FAST RESPONSE NANOFIBER ARTICLES WITH TUNABLE WETTABILITY AND

BULK PROPERTIES

CROSS-REFERENCE TO RELATED APPLICATION The present application claims the benefit of U.S. Provisional Application Serial No. 61/528,040, filed August 26, 2011, which is hereby incorporated by reference herein in its entirety, including any figures, tables, or drawings.

This invention was made with government support under Contract No. DE-AC04- 94AL85000 awarded by the Department of Energy National Nuclear Security Administration. The government has certain rights in the invention.

BACKGROUND OF THE INVENTION

Materials to form devices that can be switched between, for example, a superhydrophilic surface or a superhydrophobic surface, have garnered great attention for fundamental considerations and for applications as self-healing surfaces, selective molecular separation, controlled drug delivery, and smart textiles. In general, these switchable materials are engineered to respond to an external stimulus, such as light irradiation, pH changes, solvent exposure, electrical potential, magnetic field, mechanical force, or temperature. Thermally responsive materials are of particular interest due to the narrow temperature response and the predictable properties the materials can display upon undergoing the transition. The switchable responses result from structural changes to the material as the properties change. Although generally a single property is the focus in a study of a material, other properties of the material will simultaneously change, for example, a temperature change that switches a surface property of a material, can simultaneously switch a bulk property of the material. The rate of switching of these properties and the response profile will depend on the shape and size of the article in addition to the chemical composition of the article.

Poly(N-isopropylacrylamide) (PNIPA) has been explored extensively with respect to its temperature responsive properties. PNIPA displays a lower critical solution temperature (LCST) of 32-33 °C in water. The polymer's repeating units display a reversible hydrogen bonding preference for water molecules or other repeating units of the polymer due to enthalpic and entropic contribution to the free energy of PNIPA chains. Below the LCST, enthalpic contributions dominate over entropic contributions and the polar groups (C=0 and N-H) of PNIPA form intermolecular hydrogen bonds with water molecules, which places the PNIPA polymer chains in "extended conformations", when the polymer is dissolve in water. Above the LCST, entropic contributions dominate the enthalpic contributions of bonding with water, and hydrogen bonding occurs between repeating units of the polymer chains rather than with water molecules, which causes the PNIPA chains to exist in collapsed "globular conformations" and to precipitate from solution.

To fabricate surfaces that display reversible extreme wettability (REW) characteristics, PNIPA has been processed by layer-by-layer, hydrothermal, surface entrapment, phase separation, self-assembled monolayers, electrochemical deposition, and other methods. These techniques are complicated, typically requiring multiple process steps to produce a responsive surface for the observation of reversible wettability. Wang et ah, Macromol. Rapid Comm., 2008, 29, 485-89, teaches the electrospinning of a poly(N- isopropylacrylamide)/polystyrene composite film. The films were spun from tetrahydrofuran solutions, leaving a combination of microparticles and nano fibers. The use of a composite solution high in poly(N-isopropylacrylamide) (6: 10:90 PNIPA/PS/THF) resulted in poor spinibility dominated by microfibers with a size distribution of 0.5 to 2 μπι with connected microparticles with diameters in excess of 10 μηι, whereas a composite high in polystyrene (1 : 10:90 PNIPA/PS/THF) did not display switchable wettability and little nanofiber content with microparticles having diameters of 5 to 25 μηι. At an intermediate composition (2: 10:90 PNIPA/PS/THF), a switchable wettability was achieved although spinning still resulted in a combination of microparticles and nanofibers, where microparticles dominated the structure and were 3.5 to 30 μηι in diameter.

