemistry, Clemson University, Clemson, South Carolina, USA Correspondence to: Phillip J. Brown, Ph.D. email: pjb@clemson.edu Igor Luzinov, Ph.D. email: luzinov@clemson.edu

ABSTRACT It is well established that the water wettability of materials is governed by both the chemical composition and the geometrical microstructure of the surface.1 Traditional textile wet processing treatments do indeed rely fundamentally upon complete wetting out of a textile structure to achieve satisfactory performance.2 However, the complexities introduced through the heterogeneous nature of the fiber surfaces, the nature of the fiber composition and the actual construction of the textile material create difficulties in attempting to predict the exact wettability of a particular textile material. For many applications the ability of a finished fabric to exhibit water repellency (in other words low wettability) is essential2 and potential applications of highly water repellent textile materials include rainwear, upholstery, protective clothing, sportswear, and automobile interior fabrics. Recent research indicates that such applications may benefit from a new generation of water repellent materials that make use of the “lotus effect” to provide ultrahydrophobic textile materials.3,4 Ultrahydrophobic surfaces are typically termed as the surfaces that show a water contact angle greater than 150°C with very low contact angle hysteresis.4 In the case of textile materials, the level of hydrophobicity is often determined by measuring the static water contact angle only, since it is difficult to measure the contact angle hysteresis on a textile fabric because of the high levels of roughness inherent in textile structures. INTRODUCTION Barthlott and Neinhuis revealed the interdependence between surface roughness, reduced particle adhesion and water repellency based on experimental data obtained on microscopically smooth and rough plants.4 It was also demonstrated that hydrophobic substrates that are rough on a micro and nanoscale tend to be more hydrophobic than smooth ones because of the
Journal of Engineered Fibers and Fabrics Volume 3, Issue 4 - 2008

reduced contact area between the substrate and the liquid and vice versa for hydrophilic substrates. It is clear that wettability strongly depends on two properties the surface free energy and the surface roughness.6-9 Surface free energy is an intrinsic property of the material that can be controlled by chemical modification, such as fluorination9 and other hydrophobic coatings.10,11 In particular a variety of fluorine-based polymers have been used because of their high water and oil resistances, organic solvent resistance, and lubricity.12 Fluoro-polymers/coatings have been commonly used for hydrophobic applications because of their lowest surface free energy property. It has been reported that the surface free energy decreased in the order –CH2 > -CH3 > -CF2 > -CF2H > CF3, which predicts that the closest hexagonal packing of -CF3 groups gives the lowest surface free energy of the materials.13 Hence, ultrahydrophobic surfaces have been generally prepared by modifying the surfaces with various fluorinated polymers, such as PTFE coatings,9,14 fluoroalkylsilanes,15,16 and perfluorinated polymer monolayers.17 The focus of our research was to explore the possibility of achieving the ultrahydrophobic effect on fabrics using nanoparticles as the roughness initiating component and a non-fluorinated hydrophobic polymer (polystyrene) as the low surface free energy component. The effect of fabric roughness due to the different fabric constructions on achieving the lotus effect was also studied. In our fundamental approach we have employed different methods to fabricate ultrahydrophobic textile materials. By using combinations of polystyrene grafted layers (the low surface free energy component) and silver/silica/calcium carbonate nanoparticles (roughness initiation component) we have created textile materials that demonstrate ultrahydrohttp://www.jeffjournal.org

