Methods for treating a polycarbonate glass surface and forming directed hierarchical nanopatterning and increasing hydrophobicity

Abstract

A method of treating a polycarbonate glass surface, such as a bisphenol A polycarbonate, whereby the glass surface is immersed in a liquid phase polar aprotic solvent, such as dichloromethane, and exposed to a vapor phase polar aprotic solvent, such as acetone thus obtaining a textured glass surface with a hierarchical patterned nanoporous structure wherein the textured glass surface has a higher surface hydrophobicity and a marginally reduced optical light transmittance relative to the polycarbonate glass surface prior to the immersion, the exposure, or both.

Claims

1. A method of treating a glass surface comprising a polycarbonate, comprising: immersing the glass surface in liquid phase dichloromethane for about 2 seconds or less to form a treated glass surface comprising nanopores; and exposing the treated glass surface to vapor phase acetone for less than 4 minutes to form a textured glass surface with a hierarchical patterned nanoporous structure; wherein the textured glass surface has a higher surface hydrophobicity than the glass surface prior to the immersing, the exposing, or both; and wherein the textured glass surface has an optical light transmittance that is reduced by no more than 25 percentage points relative to the optical light transmittance of the polycarbonate glass surface prior to the immersing, the exposing, or both.

2. The method of claim 1, wherein the polycarbonate is produced from the precursor monomer bisphenol A.

3. The method of claim 1, wherein the immersing is performed for a time period of 1.0-2.0 seconds and the exposing is performed for a time period of 0.8-1.5 minutes.

4. The method of claim 1, wherein the treated glass surface comprises nanopores with an average diameter in the range of 100-800 nm and an average depth in the range of 2-15 nm.

5. The method of claim 1, wherein an average distance between the nanopores of the treated glass surface is in the range of 1-10 m.

6. The method of claim 1, wherein the textured glass surface with a hierarchical patterned nanoporous structure comprises pores with an average diameter of 200-1000 nm and an average depth of 20-150 mm.

7. The method of claim 1, Wherein the textured glass surface with a hierarchical patterned nanoporous structure comprises spherules with an average width of 5-20 m and an average height of 0.2-5 m.

8. The method of claim 7, wherein the surface of the spherules is textured and comprises fibers with an average diameter of 200-600 nm and an average height of 20-200 nm.

9. The method of claim 1, wherein the textured glass surface has an average water droplet contact angle of greater 75.

10. The method of claim 1, wherein the treated glass surface has an optical light transmittance of greater than 85% and the textured glass surface has an optical light transmittance of greater than 75%.

11. The method of claim 1, wherein the textured glass surface has a roughness root mean square value in the range of 100-500 nm.

12. The method of claim 1, wherein the exposing is performed for a time period of 1 minute or less.

13. A method of treating a glass surface comprising a polycarbonate, comprising: immersing the glass surface in a liquid phase polar aprotic solvent for less than 3 seconds to form a treated glass surface comprising nanopores; exposing the treated glass surface to a vapor phase polar aprotic solvent for less than 4 minutes to form a textured glass surface with a hierarchical patterned nanoporous structure, wherein the textured glass surface has a higher surface hydrophobicity than the glass surface prior to the immersing, the exposing, or both, and wherein the textured glass surface has an optical light transmittance that is reduced by no more than 25 percentage points relative to the optical light transmittance of the polycarbonate glass surface prior to the immersing, the exposing, or both; and dip coating the textured glass surface in a sol gel comprising 1,1,1,3,3,3-hexamethyl disilazane (HMDS) and tetraethyl orthosilicate (TEOS) to form a coated textured glass surface.

14. The method of claim 13, wherein the coated textured glass surface has an average water droplet contact angle of greater than 130.

15. The method of claim 13, wherein the coated textured glass surface has an optical light transmittance of greater than 45%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) A more complete appreciation of the disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:

(2) FIG. 1 is a 3D atomic force microscopy (AFM) topography image of a smooth untreated polycarbonate glass surface.

(3) FIG. 2 is a 2D second order flattened topography micrograph of a smooth untreated polycarbonate glass surface.

(4) FIG. 3 is a 2D AFM line profile of a smooth untreated polycarbonate glass surface

(5) FIG. 4 is a 3D AFM topography image of a smooth untreated polycarbonate glass surface after ultrasonication for 15 minutes in isopropyl alcohol on a 1.0 m scale.

(6) FIG. 5 is a 3D AFM topography image of a polycarbonate glass surface after immersing in dichloromethane for 2 seconds.

(7) FIG. 6 is a line profile taken through an AFM topography image of a polycarbonate glass surface after immersing in dichloromethane for 2 seconds across pores.