To exploit reversible wetting properties (REW) or other surface properties, and/or bulk properties for practical applications on a large scale, a simple fabrication technique is required that can achieve a structural consistency, where the structure is superior to that presently achieved for these materials, for example, a structure that is very small and controllable so that the switching rate can be designed and rapid. BRIEF SUMMARY OF THE INVENTION

Embodiments of the invention are directed to a fibrous properties-switching article whose properties rapidly and reversibly switch over a range of temperatures. The article comprises a mat consisting of fibers of at least one polymer, copolymer, polymer blend, and/or polymer network with narrow fiber size distribution, having a diameter of about 2 μηι or less, where the material undergoes a structural change over the range of temperatures, which causes the surface and/or bulk property of the mat to change over the range of temperatures. In exemplary embodiments of the invention, the structural change is a conformational change in N-isopropyl acrylamide units of poly((N-isopropylacrylamide), where the hydrogen bonding of the amide switches from bonding with water at low temperatures to intramolecular bonding between repeating units of the polymer at higher temperatures. Fiber mats of a polymer blend of polystyrene and poly((N- isopropylacrylamide) (bl-PS/PNIPA) and of crosslinked poly(N-isopropylacrylamide-co- methacylicacid) (xl-PNIPAMAA) display dramatic changes in their hydrophilicity over a relatively narrow temperature range. The switching speed that can be achieved depends on the diameter of the fibers in the mat, with very high switching speeds possible for very small diameter fibers.

Embodiments of the invention are directed to the preparation of mats of very small fibers by electrospinning. By the proper choice of parameters, including the polymer concentration and the solvent, a mat is formed that displays exclusively fibers by SEM. The bl-PS/PNIPA fiber mat is spun from dimethylformamide (DMF), which, suprisingly, gives exclusively fibers with no particles being observed, as is the case when a THF solvent is employed. A PNIPAMAA fiber mat is spun from DMF and subsequently heated to crosslink the fibers.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows digital photographic images of dye solutions placed on a) a blended polystyrene/poly((N-isopropylacrylamide) (bl-PS/PNIPA) fiber mat according to an embodiment of the invention and b) a crosslinked poly(N-isopropylacrylamide-co- methacylicacid) (xl-PNIPAMAA) fiber mat according to an embodiment of the invention showing reversible, extreme wettability (REW) properties. Figure 2 shows scanning electron microscopy (SEM) images of a) a bl-PS/PNIPA fiber mat according to an embodiment of the invention and b) xl-PNIPAMAA fiber mat according to an embodiment of the ivention, and c) a transmission electron microscopy (TEM) image of the bl-PS/PNIPA fiber mat where the PS and PNIPA blending at the nanoscale dimensions are apparent.

Figure 3 shows a plot of the contact angle (CA) over a range of temperatures for bl- PS/PNIPA and xl-PNIPAMAA fiber mats according to embodiments of the invention.

Figure 4 shows a plot of CA against temperature during cycling of the temperature for bl-PS/PNIPA and xl-PNIPAMAA fiber mats according to embodiments of the invention, where the bl-PS/PNIPA fiber mats were cycled between 15 °C and 65 °C and the xl- PNIPAMAA fiber mats were cycled between 20 °C and 95 °C.

Figure 5 shows SEM images of bl-PS/PNIPA fiber mat according to an embodiment of the invention, with fibers of diameter: a) 380; b) 990; c) 1500; and d) 16000 nm.

Figure 6 shows photographs of water droplets on a 380 nm diameter fiber bl- PS/PNIPA fiber mat, according to an embodiment of the invention at 65 °C and 25 °C, where the mat is superhydrophobic and superhydrophilic, respectively.

Figure 7 shows selected photographic images taken at the indicated time in seconds after placing a fiber mat, according to an embodiment of the invention, supporting a water droplet on top a metal bar maintained at -30±3, where a) a 380 nm fiber bl-PS/PNIPA mat transformed from superhydrophobic to superhydrophilic within 5 seconds, and where b) a 16000 nm fiber bl-PS/PNIPA mat resulted in freezing of the water droplet before wetting of the surface to an appreciable degree.

Figure 8 shows DSC plots of PNIPAMAA dissolved in water and hydrated xl- PNIPAMAA fibers.