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Model DSA10) to determine the extent of water repellency.phobicity. Inc.4 wt% of reactive maleic anhydride (MA) groups.).jeffjournal. and Rg = 6. Poly (styrene-b(ethylene-co-butylene)-b-styrene) (SEBS. The high level of roughness (microns) and the non-homogeneous distribution of the bumps on these leaves meant that good imaging using AFM was difficult.) were used as a model substrate for flat surfaces. Silica Microspheres of uniform size of 150nm were obtained from Polysciences Inc. The fabric wetting properties after the surface modification were studied using a Textest FX3300 Air permeability tester. Polystyrene (PS) (45900 g/mol) with monofunctional carboxy termiJournal of Engineered Fibers and Fabrics Volume 3. The multi-dimensional nature of roughness arises in these fabrics due to surface modification with nanoparticles along with fiber size and the macroscopic fabric structure.21 Silica nanoparticles of sizes about 50 and 100 nm were obtained from Nissan Chemicals. PDI 1. INSTRUMENTATION The polyester fabrics were initially functionalized using either a Harrick plasma cleaner/ sterilizer PDC32G or a Sicatech corona generator (Unisystems LFI). first the roughness of the lotus leaf (nelumbo nucifera) was studied using scanning probe microscopy. Several thermodynamic models have been proposed to study the depth of water penetration onto such rough surfaces and predict the degree of repellency. However in this paper we did not investigate the antimicrobial nature of the treated fabrics and the silver nanoparticles were synthesized to have the desired range of particle sizes for this studies primary concern. Unfortunately the SPM did not lead to consistent measurements and the study showed that the leaf surface is “very rough” in fact too rough in our case for the SPM tip to track the surface profile.org . Silver nanoparticles of various sizes 52. SEM studies were performed using a FESEMHitachi S4800. The block copolymer was reported to have Mn=41. All of the polymer coatings were performed using a dip coater (Mayer Fientechnik D3400).16. ACS grade toluene. However. where Rg is the radius of gyration of SEBS macromolecules.. the cost of silver is not unsubstantial and therefore cheaper particle technologies were also investigated including silica and calcium carbonate. Kraton FG1901X) triblock copolymer was obtained from Kraton Polymers US LLC. Silicon tips with spring constants of 50 N/m were used to scan the surfaces.20 The polymer was analyzed with gel permeation chromatography employing polystyrene standards.e. i. 84.7 (obtained from GPC)). Thus in this study attempts were made to reproduce artificial lotus surfaces by making use of submicron particles and we restricted ourselves to preparing homogeneous rough surfaces in the order of nanometer/submicron levels using polymer thin films and a variety of particles. Roughness gives rise to the phenomena of limited impregnation (water penetration into the rough structures) and is greatly responsible for obtaining higher levels of repellency. MATERIALS Polyester (PET) fabrics style # 777H (Fabric 1). To initiate this study. Mw/Mn=1.18 The authors recognize that silver has long played a role in antimicrobial finishing products.000 g/mol.24 000 g/mol. Highly polished single-crystal silicon wafers of {100} orientation (Semiconductor Processing Co.3 nm. explained that a liquid film deposited on a porous substrate recedes via two separate mechanisms: suction and dewetting. The polymer contained ~29 wt% of styrene and 1. Issue 4 .) at an incidence angle of 70°. Poly (2-vinylpyridine) (PVP) was obtained from Aldrich (Mn. Glycidyl methacrylate (GMA) obtained from Aldrich was polymerized using free radical polymerization to obtain poly (glycidyl methacrylate) (PGMA) (Mn.19 The detailed behavior of the roughness levels and the wetting behavior are not discussed here. #703 (Fabric 2) and a PET microfiber fabric (Fabric 3) were obtained from Testfabrics Inc. Despite such difficulties the RMS roughness (root mean square roughness value) could still be approximated and was found to vary considerably in different areas of the leaves (microns). We considered that micron level modifications may lead to deterioration of the properties of the textile fibers and fabrics and in addition mimicking nature’s non-homogenous rough surface seemed overly complex. ultrahydrophobicity. Scanning probe microscopy (SPM) was used to analyze the morphologies obtained on silicon wafer using Dimension 3100 microscope (Digital Instruments. Ellipsometry measurements were done to measure the thickness of the polymer films after coating on model silicon wafer substrates using a COMPEL discrete polarization modulation automatic ellipsometer (InOmTech Inc. The hydrophobic polymer then provides “the icing on the cake” to give the ultrahydrophobic fabric response. tetrahydrofuran (THF) and methyl ethyl ketone (MEK) were obtained from VWR and used as received. Calcium carbonate nanoparticles of different shape and size were donated by Solvay chemicals. 96 and 105 nm were synthesized by procedure described by Evanoff et al. Textest FX3000 Hydrostatic pressure 2 http://www. Water contact angle (WCA) was measured using a goniometer (Kruss. All of the imaging was done at a scan rate of 1 Hz employing tapping mode.2008 nated end groups was obtained from Polymer Source Inc.37500 g/mol). De Gennes et al.

Step 3: The substrate was then exposed to an aqueous suspension of silver nanoparticles under constant ultrasonication for about 3 hours. toluene. The determination of the fabric stiffness was performed using a cantilever-bending tester.2008 3 http://www. The PGMA/PVP morphology formed on the silicon substrate was then studied using SPM. Both plasma and corona treatments add surface functionalities that increase the reactivity of the PET fiber/fabric surfaces and they were performed to ensure that any subsequent grafting processes were successful. After optimizing treatment conditions on the model silicon wafer substrates. The corona treatment was performed at standard conditions (70°F/21°C temperature and 65% relative humidity) with the fabric swatch placed exactly 1 cm below the corona treatment head. Silicon Wafer Preparation Silicon wafer substrates before applying the surface modification processes were initially cleaned with de-ionized water in an ultrasonic bath for 30 minutes. 84 nm. and the tensile properties using Instron (Model 1125). acetone.jeffjournal. Crosslinking of PGMA stabilizes the microstructure of the blend. corona treatments were used as an alternative for the plasma discharge due to the limited capacity of the plasma equipment. SILVER NANOPARTICLES APPROACH Preparation of hydrophobic substrates using silver nanoparticles approach The following procedure illustrated below (Figure 1) was performed on clean silicon wafers to optimize the experimental procedure and later the optimized procedure was applied to the PET fabrics. the same treatments were then implemented on three different polyester fabrics. Step 2: The annealed substrate was treated with ethanol (good solvent for PVP) to ensure the presence of PVP on the surface. S ilv e r N a n o p a r tic le G r a fte d P S B r u s h P G M A /P V P PET PGM A FIGURE 1. The wafer was then placed in piranha solution (3:1 concentrated sulfuric acid/30% hydrogen peroxide) for approximately one hour. and then rinsed several times with de-ionized water. 96 nm and particles greater than 105 nm respectively (Table I).tester. each having an inherently different fabric roughness.8 W power for 2 minutes at a pressure of about 200 torr. The plasma/corona treated fabrics were then rinsed in THF to remove any low molecular weight remnants formed due to the chain scission process during the treatment. After rinsing. % PGMA in MEK). For larger sample sizes. Issue 4 . PVP is responsible for the adsorption of the nanoparticles providing a metal-ligand complex22 between the silver nanoparticle and PVP. Fabrics were later subjected to an air plasma discharge (frequency 13.56MHz) 6.1 wt.org . Fabrics were thoroughly rinsed in de-ionized water for about 1 hour to remove water soluble residuals and dried in an oven at 80°C until they achieved constant weight. Schematic representation of the lotus approach using silver nanoparticles to achieve lotus effect. Here the effect of nanoparticle size on the wettability was studied by exposing four model substrates (simultaneously prepared) with four aqueous suspensions of silver nanoparticles that differed in the nanoparticle size. Each of the four aqueous suspensions contained approximately 1010 particles/ml with particles sizes of 52 nm. Step 4: The substrate was then dip coated with a second layer of PGMA (0. the substrates were dried under a stream of nitrogen in clean room 100 conditions. EXPERIMENTAL Model Substrates Silicon wafers were used as model (flat) substrates to optimize the experimental conditions required to create surfaces with high repellency. PET Fabric Preparation The three polyester fabrics were initially rinsed in the following solvents (water. and ethanol) to remove surface contaminants.2 wt/vol %) and then annealed at 110°C for 10 minutes to aid self crosslinking of the epoxy groups of PGMA. These wafers were chosen as model substrates to study polymer grafting thickness and nanoparticle adsorption. Journal of Engineered Fibers and Fabrics Volume 3. Step 1: The cleaned substrate was dip coated using different blend compositions of the PGMA/PVP solution prepared in MEK (0.