(8) FIG. 7 is a 3D AFM micrograph at 20 m scale of a polycarbonate glass surface after immersing in dichloromethane for 2 seconds.

(9) FIG. 8 is a 2D AFM micrograph at 20 m scale of a polycarbonate glass surface after immersing in dichloromethane for 2 seconds.

(10) FIG. 9 is a 3D AFM topography image of a polycarbonate glass surface after immersing in dichloromethane for 5 seconds.

(11) FIG. 10 is a 3D topography AFM image of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 10 m scale.

(12) FIG. 11A is a 3D topography AFM image of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 20 m scale.

(13) FIG. 11B is a 3D topography AFM image of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 5 m scale.

(14) FIG. 12 is a 2D topography AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 20 m scale.

(15) FIG. 13 is a line profile texture micrograph taken through an AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 20 m scale.

(16) FIG. 14 is a 2D topography AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 5 m scale.

(17) FIG. 15 is a line profile texture micrograph taken through an AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 5 m scale.

(18) FIG. 16A is a 3D topography AFM image of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors at 20 m scale.

(19) FIG. 16B is a 3D topography AFM image of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors at 5 m scale.

(20) FIG. 17 is a 2D topography AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors at 20 m scale.

(21) FIG. 18 is a line profile texture micrograph taken through an AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors at 20 m scale.

(22) FIG. 19 is a 2D topography AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors at 5 m scale.

(23) FIG. 20 is a line profile texture micrograph taken through an AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors at 5 m scale.

(24) FIG. 21 shows all the transmittance curves for the four samples including an untreated polycarbonate glass surface and a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute (B.sub.1), 2 minutes (B.sub.2) and 4 minutes (B.sub.4) to acetone vapors.

(25) FIG. 22 is a graphical representation depicting that by increasing the exposure time to the acetone vapor (1 minute, 2 minutes, 4 minutes), the transmittance of a patterned polycarbonate glass surface decreases.

(26) FIG. 23 is an optical microimage of a water droplet on an untreated sample polycarbonate glass surface for contact angle measurements.

(27) FIG. 24 is an optical microimage of a water droplet on a sample polycarbonate glass surface immersion for 2 seconds in dichloromethane for contact angle measurements.

(28) FIG. 25 is an optical microimage of a water droplet on a sample polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors for contact angle measurements.

(29) FIG. 26 is an optical microimage of a water droplet on a sample polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 2 minutes to acetone vapors for contact angle measurements.

(30) FIG. 27 is an optical microimage of a water droplet on a sample polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors for contact angle measurements.

(31) FIG. 28 is the Fourier-transform Infrared (FT-IR) spectra of the four samples including an untreated polycarbonate glass surface and a polycarbonate glass surface after immersion for 2 seconds in dichloromethane and exposure for 1 minute (B.sub.1), 2 minutes (B.sub.2) and 4 minutes (B.sub.4) to acetone vapors.

(32) FIG. 29 is the equation for the hydrolysis of tetraethyl orthosilicate (TEOS)

(33) FIG. 30 is the equation for the reaction between a SiOH functionality and 1,1,1,3,3,3-hexamethyldisilazane (HMDS) to form the hydrophobic bond.

(34) FIG. 31 is an optical microimage of a water droplet on a sample polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 1 minute to acetone vapors and coating with a TEOS/HMDS sol gel for contact angle measurements.

(35) FIG. 32 is a 2D topography AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 1 minute to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale.

(36) FIG. 33 is a 3D topography AFM micrograph image of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 1 minute to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale.

(37) FIG. 34 is a line profile texture micrograph taken through an AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 1 minute to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale.

(38) FIG. 35 is an optical microimage of a water droplet on a sample polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 2 minutes to acetone vapors and coating with a TEOS/HMDS sol gel for contact angle measurements.

(39) FIG. 36 is a 2D topography AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 2 minutes to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale.

(40) FIG. 37 is a 3D topography AFM micrograph image of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 2 minutes to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale.

(41) FIG. 38 is a line profile texture micrograph taken through an AFM micrograph of a polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 2 minutes to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale.

(42) FIG. 39 shows the transmittance curve for a polycarbonate glass surface after immersion for 2 seconds in dichloromethane, exposure for 1 minute to acetone vapors and coating with a TEOS/HMDS.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(43) Embodiments of the present disclosure will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all of the embodiments of the present disclosure are shown.