Figure 9 shows SEM images of the sections of fiber mats in the presence of water after the heating and cooling cycles that are illustrated in Figure 4 were carried out, for mats of a) bl-PS/PNIPA and b) xl-PNIPAMAA according to embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the invention are directed to preparing and using articles having surface and/or bulk properties that change upon a change of temperature. In an embodiment of the invention, a fiberous surface that displays reversible extreme wettability (REW) is formed by electrospinning, as shown in Figure 1 for exemplary embodiments. The electrospinning readily produces a mat of fibers, where the rate of response and the switching rate of the resulting fiber mat is controlled by the diameter of the fiber. In exemplary embodiments of the invention, the fibers have diameters that range from about 100 nm to about 2 μιη in diameter depending on predetermined conditions employed. This process involves the imposition of a high electrical field, for example, l-5kV/cm, to a polymer droplet as it exits an orifice, for example, the end of a needle. The applied high electrical force overcomes the surface energy of the droplet and forms a Taylor cone where a stream of liquid erupts from the droplet. Subsequently, as the liquid stream dries in flight, the mode of current flow changes from ohmic to convective as the charge migrates to the surface of the fiber. The stream is elongated by a whipping process caused by electrostatic repulsion initiated at small bends in the fiber, until the fibers are deposited on a grounded collector. The elongation and thinning of the fiber, resulting from bending instability, leads to formation of uniform fibers, often displaying nanometer-scale diameters, and results in a mat of fibers on the collector that possess a high surface area to mass ratio.

In exemplary embodiments of the invention, properties switching articles are prepared from polystyrene/poly(N-isopropylacrylamide) blends (bl-PS/PNIPA), and poly(N-isopropyl acrylamide-co-methacylicacid) (PNIPAMAA) are used to produce REW articles by electrospinning. The fiber mats of blended PS/PNIPA (bl-PS/PNIPA) and crosslinked PNIPAMAA (xl-PNIPAMAA) display REW properties while maintaining integrity at temperature ranges that are broad. In one embodiment of the invention a fiber mat was produced from bl-PS/PNIPA that exhibited exclusively fibers, as shown in Figure 2a. This contrasts with the mat observed by Wang et ah, Macromol. Rapid Comm.,2008, 29, 485-89 where it was not possible to achieve exclusively fiber structures. In an embodiment of the invention, the fiber mat was produced by electrospinning the blend from a dimethylformamide (DMF) solution of the bl-PS/PNIPA, indicating that the nature of the solvent is critical to the electrospinning of fibers. Analysis by TEM of the bl-PS/PNIPA fiber mat displays a blended structure where two distinct polymer phases with nanometer dimentions are apparent, as can be seen in Figure 2c. For exemplary embodiments of the invention, the surface morphologies of the bl-PS/PNIPA and xl-PNIPAMAA fiber mats, as shown by the SEM images in Figure 2, indicate that the fiber mats are exclusively fibers that have a uniform size distribution and a mean fiber diameter of 1950 nm for the mat from bl- PS/PNIPA and 870 nm for the mat from xl-PNIPAMAA.

Response times of hydrogels have been shown to be directly proportional to the square of the gel dimension and inversely proportional to the network diffusion coefficient: τ = r ² /D _coop Equation 1

where, r is the characteristic swelling time for diffusion to achieve equilibrium, r represents the smallest gel dimension, and D _coop is the cooperative diffusion coefficient of the network, Tanaka et al. J. Phys. Rev. Lett. 1985, 55, (22), 2455-8. The value of D _C00p for PNIPA varies between 10 ^*12 and 10 ^"10 m ² s ^"1 depending upon the crosslinking density, polymer concentration, and temperature, with an inverse correlation between D _coop and temperature, and with an order of difference in diffusion coefficients, 5>< 10 ^"12 and 2x l0 ^"n m ² s ^"1 , for de- swollen gel at temperatures greater than 32 °C and water swollen gel at temperatures less than 32 °C, respectively. As it is difficult to increase the value of D _coop by a factor of 10 ² or more, the actual response time of a hydrogel largely depends upon gel thickness, or the fiber diameter for the fiber mats, according to an embodiment of the invention.