jeffjournal. (a) Fabric 1 with 335 g/m2 density. Four samples of each of the 3 fabrics were prepared to study the adsorption effect of each of the 4 different sized nanoparticle suspensions (as shown in Table II). Preparation of hydrophobic and ultrahydrophobic PET fabrics using silver nanoparticles SEM images of the three different PET fabrics used in this study are shown in Figure 2. Scanning probe microscopy (SPM) analysis was performed on the resultant substrates after each step. (b) Fabric 2 with 122 g/m2 density and (c) Fabric 3 made from Polyester microfibers. Unreacted PS was later removed by multiple rinses in toluene. Polyester Fabrics of different constructions. TABLE I. Listing of the Experimental Design on Silicon Wafer Substrates Name Substrate 1 Substrate 2 Substrate 3 Substrate 4 Step 1 PGMA/PVP dipcoating PGMA/PVP dipcoating PGMA/PVP dipcoating PGMA/PVP dipcoating Step 2 Ethanol treatment Ethanol treatment Ethanol treatment Ethanol treatment Step 3 52 nm silver nanoparticle suspension 84 nm silver nanoparticle suspension 96 nm silver nanoparticle suspension > 105 nm silver nanoparticle suspension Step 4 PGMA dipcoating PGMA dipcoating PGMA dipcoating PGMA dipcoating Step 5 PS grafting PS grafting PS grafting PS grafting (a) (b) (c) 1 mm 1 mm 500 µm FIGURE 2. Fabric 1 and Fabric 2 had different fabric densities at 335 g/m2 and 122 g/m2 respectively. Listing of the Experimental Design on PET Fabrics Name Fabric 1 Fabric 2 Fabric 3 Step 1 (70: 30) PGMA/PVP dipcoating (70: 30) PGMA/PVP dipcoating (70: 30) PGMA/PVP dipcoating Step 2 Ethanol treatment Ethanol treatment Ethanol treatment Step 3 52 nm/ 84 nm/ 96 nm/ > 105 nm silver nanoparticle suspension 52 nm/ 84 nm/ 96 nm/ > 105 nm silver nanoparticle suspension 52 nm/ 84 nm/ 96 nm/ > 105 nm silver nanoparticle suspension Step 4 PGMA dipcoating PGMA dipcoating PGMA dipcoating Step 5 PS grafting PS grafting PS grafting Journal of Engineered Fibers and Fabrics Volume 3.org . Step 5: Carboxy terminated PS (using 0.5 wt.% PS solution in toluene) was then grafted to the uncrosslinked epoxy functionality of the top layer at 150ºC for approximately 4 hours via reaction of the PS carboxylic groups with the epoxy groups of PGMA. The third fabric (Fabric 3) is composed of PET microfibers. Issue 4 . Scanning electron microscopy (SEM) was used to verify nanoparticle coverage. The formation of a “nanoparticle sandwich” ensures nanoparticles entrapment and it is assumed that this arrangement is very robust and durable.This second layer traps silver particles in a cage between the first PGMA/PVP layer and PGMA layer. The hydrophobicity of these fabrics after PS grafting was studied using WCA measurements. TABLE II. Based on the results obtained on the samples using the above procedure the experimental conditions were optimized.2008 4 http://www. The wettability characteristics of these substrates after the final step of PS grafting were studied using the static contact angle measurements.