(44) According to a first aspect, the present disclosure relates to a method of treating a glass surface comprising a polycarbonate, the method comprising i) immersing the glass surface in a liquid phase polar aprotic solvent for less than 3 seconds to form a treated glass surface comprising nanopores and ii) exposing the treated glass surface to a vapor phase polar aprotic solvent for less than 4 minutes to form a textured glass surface with a hierarchical patterned nanoporous structure, wherein the textured glass surface has a higher surface hydrophobicity than the glass surface prior to the immersing, the exposing, or both, and wherein the textured glass surface has an optical light transmittance that is reduced by no more than 25 percentage points relative to the optical light transmittance of the polycarbonate glass surface prior to the immersing, the exposing, or both.

(45) A used herein, polycarbonates (PC) are a group of thermoplastic polymers containing carbonate groups (O(CO)O) in their chemical structures. Polycarbonates are substantially transparent polymers comprising monomers containing hydrophobic phenyl and methyl groups and a hydrophilic carbonate group. As used herein, a thermoplastic or thermosoftening plastic is a plastic material, a polymer that becomes pliable or moldable above a specific temperature and solidifies upon cooling. Many polymer thermoplastics are considered glass or polymer glass (i.e. acrylic glass, polycarbonate, and polyethylene terephthalate) and are a lighter alternative to traditional glass. It is equally envisioned that the glass comprising a polycarbonate may comprise one or more additional thermoplastics. These thermoplastics may be used in addition to or in lieu of a polycarbonate. Exemplary additional thermoplastics include, but are not limited to, acrylic, poly(methyl methacrylate (PMMA), acrylonitrile butadiene styrene (ABS), nylon, polylactic acid (polylactide), polybenzimidazole, polyether sulfone, polyetherether keton (PEEK), polyetherimide (PEI), polyethylene (PE, UHMWPE, HDPE, MDPE, LDPE, XLPE, PEX), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polystyrene, polyvinyl chloride, Teflon, and the like.

(46) In a preferred embodiment, the polycarbonate is produced from the precursor monomer bisphenol A. Often the majority of polycarbonate materials are produce by the reaction of bisphenol A (BPA) with phosgene COCl.sub.2. As used herein, bisphenol A refers to an organic synthetic compound with the chemical formula (CH.sub.3).sub.2C(C.sub.6H.sub.4OH).sub.2 belonging to the group of diphenylmethane derivatives and bisphenols, with two hydroxyphenyl groups. It is equally envisioned that one or more additional precursor monomers may produce the polycarbonate. Exemplary additional precursor monomers that may be used in addition to, or in lieu of bisphenol A, include, but are not limited to, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C 2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, MBHA, BisOPP-A, PHBB, 2,4-BPS, TGSA, BPS-MAE, BPS-MPE, 4-hydroxyphenyl, and the like.

(47) As used herein, a polar solvent refers to a solvent having large dipole moments or partial charges often containing bonds between atoms with very different electronegativities. As used herein, a polar aprotic solvent refers to a solvent that may have hydrogens by that lacks OH or NH bonds and therefore cannot hydrogen bond with itself. Exemplary polar aprotic solvents include, but are not limited to, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, N,N-dimethylformamide, acetonitrile, dimethyl sulfoxide and the like. In a preferred embodiment, the liquid phase polar aprotic solvent is dichloromethane. In a preferred embodiment, the vapor phase polar aprotic solvent is acetone. In a most preferred embodiment the liquid phase polar aprotic solvent is dichloromethane and the vapor phase polar aprotic solvent is acetone.

(48) In one step the glass surface is immersed in a liquid phase polar aprotic solvent, preferably dichloromethane, for less than 3 seconds, preferably less than 2.8 seconds, preferably less than 2.4 seconds, preferably less than 2.2 seconds, or about 2.0 seconds to form a treated glass surface comprising nanopores.

(49) The treated glass surface comprising nanopores are first generated by immersing the polycarbonate glass in a polar aprotic solvent, preferably dichloromethane. In most instances, the immersing duration is important for maintaining the optical properties of the material to be useful in photovoltaic solar panels. After 2 seconds of immersion in dichloromethane the polycarbonate glass surface or treated glass surface maintains at least 80% transmittance. Therefore a 2 second immersion duration in dichloromethane is considered advantageous for this step.

(50) In a preferred embodiment, the treated glass surface comprises nanopores with an average diameter or width in the range of 100-800 nm, preferably 120-700 nm, preferably 140-650 nm, preferably 160-625 nm, preferably 180-600 nm. In another embodiment, the average diameter or width does not exceed 10 m, preferably 8 m, preferably 6 m, preferably 4 m, preferably 2 m, preferably 1 m. In a preferred embodiment, the treated glass surface comprises nanopores with an average depth in the range of 2-15 nm, preferably 2.5-10 nm, preferably 3-8 nm, preferably 3.5-6 nm, preferably 4-5 nm. In another embodiment the average depth does not exceed 8 nm, preferably 6 nm, preferably 5 nm, preferably 4 nm, preferably 3 nm. In a preferred embodiment, the average distance between the nanopores of the treated glass surface is in the range of 1-10 m, preferably 2-8 m, preferably 3-6 m, preferably 4-5 m. This is shown in FIG. 5, FIG. 6, FIG. 7, and FIG. 8.