Because the fiber diameter can be controlled, the response time can be controlled. As calculated in Table 1 , below, the rate at which the fiber can switch depends on heat transfer and/or water (or other chemical) diffusion through the fiber, which are processes whose rates vary with the cross-sectional area of the fiber. As can be seen in Table 1, the rate of switching can be dramatically decreased as the fiber's diameter decreases, allowing switching times that can occur in milliseconds or less when fiber diameters drop below a micrometer (μπι). As surface properties, such as wettability, and bulk properties, such as elastic modulus, can vary dramatically, such materials can be useful in applications where an article comprising a polymeric material must respond to the environment it experiences, for example, a tire. The property change results from a structural change of the material comprising the fiber; for example, the fiber can be constructed of a polymer that has functionality that undergoes a conformational change, a change in association, or a change in solvation. The fibers can be those of a homopolymer, a copolymer, a polymer blend, or a polymer network. In embodiments of the invention, the polymer changes structure from a polymer hydrogen bonded to water at low temperatures to a self hydrogen bonding polymer at higher temperatures, such that water is released when the polymer adapts a conformation for intramolecular hydrogen bonding. Table 1 Calculated switching response times for fibers of different diameters.

Fiber Diameter (nm) x ^l (μη ) Calc Response time (msec)

10,000 2.5 833

1,000 0.25 8.3

100 0.025 0.083

Contact angle (CA) measurements were undertaken for the 870 nm fiber bl- PS/PNIPA and the 1950 nm fiber xl-PNIPAMAA electrospun fiber mats, according to embodiments of the invention. At 15 °C, the bl-PS/PNIPA fiber mat shows a response consistent with a superhydrophilic surface, which is defined as a surface with a CA value of <5°. At 65 °C, a 138.0°±4.5 CA is observed, which is near the value, >150°, considered to indicate a superhydrophobic surface. The CA values for the bl-PS/PNIPA and xl- PNIPAMAA fiber mats at various temperatures are given in Table 2, below, and shown as a plot in Figure 3. The switching occurs between 30 °C and 45 °C for the fiber mat of bl- PS/PNIPA. At 45 °C, the bl-PS/PNIPA sample displays a CA that is 90 % of the steady state CA value for higher temperatures. This REW of bl-PS/PNIPA and xl-PNIPAMAA fiber mats are shown in Figure 4 for the data of Table 3, below, for wetted fiber mats, where the temperature is cycled 5 times between temperatures displaying hydrophilic or superhydrophilic behavior and hydrophobic or superhydrophobic behavior.

Table 2 CA values of bl-PS/PNIPA and xl-PNIPAMAA fiber mats at various temperatures.

870 nm bl-PS/PNIPA Fiber Mat 1950 nm xl-PNIPAMAA Fiber Mat

Temperature (°C) CA±SD (°) Temperature (°C) CA±SD (°)

15 0.0±0.0 20 20.5±6.3

25 0.0±0.0 40 16.6±3.8

30 0.0±0.0 60 63.2±4.4

35 65.4±6.1 70 82.2±3.6

40 101.8±4.3 75 87.8±3.1

45 124.2±7.8 80 87.7±6.7

55 134.5±3.6 85 87.4±4.2

65 138.1±4.4 90 89.5±2.7

- - 95 87.3±2.7 Table 3 Temperature responsive reversibility CA values of bl-PS/PNIPA and xl-PNIPAMAA fiber mats where each cycle was between 15 °C and 65 °C for bl-PS/PNIPA fiber mats and 20 °C and 95 °C for the xl-PNIPAMAA fiber mats.

Number of bl-PS/PNIPA fiber mat xl-PNIPAMAA fiber mat cycles CA±SD (°) CA±SD O

0 o.o±o.o 19.7±1.0

0.5 144.0±6.3 90.7±2.6

1 0.0±0.0 17.2±2.3

1.5 144.7±9.4 88.1 ±1.6

2 0.0±0.0 22.3±1.7

2.5 140.0±9.1 88.5±4.8

3 0.0±0.0 12.2±1.9

3.5 133.4±4.4 87.3±3.6

4 0.0±0.0 17.1 ±5.1

4.5 136.8±4.5 90.9±1.6

5 0.0±0.0 15.3±1.6

CA measurements carried out on electrospun PS/PNIPA fiber mats, shown in Figure 5, with different diameter fibers, according to an embodiment of the invention, are reported in Table 4, below. The interaction between a liquid droplet and a porous structure conforms to the Cassie-Baxter (CB) model, where the relationship between CA and the porosity of a material is:

cos 0 _C3 = fX± -t cos θγ - 1 Equation 2

where 6CB is the apparent contact angle on a rough surface, θγ is the equilibrium (Young's) contact angle on a smooth surface, and f _s is the fraction of the wet solid contact area. The electrospun fiber mats are a nonwoven fiber network with three dimensionally interconnected pores and grooves between the fibers. The CA values at 65 °C given in Table 4 agree with values calculated using the CB model where a reduction in the fiber's diameter reduces the fraction of fiber area in contact with the water droplet such that a fiber mat constructed of sufficiently fine diameter fibers displays superhydrophobicity, with water CA values 150°, as given in Table 4. Electrospun PS/PNIPA fiber mats, according to an embodiment of the invention, show superhydrophobic to superhydrophilic switching. Table 4. Response time on PS/PNIPA blended fiber mats with different diameter fibers

Fiber dia Mat thickness Fraction of wet 9 _c at 65 °C Cold source ^b Response time (nm) w/Al-foil (μηι) solid contact (°) ^a (sec) area (f _s )

380±100 44±6 0.39±0.03 144 ±5 metal bar 4.2±0.9

990±300 55±10 0.39±0.02 146±4 metal bar 4.3±0.6

1.5K±900 53±10 0.40±0.01 140±4 metal bar 4.8±0.7

16K±1.2 70±10 0.48±0.03 135±6 metal bar >25-30 ^c

16K±1.2K 70±10 - 135±6 stage 47.4±1.9

380±100 44±6 - 144 ±5 stage 13.3±0.9 ^a At 24 °C the contact angle (CA) was 0° for all the fiber mats; 9 _C : contact angle, ^b Metal bar temperature was maintained at -30±3 °C using liquid N ₂ ; stage temperature was maintained at 24±1 °C using cold water bath-circulator; ^c frozen.

The response time for a change from the maximum CA to the minimum CA for the PS/PNIPA blended fiber mats from different diameter fibers given in Table 4, above, corresponds to the change of a water droplet as illustrated in Figure 6. Figure 7 graphically displays this transformation for a mat of a) 380 nm diameter fibers and of b) 16 μιη diameter fibers. Table 4 gives the fiber diameter, fiber mat thickness, CA value measured at 65 °C, and the cold source used to study response time. All fiber mats are superhydrophilic with a 0° CA value at 25 °C. All mats displayed response times below one minute, and mats with fiber diameters of 380, 990 and 1.5K nm display a fast response time, of < 4-5 seconds, while the mats with fiber diameter of 16K nm displayed a significantly slower response time, where the droplet froze within 30 s on the low temperature cold bar before wetting of the fibers could proceed, where movement of the ice drop at 35 seconds is shown in Figure 7b.

The REW properties of the xl-PNIPAMAA fiber mats is indicated by a transition temperature that can be observed in a DSC measurement and occurs at the temperature where the fiber mat's surface changes from hydrophilic to hydrophobic during heating and from hydrophobic to hydrophilic properties during cooling. The xl-PNIPAMAA fiber mat exhibits an upward shift in transition temperature, observed as a strong broad peak at 82.7 °C in a DSC plot, which differs from that of -32 °C for the transition displayed by PNIPAMAA in water, indicating that transition temperature for the material increases upon crosslinking, as indicated in Figure 8. Additionally, the presence of PVA in xl-PNIPAMAA causes the fiber mat to be more hydrophilic than in the absence of PVA, shifting the transition point to a higher temperature. In contrast to bl-PS/PNIPA fiber mats, the CA measurements of the xl- PNIPAMAA fiber mat reveal a response between hydrophilic and nearly hydrophobic, where hydrophobicity is indicated by CA value that is >90°. The CA values vary from 20.5°±6.5 to 87.0°±3.0 for the xl-PNIPAMAA fiber mat as the temperature varies from 20 °C to 95 °C, as indicated in Table 2, above, and plotted in Figure 3. The transition point observed for the xl- PNIPAMAA fiber mat, as determined by DSC, was -83 °C, although the CA measurements for the xl-PNIPAMAA fiber mat attained 94 % of the steady state CA value at 70 °C over a relatively broad switching temperature range of 40 to 70 °C, as indicated in Table 3, above. Figure 4 shows that the temperature cycling of the xl-PNIPAMAA results in a switching between hydrophilic and nearly hydrophobic behavior of the mat's surface.