30x. the substrates (Si wafter/fabrics) were rinsed in 10 wt % acetic acid (AA) to dissolve the calcium carbonate nanoparticles. The wettability of the substrates 5 http://www.2 wt % aqueous suspension as follows:. The CaCO3 nanoparticles were applied to silicon wafer substrates but studies were not extended to fabrics.jeffjournal. The fabrics were then exposed to a suspension of CaCO3 nanoparticles (~ 100 nm to 200 nm) dispersed in 2% SEBS polymer solution prepared from toluene. 40. In concept if this is found to work well. under constant ultrasonication for 3 minutes. The substrates (silicon wafers/fabrics after initial sample preparations) were dip coated under constant ultrasonication in PGMA solutions in MEK (0. Effect of the shape of CaCO3 nanoparticles on ultrahydrophobicity The effects of cube-like and needle-like CaCO3 nanoparticles23 as shown in Figure 4 (of different sizes) were used for the study. and also 1800x). This approach was performed to verify if the creation of ultrahydrophobic textiles using nanoparticles could be prepared from other nanoparticle materials. Taking one further step. Issue 4 . Different concentrations of nanoparticles suspensions were prepared by diluting the initial 5. then the nanoparticles can be removed from the substrates after initial modification and as a result the may improve the handle and comfort properties of the fabrics. Schematic of the lotus approach using calcium carbonate nanoparticles (represented by blue spheres) and SEBS polymer micro-pores (in the form of dimples) in place of the nanoparticles that had previously made the surface bumpy/rough. This empirical optimization approach was used to evaluate which nanoparticle concentration would give the highest contact angle on the silicon wafer. The substrates after the modification were analyzed using SPM to study the nanoparticle distribution. The nanoparticle application procedure (as explained above) was also used for CaCO3 nanoparticles.org .2 wt/vol %) for 3 minutes. The PGMA coated fabrics were annealed at 110°C for 10 minutes. 300x.SILICA NANOPARTICLES APPROACH The application procedure described for the silver nanoparticles approach above was also applied for silica nanoparticles. 50x.(10x. Optimization of surface roughness on silicon wafer via silica nanoparticles approach Silicon wafer substrates were treated using silica microspheres of size 150 nm ± 30 nm (Polysciences Inc). Scanning probe microscopy (SPM). The amount of CaCO3 nanoparticles added to the SEBS solution was varied at different % concentrations by volume (30.2008 Ss n il o S ic a e W f r Dip coating in SEBS polymer solution containing CaCO3 nanoparticles er o lym SP E S B r a fe n W ilic o S FIGURE 3. This study was only intended to investigate the effect of nanoparticle shape on surface properties. to create the macromolecular anchoring layer. Variations in the % composition of CaCO3 nanoparticles to SEBS helped empirically optimize the nanoparticle content and identify the best combination of the nanoparticle and the SEBS polymer. This nanoparticle concentration would then be applied to the three different PET fabrics. This in-turn left Journal of Engineered Fibers and Fabrics Volume 3. 20x. CALCIUM CARBONATE (CaCO3) NANOPARTICLES APPROACH Synthesis of ultrahydrophobic silicon wafer substrates/polyester fabrics using CaCO3 nanoparticles In an attempt to reduce the number of steps to prepare ultrahydrophobic fabrics as compared to the multi-step approach using silver/silica nanoparticles the following procedure was used. The compositions of both the cube-like and needle-like nanoparticles were varied with respect to the hydrophobic SEBS polymer concentration. The presence of CaCO3 nanoparticles along with the SEBS polymer on the silicon wafer/fabric provides a rough/bumpy profile as illustrated in Figure 3. 60 and 70) with respect to the SEBS polymer concentration. The porous surface was then studied as a reverse lotus template and was examined in order to verify if dimpled surface profiles are sufficient to increase water contact angle. scanning electron microscopy (SEM) analysis and contact angle measurements were performed to analyze the nanoparticle distribution and the wetting behavior of the substrates after the modification. 50.