(51) In another step the treated glass surface is exposed to a vapor phase polar aprotic solvent, preferably acetone for less than 4 minutes, preferably less than 3.5 minutes, preferably less than 3 minutes, preferably less than 2.5 minutes, preferably less than 2.0 minutes, preferably less than 1.5 minutes, preferably less than 1.25 minutes, or about 1.0 minute to form a textured glass surface with a hierarchical patterned nanoporous structure. In one embodiment, the vapor phase polar aprotic solvent is not dichloromethane, methyl ethyl ketone, or ethyl acetate.

(52) As used herein, hierarchical patterned structure or hierarchical patterned nanoporous structure refers to exhibiting structure on more than one length scale, and thus, the structural elements themselves having structure. For example, polymers can exhibit structural hierarchy on the molecular, ultrastructural, microstructural, and/or nanostructural level. Polymers may have spherules on the scale of m while the spherules themselves contain an ordered texture on the scale of nm.

(53) Accordingly, nucleation occurs at the initial stage of vapor phase polar aprotic solvent, preferably acetone, induced crystallization and poor crystals become perfect through segment reorganization with increasing exposure time and spherulites' growth at elongated periods of exposure. The generation of spherules with needle-like textured structure is related back to a molecular or atomic rearrangement process that takes place in order to achieve stable orientations, which is termed a crystallization process. High spherules density increases drastically the surface roughness and hydrophobicity at the expense of the optical properties. A large number of spherules that cover the whole surface to improve the hydrophobicity will reduce the surface transmittance and hence limit its applicability in photovoltaic solar panels. It is envisioned that polar aprotic solvent vapors, preferably acetone, reduce the crystallization dynamic time since much less polar aprotic solvent is available at the surface which prevents absorption by the surface layer compared to liquid polar aprotic solvent.

(54) In a preferred embodiment, the vapor phase polar aprotic solvent is acetone and the acetone source is heated to greater than 24 C., preferably greater than 26 C., preferably greater than 28 C., preferably greater than 30 C., preferably greater than 32 C., preferably greater than 33 C. to enhance evaporation

(55) In a preferred embodiment, the textured glass surface with a hierarchical patterned nanoporous structure comprises pores with an average diameter or width of 200-1000 nm, preferably 250-990 nm, preferably 300-980 nm, preferably 350-970 nm, preferably 400-950 nm, preferably 450-900 nm, preferably 500-800 nm. In a preferred embodiment, the textured glass surface with a hierarchical patterned nanoporous structure comprises pores with an average depth in the range of 20-150 nm, preferably 30-130 nm, preferably 40-120 nm, preferably 50-100 nm, preferably 60-90 nm. In another embodiment, the average depth does not exceed 120 nm, preferably 115 nm, preferably 110 nm, preferably 105 nm, preferably 103 nm. This is shown in FIG. 10, FIG. 11A, FIG. 11B, FIG. 12, FIG. 13, FIG. 14, and FIG. 15.

(56) In certain embodiments, the textured glass surface with a hierarchical patterned nanoporous structure comprises spherules with an average width of 5-20 m, preferably 8-18 m, preferably 10-15 m, or about 13 m. In certain embodiments, the textured glass surface with a hierarchical patterned nanoporous structure comprises spherules with an average height of 0.2-5 m, preferably 0.5-2.5 m, preferably 1.0-2.0 m, or about 1.5 m. In certain embodiments, the surface of the spherules is textured and comprises fibers with an average diameter of 200-600 nm, preferably 300-550 nm, preferably 400-500 nm, or about 450 nm and an average height of 20-200 nm, preferably 50-180 nm, preferably 100-160 nm, preferably 125-150 nm. This is shown in FIG. 16A, FIG. 16B, FIG. 17, FIG. 18, FIG. 19, and FIG. 20.