The fiber mats, according to embodiments of the invention, are those where the solubility of the fiber mat in water is inhibited. In one embodiment, the solubility is inhibited by blending a polymer that is water soluble below the LCST with a polymer that is insoluble in water at all temperatures. In another embodiment, a water soluble polymer is crosslinked to a water swellable, yet insoluble material. Leaching experiments were carried out where vacuum dried fiber mats were water washed with stirring at 10 °C for 24 hours and agian vacuum dried. Result of the experiments, as inidicated in Table 5, below, suggest that other factors than just the dissolving of water soluble portions of the mats affected the results. For example, the 83.3 % weight loss of the bl-PS/PNIPA indicated a retention of only 16.7 % of the mass, even though approximately 70 % of the mat's mass was blended polystyrene, which is water insoluble. In contrast, the xl-PNIPAMAA fiber mat lost 53.3 % of its mass upon washing, although it was, in principle, a crosslinked mass that should swell but not dissolve in water.

Table 5 Weight loss by water washing of bl-PS/PNIPA and xl-PNIPAMAA mats at 10 °C.

Fiber mat sample % Mass loss % Retained Mass

Bl-PS/PNIPA 83.3±4.2 16.7±4.2

xl-PNIPAMAA 53.3±0.5 46.7±0.5

The integrity of the bl-PS/PNIPA and xl-PNIPAMAA fiber mats in areas where the fiber mats had experienced the heating and cooling cycles to determine REW by CA measurements was determined by SEM analysis. As can be seen in Figure 9a, the bl- PS/PNIPA fiber mat displays damage to the fibrous structure. In contrast, the xl- PNIPAMAA fiber mat retains its structure after experiencing heating and cooling cycles, as can be seen in Figure 9b. Interestingly for the bl-PS/PNIPA, even though fiber damage occurred, the fiber mat continued to demonstrate consistent REW properties over all tested cycles, as indicated in Figure 4.

The crosslinking reactions that occur in PNIPAMAA can include: anhydride formation between carboxylic acid groups of PNIPAMAA; esterification between carboxylic acid groups of PNIPAMAA and alcohol groups of poly(vinyl alcohol) (PVA); and/or imidization between carboxylic acid groups and amide groups of PNIPAMAA. It is reasonable that all three of the reactions with the carboxylic acid groups contribute to crosslinking the electrospun PNIPAMAA fibers during heat treatment at 160 °C in a vacuum oven.

MATERIALS AND METHODS

Materials

Polystyrene (PS) (M _n 170,000 g/mol and M _w 350,000 g/mol), polyfN- isopropylacrylamide-co-methacrylic acid) (PNIPAMAA) (M _n 60,000 g/mol, 90 mol % PNIPA and 10 mol % MAA), disodium hydrogen phosphate (DSHP), and dimethylformamide (DMF) were used as received from Sigma-Aldrich. PolyfN- isopropylacrylamide) (PNIPA) (M _v -40,000 g/mo) was used as received from Polyscience Incorporation. Polyvinyl alcohol) (PVA) (75 % hydrolyzed and MW 2,000) was used as received from Acros Organics. Glacial acetic acid (99.9 % HOAc) was used as received from Fisher.

Preparation of PS/PNIPA Blended Fiber Mat

A 15 % wt blend solution of PS and PNIPA (PNIPA/PS 30/70 wt/wt) was prepared by dissolving the polymers in DMF. The blend solution was placed in a 3 mL syringe, fitted with an 18-gauge stainless steel needle (inner diameter of 0.965 mm). The syringe was fixed horizontally on a syringe pump (Model: BSP-99M, Braintee Scientific Inc.), and an electrode connected to a high voltage power supply (Model: ES30N-5W, Gamma High Voltage Research) was attached to the tip of the metallic needle. A grounded stationary square collector (10 cm x 10 cm) covered by a piece of clean aluminum foil was used for fiber collection. Electrospinning, to produce bl-PS/PNIPA with 870 nm fibers, was carried out using the blend solution under the following operating conditions: a flow rate (FR) of 0.90 mL/h; an electric field (EF) of 0.8 kV/cm; and a distance between the needle and the collecting plate (Dcp) of 1 1 cm. Electrospinning was performed for about 30 mins.