After the test. AATCC standard reference detergent was used as the surfactant. the fabrics were thoroughly washed with distilled water (numerous rinses) for several hours to remove all the surfactant and thereafter the WCA was measured on these fabrics. hydrostatic pressure test. 2. Different blend percentages of the PGMA/PVP system were also experimented with. (a) (b) FIGURE 4.jeffjournal. This dynamic test Journal of Engineered Fibers and Fabrics Volume 3.org . The modified fabrics were washed once in 0. The second layer of PGMA had a thickness of around 2 nm and the final polystyrene layer thickness ranged between 5 to 15 nm.1% detergent solution at 60°C for 2 hours. 2. 3 and the nanocoated fabric. RESULTS AND DISCUSSION Silver Nanoparticles Approach Characterization of the hydrophobic silicon wafer substrates The thickness of the PGMA/PVP polymer layer (after step 1) was 4. The PGMA/PVP blend morphology of the substrates after step 2 (ethanol treatment) showed dispersed morphology due to the immiscibility of the polymers. All of the four samples were tested at a gradient pressure of 10 mbar/min. and the PET fabric after modifying with nanoparticles and polymer coating (Nanocoated fabric). All tests were performed on fabrics before and after the modification processes.. It was found that the silver nanoparticle adsorption was dependent on the size of the PVP domains formed in the PGMA matrix. The initial fabrics samples prepared using the above mentioned approaches were of smaller size (~ 2 x 5 cm). (a): cube like CaCO3 nanoparticles of size 40-70 nm and (b) needle like CaCO3 nanoparticles of size 200-350 nm. 3 and the nanocoated fabric. Thus new samples of size 25 x 25 cm were prepared for performing these tests. stiffness test and wash tests.2008 Wash Test A slightly modified version of AATCC wash test method 124-1996 was used to estimate the durability of the nanoparticle treatment. 2. The ideal PVP inclusion size was expected to be at least 100 nm (as it approximately matched the size of the largest nanoparticles used) and such domains should ensure a good cover6 http://www. cleaned PET fabric with polymer (SEBS) coating only (Control 3).was verified using the water contact angle measurements. Clearly larger sample sizes were needed to test these bulk fabric properties. step 2 (Figure 5b) and step 3 (Figure 5c). PET fabric 2 was chosen for the study and was divided into 4 samples such as. Varying the amount of PVP in the PGMA/PVP blend also regulated the density of silver nanoparticles adsorbed.0 ± 1 nm as measured by Ellipsometry24 on the model silicon wafer substrate. Tests were performed in both the warp and weft direction. Air Permeability Test ASTM test method D-737 was used for this study at a test pressure of 125 pascal.e. the fabric “as is” (Control 1). This test was used as an objective measure of the air permeability of the fabrics before and after the nanoparticle modification using the four samples of fabric 2 described above (control 1. 3 and nanocoated fabric). fabric after cleaning to remove fabric finishes before the modification (Control 2). Samples of 1” x 6” were cut from each fabric i. strip test. Figure 5 shows the SPM images after step 1 (Figure 5a). controls 1.. Issue 4 . measures the resistance of the fabrics to water penetration. The results are reported in terms of cubic feet per minute (CFM). EVALUATION OF THE FABRIC PROPERTIES AFTER NANO-PARTICLE MODIFICATION It could be expected that adsorption of the nanoparticles onto fiber surfaces could adversely change other fabric properties.e. In order to estimate the deterioration of some other fabric properties the following test methods were employed: air permeability test. Strip Test ASTM test method D-5035 was used for this study to analyze the change in fabric strength before and after the modification. controls 1. Hydrostatic Pressure Test AATCC test method 127-1998 was used for this study. i. Stiffness Test ASTM test method D-1388 utilizing a cantilever bending tester was used for this study to test each of the fabrics.

2008 7 http://www. Issue 4 . Silicon wafer modified with: (a) PGMA/PVP (70/30). Figure 6 shows the SEM micrographs of polyester fabric 1 samples (after step 3) obtained using aqueous nanoparticle suspensions of size 52 nm. Here it should be noted that the PVP inclusion size ranged from 100 to 150 nm (as measured on the silicon wafer substrates). (c) 96 nm Journal of Engineered Fibers and Fabrics Volume 3. (c): PS grafted on the top PGMA layer.e. (b) 84 nm. Fabrics 2 and 3. (a): 52 nm. From Figure 7. (a) (b) (c) FIGURE 5.jeffjournal. Figure 7 shows the SEM micrographs of fabric 1 (after step 3) using nanoparticles with a size greater than 105 nm. It can be observed from Figure 6. The distribution density of nanoparticles (size > 105 nm) was manually calculated from the SEM micrograph in Figure 7c and was found to be in the range of 20 ± 5 nanoparticles/µm2. c): 200 nm. We do not claim this distribution is the same for all fibers in the fabric as it is expected that varied nanoparticle adsorption will occur on the individual fibers and yarns that make up the fabric. Silver nanoparticles of different size adsorbed on PET fabric (1) at 10k magnification. Vertical scale (a): 10 nm.org . Also observed from the Figures 6. that not all 3 different sizes of the nanoparticles show complete and even surface coverage.22 The adsorption of the silver nanoparticles (post Figure 5a) and thus coverage on the 70/30 composition can be seen in the SPM morphologies Figure 5b. (a) (b) (c) 5 µm 5 µm 5 µm FIGURE 6. The PVP islands successfully immobilized silver particles (after overnight exposure to a suspension of silver nanoparticles in deionized water) due to the affinity of pyridyl groups to silver through metal ligand interactions of the nitrogen atoms. (b): silver nanoparticles sandwiched between PVP/PGMA and PGMA layers. Fabric 1 showed water contact angles (WCA) of about 150° ± 5°. Other blend ratio’s showed varied sizes and inconsistent phase separations.age of the surface with the silver nanoparticles. This calculation was made only on this fiber surface and is at best an indicator of particle distribution. c) SPM topography images. it was also observed that the nanoparticles stayed intact after the PS grafting and after several rinses of the sample in toluene to remove the ungrafted PS polymer. 1 X 1 µm (a) and 3 X 3 µm (b.. it can be observed that this particle size gave more even nanoparticle coverage on the fiber surface than the smaller sized particles. Similar adsorption behaviors were observed for the other fabrics i. 84 nm and 96 nm. However the water contact angles measured after the final modification step (step 5) was different for all of the 3 fabrics. Polyester (PET) lotus fabrics obtained from silver nanoparticle approach Although silver is a well known antimicrobial agent the primary objective for using silver nanoparticles was to obtain the appropriate surface roughness. 7 was that the density of silver nanoparticles adsorbed on fiber surfaces increases as the nanoparticle size increases and was a maximum for the nanoparticles with size greater than 105 nm. Though the fabrics covered with the silver nanoparticles might indeed render some anti-microbial properties. From Figure 5c. Hence it was decided to use this particular composition of 70/30 blend ratio for further studies. The 70/30 blend ratio of the PGMA/PVP system was found to form PVP inclusion size of approximately 100 to 150 nm (measured from the SPM morphology in Figure 5a). (b. these studies were not undertaken. whereas fabric 2 showed WCA of 160° ± 8° and fabric 3 showed WCA of about 138° ± 3°.

Figure 9 shows the SPM topography images after the nanoparticle modification at different dilution rates as described in the experimental section. Silver nanoparticles of different size adsorbed on PET fabric (1) at 10k magnification. the optimum RMS value was found to be around 40 to 50 nm and corresponds to the 30-50 times dilution range. fabric 2 can be considered to show ultrahydrophobic properties as the contact angle is above the 150° mark. Using the SPM software. The data shown in Figure 10 identified the RMS values that give the highest WCA. As observed in Figure 10.2008 bicity of PS polymer and the roughness caused by the silver nanoparticles. (b): ultrahydrophobic fabric. Static water contact angle on (a): PET fabric grafted with PS only (no silver). The contact angle of the fabric increased from 113° ± 4° (Figure 8a) for the PET fabric with PS only to 157° ± 3° for PS/silver multilayer system (Figure 8b). this RMS value was chosen as the empirical optimum value. Fabric 1 was observed to be in the border line of ultrahydrophobicity while the PET microfiber fabric (3) is well below the ultrahydrophobic border. 8 http://www. A static contact angle analysis (Figure 8) was performed on the PET fabric having the PS/silver multilayer treatment and on a PET fabric modified with only PS (no silver). (b) 84 mn. but we consider that such assumptions are in any case reasonable due to the fact that water contact angle measurements are not accurate for any textile surface that has a high degree of roughness.jeffjournal. (a): 52 nm. Silica Nanoparticles Approach Optimization of surface roughness on silicon wafer A variety of rough surfaces were created on the model silicon wafer substrate using different dilution rates of the silica nanoparticles of approximately 150 nm size. The WCA was measured for all of the samples and the results were plotted against the RMS values. In this case it appears that a combination of ultrahydrophobic treatments on fabrics of sufficient inter-yarn spacing leads either to increased treatment efficacy or a greater entrapment of air within the fabric structure (or both) to apparently increase levels of hydrophobicity as measured by water contact angle measurements. After the samples were prepared SPM was used to analyze the RMS roughness values of the surface. (c) 96 nm The differences in the WCA values could be attributed to the difference in the fiber and fabric structures. the RMS values of the samples were measured. On comparing SEM’s of fabrics 1 and 2 it can be seen that fabric 2 is a more open fabric (Figure 2). From the WCA measurements. the multilayered PS/PGMA/SILVER/ PVP/PGMA system on the PET fabric is appears to have reasonable robustness since the particles did not detach at high temperature (during PS grafting) or in toluene under ultrasonic treatments. It is acknowledged that the error bars are high for these fabrics. Issue 4 . Thus the reason for the dramatic increase in the WCA of the fabric (making it to be classified as ultrahydrophobic) must be attributed due to the synergistic effect of the hydrophoJournal of Engineered Fibers and Fabrics Volume 3. The openness of the yarns (in both warp and weft directions) leads to larger inter-yarn spaces. (a) (b) FIGURE 8. Such roughness is present in the form of protruding fibers and also due to the weave pattern. As an aside.10 µm 5 µm 2 µm FIGURE 7.org . For nano-level roughness.

shows the adsorption of the silica nanoparticles on the PET fiber surfaces on fabric 1. This implies that the roughness of the fabric 3 (microfiber fabric) did not in combination with the nano-rough surface modified fiber/fabric contribute sufficiently to achieve ultrahydrophobicity. Issue 4 .PET lotus fabrics obtained from silica nanoparticle approach The three PET fabric types (335. WCA (Water contact angle) Vs. Figure 12. RMS roughness plot of silicon wafer modified with silica nanoparticles and SEBS polymer.jeffjournal. Vertical scales are (a. Journal of Engineered Fibers and Fabrics Volume 3.org . (a) 30 x dilution (b) 50 x dilution and (c) 300 x dilution.2008 9 http://www. In the case of the PET microfiber fabric. FIGURE 9. b) 300 nm and (c) 100 nm 135 Contact Angle. 122 gsm fabric and also PET microfiber fabric) were then treated using the optimized procedure described above and the apparent WCA measurements after the modification are shown in Figure 11. SPM topographies of homogeneous rough surfaces created via silica nanoparticles approach at various dilution rates. nm FIGURE 10. degrees 130 125 120 115 110 105 100 30 35 40 45 50 55 Roughness. the WCA was observed to be ca. 135° ± 3°. The 335 gsm fabrics showed a WCA of 150° ± 5° suggesting that the fabric is of borderline ultrahydrophobicity. the 122 gsm fabrics showed ultrahydrophobicity with contact angles well above 150° with a WCA at 165o.