PS/PNIPA blended fiber mats with diameter of the fiber 380, 990, 1.5K and 16K nm were fabricated by varying the blend solution concentration, flow rate, distance between the needle tip and collector surface (Dcp) or gap distance, electric field, and needle gauge in electrospinning given in Table 6, below. Attempts to produce higher diameter fibers yielded fibers that were fused together.

Table 6. PS/PNIPA 70/30 w/w preparation conditions, and the fibers and mats produced.

Wt % Flow rate DCP EF in Needle Time in Fiber dia. Mat thickness blend in μΙ7ηπη. in cm kV/cm Gauge min. in nm in μιτι

15 3 20 0.43 24 180 380±100 44±6

15 3 20 0.43 18 150 990±300 55±10

15 15 1 1 0.77 18 45 1500±900 53±10

30 150 1 1 0.77 18 5 16000±1200 70±10

15 3 20 0.43 18 60 1500±400 83±14

15 3 20 0.43 18 180 600±100 163±16

15 3 20 0.43 18 600 800±200 258±32 Preparation of Crosslinked PNIPAMAA Fiber Mat

Water stock solutions of 15 % wt NIPAMAA/HOAc, 15 % wt PVA/DI water, and 10 % wt DSHP/DI were prepared. A formulation was generated by mixing 0.68 g of the PNIPAMAA/HOAc solution with 15 % wt PVA/DI water to yield 5 % wt PVA relative to PNIPAMAA and 30 % wt DSHP relative to PVA. Electrospinning was carried out using the formulation under the following operating conditions: FR of 0.43 mL/h; EF of 1 kV/cm; and Dc of 20 cm. Electrospun fibers were collected on a 1 mm thick glass slide (size 7.6 cm x 2.5 cm) for 3 mins. The bottom of the glass slide was fixed to aluminum foil using a double- sided copper tape. The collected electrospun fiber mats were kept in a vacuum oven at room temperature (RT) overnight, followed by a heat treatment at 160 °C for 30 minutes in a vacuum oven. Subsequently, samples were washed in cold water (10 °C) followed by hot water (100 °C) and this washing cycle was repeated two additional times. Contact angle (CA) measurements were carried out on the fiber mats collected on a glass slide. Surface Morphology and Structure Analysis

The surface morphology of bl-PS/PNIPA and xl-PNIPAMAA fiber mats were examined using a field emission gun SEM (Model: 6335F, Jeol), where a small portion of electrospun fiber mat was cut and fixed to a SEM stub using a double-sided adhesive carbon tape. Sample was sputter coated with a thin film of gold-palladium to aid in SEM analysis, and analyzed in SEM with an accelerating voltage of 10 kV. Additionally, the blended structure of bl-PS/PNIPA fiber mat was examined using TEM (Philips CM30), where a thin web of electrospun sample was collected on a copper grid and directly examined in TEM at an accelerating voltage of 300 kV.

Contact Angle Measurements

CA measurements were carried out on electrospun samples using a Goniometer (Model: VCA Optima, AST Products, Inc.) instrument equipped with an automated dispensing system and a 30 gauge flat-tipped stainless steel needle. The probe fluid, water, having resistivity >18 ΜΩ-cm was collected using a nanopure Milli-Q purification system (Millipore Inc.). Sessile drop images were captured, by placing 2 μΕ or 4 μΕ water droplets onto the fiber mat at 5 different places. The CA data were then obtained by Drop-Snake analysis, a plug-in for Image J software.

Water Resistance of Mats

About 10 mg of the bl-PS PNIPA or xl-PNIPAMAA vacuum dried fiber mat was added to a vial containing de-ionized water (25 mL at 10 °C) and stirred at 50 rpm for 24 h. Subsequently, the fiber mat was removed from the vial and dried overnight in a vacuum oven at RT.