(a) (b) 10 µm 5 µm FIGURE 12. % ) FIGURE 13.org . Issue 4 . (a) 5k and (b) 10k magnifications. % CaCO3 composition plot on silicon wafer treated substrates. Silica nanoparticles (100 nm) adsorbed on the PET fiber surface of fabric 1. WCA (Water contact angle) Vs. Water contact angles on the 3 different PET fabrics after silica nanoparticle modification(a): Fabric 1 with WCA ~ 150°. degree 145 140 135 130 125 120 115 110 30 40 50 60 70 80 90 B e fo r e A A R IN S E A te r A A R IN S E % C A C O 3 ( V o l.2008 10 http://www.jeffjournal. 155 150 Contact Angle. (b): Fabric 2 with WCA ~ 165° and (c) Fabric 3 with WCA ~ 135°. Journal of Engineered Fibers and Fabrics Volume 3.(a) (b) (c) FIGURE 11.

See magnifications. buildings. As seen in Figure 15. But after the nanoparticles were dissolved using 10 % acetic acid (AA). i. housing. and hence the substrates show the “lotus effect. Hydrophobic and Ultrahydrophobic silicon wafer substrate obtained from CaCO3 nanoparticle approach Figure 13 shows the effect of % composition of the CaCO3 nanoparticles on the WCA. the WCA drastically dropped as observed from Figure 13. perfectly flat surface. (a) 100 and (b) 5k magnifications. Formation of CaCO3 nanoparticle aggregates was observed on silicon wafer substrates.” FIGURE 16. Different % compositions by volume of CaCO3 nanoparticles to SEBS were prepared to create numerous surface topographies.2008 11 . The thickness of the PGMA layer was found to be 2. Figure 14 shows the ultrahydrophobic WCA obtained on the silicon wafer substrate before dissolving the nanoparticle. For example if the nanoparticles rest mainly in the topmost part of the film and are just touching the SEBS hydrophobic layer instead of the nanoparticles being half immersed in the SEBS layer the roughness levels will not be maintained after the removal of the nanoparticles. Issue 4 . This shows that the high level of roughness obtained in the form of bumps (with the presence of nanoparticles) are not replicated in the form of pores (i.org FIGURE 14. CaCO3 nanoparticles (~100 to 200nm) adsorbed on the PET fiber surface. a reverse lotus effect after dissolving the nanoparticles).. It was observed that certain volume 70% concentrations of CaCO3 nanoparticles gave increased hydrophobic http://www. It is also important to note that these high contact angles are achieved on the modification of a virtually Journal of Engineered Fibers and Fabrics Volume 3. Though this approach showed promising results.e. Water droplet suspended on PET fabric of different fabric structures with CaCO3/SEBS coating. silicon wafer without using any fluorinated polymers. Figure 17 illustrates the SPM analysis of the model silicon substrate covered with CaCO3 nanoparticles dispersed in SEBS matrix. It is thought that this might be due to depth distribution issues. Obtaining ultrahydrophobicity on a flat surface without fluoropolymers opens way for other applications such as automobile exterior surfaces.0 ± 1 nm and the final SEBS polymer layer thickness was measured to be between 100 and 200 nm.Calcium Carbonate Nano-Particles Approach The CaCO3 nanoparticles approach (as described in the experimental section) uses less application steps in the fabrication process compared to our previous approaches. Water droplet suspended (158°) on a CaCO3 modified silicon wafer substrate. though aggregation was a problem using this approach the WCA obtained on all of the substrates such as wafer and also both fabrics (1 and 2) showed ultrahydrophobic properties. Effect of CaCO3 nanoparticles shape on obtaining ultrahydrophobic effect The effect of shape was studied on the silicon wafer substrate. airplane surfaces hornings and many more.. 500 µm 10 µm FIGURE 15.jeffjournal. the RMS roughness values increases abruptly to a sub-micron or micron level roughness. CaCO3 nanoparticles with % compositions of 60 and 70 exhibit ultrahydrophobic water contact angles < 150° even on the model silicon wafer substrates. the nanoparticles did tend to form aggregates and this could then lead to undesired variability in coating consistency.e. walls. With aggregation of the nanoparticles on both the silicon wafer and fabric substrates.