Mean Fiber Size Analysis

Mean fiber diameters of electrospun fiber mats were analyzed using Image J, a general purpose image processing software. Ten SEM images were obtained at different sites on each fiber mat. All fibers present in an image were measured for determining mean fiber diameter, where at least 150 individual fibers were measured for the analysis of each fiber mat.

Determination of Transition Temperature

Hydrated xl-PNIPAMAA fiber mats weighing -20 mg were used for DSC analysis.

Temperature scans were performed between 5 °C and 100 °C to analyze sample transition temperatures. A 7.5 % wt PNIPAMAA in DI water was analyzed by DSC to determine its transition temperature.

Temperature Dependent CA Measurements

For temperature dependent CA measurements, heating was performed using a thin- flexible Kapton® heater (Model: KH-203/10, Omega Engineering, Inc.) and cooling was performed by a cryostage (Product Number: 39467506, Subzero™ Freezing Microtome Stage, Leica) attached to a cooler maintained at 24±1 °C using a water bath-circulator. Fiber mats, either collected on aluminum foil or a glass slide, were attached to a silicon wafer by a double-sided carbon adhesive tape. The silicon wafer was fixed to a flexible heater and a cryostage using scotch tape and the entire setup was placed on Goniometer stage. A thin thermocouple (Model: SA1-K-SRTC, Omega Engineering, Inc.) connected with a temperature meter (Model: BS5001k2, Omega Electronics, Inc.) was adhered to the fiber mat to read its surface temperature. The flexible Kapton® heater was powered by a DC power supply (Model: 6218 A, Agilent HP), the temperature on the fiber mat was adjusted by controlling the voltage current. The DC power supply was switched on during heating cycles and the cryostage was switched on during cooling cycles. The temperature was measured with ±1 °C accuracy.

To impose a very quick step-function temperature reduction and, therefore, a rapid response, the 24 °C cryostage was replaced with a metal bar at a temperature of -30±3 °C, that was maintained using liquid N ₂ as the coolant. Droplets placed over 16K nm diameter fiber mats froze after 25-30 seconds, whereas response time measurements using a stage at 24±1 °C, was found to be 47.4±1.9 s. A 380 nm fiber mat's response time using the stage at 24±1 °C, was 13.3±0.9 s, which is much slower than when the metal bar was used. Due to the limitations encountered in the experimental setup, response time for nanofibers may be shorter than that measured in this study.

Determination of the Wet Solid Contact Area

The fraction of the wet solid contact area of electrospun fiber mats was obtained using Image J software. The image was first converted 32-bit type: image > type > 32-bit. The threshold level was determined by adjusting and measuring to obtain the fraction of the wet solid contact area: image > adjust > threshold. Determination of Response Time on PS/PNIPA Blended Fiber Mats

PS/PNIPA Blended fiber mats response time was investigated by capturing and analyzing the video for the transition from a maximum to minimum CA. The camera captures 60 frames per second. Fiber mat collected on aluminum (Al)-foil was glued to silicon (Si)- wafer using double-sided adhesive carbon tape to ensure a flat fiber mat surface that facilitated the response time studies. A thermocouple (Model: SA1-K-SRTC, Omega Engineering, Inc.) was glued on top of the fiber mat and was connected to a temperature meter (Model: BS5001k2, Omega Electronics, Inc.) to monitor the fiber mat's surface temperature. A fiber mat was heated to 65±1 °C by resistive heating, using a thin and flexible Kapton® heater (Model: KH-203/10, Omega Engineering, Inc.) with help of a DC power supply (Model: 6218A, Agilent HP), where upon reaching 65 °C, a 4 xL volume dye solution (50 ppm concentration Procion red dye prepared in water) was placed above the fiber mat using a pipette. The fiber mat was transferred to the top of a metal bar maintained at - 30±3 °C using liquid N ₂ . The start time was when the Si-wafer with the fiber mat assembly fully contacted the metal bar and the end time was noted when the dye solution reached a minimum CA value. The response time was determined as an average of 5 values from 5 different spots. The measurements were conducted in an enviroment with relative humidity and temperature of 45 % and 25 °C, respectively.

All patents, patent applications, provisional applications, and publications referred to or cited herein, supra or infra, are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.

It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.