In order to estimate the deterioration of the fabric properties ASTM standard textile methods were used namely. in general. Issue 4 . superior to the needle shaped particles as shown in Figure 18. which showed increased resistance to the flow of water through the fabric.jeffjournal. cubic needle Contact Angle. it was observed that though the needle shaped nanoparticles have sharp asperities than the cube shaped particles they did not exhibit high WCA for any of the CaCO3 % compositions. Control PET fabrics “as is” (Control 1). It was interesting to find that the PET fabric with only hydrophobic polymer coating (Control 3 has a WCA of about 130°) showed increase in resistance to that of the fabric modified with both nanoparticle and hydrophobic polymer coating (nanocoated fabric has a WCA greater than 150°). this type of ultrahydrophobic material relatively promotes the flow of water through the fabric structure compared to the simple hydrophobic material. The cube shaped nanoparticles were. water penetration through the fabric using the hydrostatic head test. and the tensile properties of the fabric before and after fabric modification using the strip test. bicity is desirable for many applications it seemed likely that other fabric properties may have changed during the treatments. Hydrostatic pressure test AATCC test method 127-1998 was used for this study. This very interesting result suggests that the increases in nano-roughness (due to the presence of nanoparticles and the consequential increases in fabric hydrophobicity) do not necessarily reduce the resistance to pressurized fluid flow through the fabric. The silica nanoparticles (100nm) approach was used in conjunction with fabric 2 to evaluate some basic fabric properties. degree 150 140 130 120 110 30 40 50 60 70 80 CaCO3 content. In other words. It was found that the fabric coated with hydrophobic polymer only (Control 3) and the fabric after the modification with nanoparticle and polymer coating (Nanocoated fabric) showed increased resistance to water penetration as compared to the other fabric samples (see Figure 19). Air permeability test ASTM test method D-737 was used for this study. From the results. air permeability test. PET fabric after cleaning to remove fabric finishes before the modification (Control 2). % 90 FIGURE 18. It was found that all the above fabrics recorded an air permeability reading of 15 cfm with no significant changes in the reading when tested repeatedly. (a) (10x10 µm) cube and (b) (5x5 µm) needle shaped particles. cleaned PET fabric with polymer (SEBS) coating only (Control 3). (a) (b) FIGURE 17. Effect of CaCO3 nanoparticle shape on the WCA of the silicon substrate Evaluation of fabric properties after the nanoparticle modification The main focus of this study has been to examine a number of fabric treatment methods to obtain ultrahydrophobic textile materials.org . and the PET fabric after modifying with nanoparticles and polymer coating (Nanocoated fabric) were tested.properties relative to other concentrations applied. This study limits only to CaCO3 nanoparticles and hence the shape effect does not apply to other nanoparticles like silica or silver. SPM images of silicon wafer substrates coated with shaped CaCO3 nanoparticles dispersed in an SEBS matrix. Whilst ultrahydrophoJournal of Engineered Fibers and Fabrics Volume 3.2008 12 http://www.

org . There were no significant changes in the breaking strength (measure in lbf) and elongation % for both the warp and weft direction measured for all the above fabric samples. V. It was found that the average contact angle reduced by about 5°. This showed that the nanocoating along with the hydrophobic polymer is quite robust and at least under these washing conditions the fabric did not significantly change it hydrophobic nature. it is necessary to have the correct roughness component and hydrophobic components. 1” x 6” samples were cut for each of the fabrics described above (control 1. In the case of the CaCO3 nanoparticles the effect of shape and size of these CaCO3 nanoparticles was found to have an influence on hydrophobcity. CONCLUSIONS For a fabric to show ultrahydrophobic properties. The WCA before washing was found to be around 150 to 155°. While the silica and calcium carbonate nanoparticles are relatively cheap (compared to silver) they also showed some aggregation problems. Ideally one would like a perfect dispersion of particles. Klep for the synthesis of PGMA and Solvay Chemicals for donating calcium carbonate nanoparticles of different shapes and sizes. Regarding the systems used in this study the silver nanoparticles approach was found to have little or no aggregation problems. 3 and nanocoated fabric). Fabric strength was analyzed using the strip test. Both the warp and weft direction were tested for all of the above fabric samples.Resistance to water penetration. Wash test AATCC test method 124-1996 was used for this study. ACKNOWLEDGEMENT The authors wish to thank the Department of Commerce (National Textile Center) for financial support of this work. Typically this selection process would be based on base material costs. From the results it appears that certain shapes and sizes gave increased hydrophobicity relative to other shapes and this is an area for future work. however. Resistance to water penetration vs. The wash test provided further information on the durability of the nanoparticle treatment on the PET fabric. This shows that the fabric strength did not deteriorate after the nanoparticle modification. ease of application and fabric property enhancement. Additionally we would like to acknowledge support from (CAEFF). Fabric Sample FIGURE 19 . The authors would like to thank Dr.2008 13 http://www. Issue 4 . the Center for Advanced Engineering Fibers and Films and COMSET the Center for Optical Materials Science and Engineering at Clemson University. We have described a number of methods to create surfaces that lead to ultrahydrophobicity using hydrophobic polymer/nanoparticle systems. mbar 13 12 11 10 9 8 Control 1 Control 2 Control 3 Nanocoated Fabric lotus fabric with ultrahydrophobicty may be created without the need of nanoparticles.jeffjournal. 2. The results with both the silver and silica nanoparticles independently showed that fabric construction is an important parameter to consider when attempting to create lotus type fabrics. Strip test ASTM test method D-5035 was used for this study. whereas after washing it varied between 145 to 150°. fabric sample (hydrostatic pressure test). It may be expected that by having the appropriate fabric roughness and the appropriate hydrophobic component coating a Journal of Engineered Fibers and Fabrics Volume 3. Nevertheless the addition of nano-roughness using nanoparticles gives the experimentalist another option for fabric tunability. The implication of this is very encouraging since the silicon wafer is virtually perfectly flat it clearly opens up application areas for ultrahydrophobic coatings outside those of textile materials. even though CaCO3 nanoparticles had some aggregation problems they still displayed ultrahydrophobic properties when applied to the flat model substrate (silicon wafer). In order to create a lotus fabric “the finisher” should also consider the type of nanoparticles to be used.

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