(57) In a preferred embodiment, the immersing is performed for less than 3 seconds, preferably less than 2.8 seconds, preferably less than 2.4 seconds, preferably less than 2.2 seconds, or about 2.0 seconds, such as for example 0.2-2.8 seconds, preferably 0.5-2.6 seconds, preferably 0.75-2.4 seconds, preferably 1.0-2.2 seconds, preferably 1.5-2.1 seconds and the exposing is performed for less than 4 minutes, preferably less than 3.5 minutes, preferably less than 3 minutes, preferably less than 2.5 minutes, preferably less than 2.0 minutes, preferably less than 1.5 minutes, preferably less than 1.25 minutes, or about 1.0 minute, such as for example 0.2-4.0 minutes, preferably 0.5-3.0 minutes, preferably 0.75-2.0 minutes, preferably 0.8-1.5 minutes. In a most preferred embodiment, the immersing is performed for a time period of 2 seconds and the exposing is performed for a time period of 1 minute. In a most preferred embodiment, the liquid phase polar aprotic solvent is dichloromethane and the immersing is performed for a time period of 2 seconds and the vapor phase polar aprotic solvent is acetone and the exposing is performed for a time period of 1 minute.

(58) As used herein, surface hydrophobicity is a measure of the wetting properties of a material's surface and relates to the difficulty or ease by which the surface is wet. In a number of technology fields and industrial application, materials with one or more hydrophobic surfaces or one or more super hydrophobic surfaces are advantageous due to their self-cleaning properties and relative difficulty to wet which in an antibacterial setting may reduce and minimize the contact area of bacterial fluid. One measure for surface hydrophobicity is the droplet contact angle of a liquid, common and exemplary liquids include, but are not limited to, water, glycerol and diiodomethane. As used herein, the term hydrophobic surface generally refers to surfaces which have a contact angle from 90-150 with a droplet of water, and the term superhydrophobic surface generally refers to surfaces which have a contact angle greater than 150 with a droplet of water. In a preferred embodiment, the textured glass surface of the present disclosure has a higher surface hydrophobicity than the glass surface prior to the immersing, the exposing, or both. In one embodiment, the contact angle of the polycarbonate glass surface and the textured glass surface may be determined using a contact angle goniometer.

(59) In one embodiment, the textured glass surface has an average water droplet contact angle of greater than 75, preferably greater than 76, preferably greater than 77, preferably greater than 78, preferably greater than 79, preferably greater than 80, preferably greater than 81, preferably greater than 82, preferably greater than 84, preferably greater than 860, preferably greater than 88, preferably greater than 90, preferably greater than 95, preferably greater than 100, preferably greater than 105. For example, the textured glass surface has an average water droplet contact angle in the range of 60-105, preferably 65-100, preferably 70-95, preferably 72-90, preferably 74-88, preferably 76-86, preferably 77-85, preferably 78-84, preferably 78-82. In one embodiment, the method increases the surface hydrophobicity as measured by an average water droplet contact angle of the textured glass surface by at least 0.5%, preferably at least 1.0%, preferably at least 1.5%, preferably at least 2.0%, preferably at least 2.5%, preferably at least 3.0%, preferably at least 4.0%, preferably at least 5.0%, preferably at least 6%, preferably at least 8%, preferably at least 10%, preferably at least 15%, preferably at least 20%, preferably at least 25% relative to a glass surface that is not immersed, exposed, or both (i.e. the percent increase in water droplet contact angle from the glass surface to the textured glass surface).

(60) In one embodiment, the textured glass surface has an average glycerol droplet contact angle in the range of 40-120 preferably 60-105, preferably 65-100, preferably 70-95, preferably 72-90, preferably 74-88, preferably 76-86, preferably 77-85, preferably 78-84, preferably 78-82. In one embodiment, the method increases the surface hydrophobicity as measured by an average glycerol droplet contact angle of the textured glass surface by at least 0.5%, preferably at least 1.0%, preferably at least 1.5%, preferably at least 2.0%, preferably at least 2.5%, preferably at least 3.0%, preferably at least 4.0%, preferably at least 5.0%, preferably at least 6%, preferably at least 8%, preferably at least 10%, preferably at least 15%, preferably at least 20%, preferably at least 25% relative to a glass surface that is not immersed, exposed, or both. In one embodiment, the textured glass surface has an average diiodomethane droplet contact angle in the range of 40-120, preferably 60-105, preferably 65-100, preferably 70-95, preferably 72-90, preferably 74-88, preferably 76-86, preferably 77-85, preferably 78-84, preferably 78-82. In one embodiment, the method increases the surface hydrophobicity as measured by an average diiodomethane droplet contact angle of the textured glass surface by at least 0.5%, preferably at least 1.0%, preferably at least 1.5%, preferably at least 2.0%, preferably at least 2.5%, preferably at least 3.0%, preferably at least 4.0%, preferably at least 5.0%, preferably at least 6%, preferably at least 8%, preferably at least 10%, preferably at least 15%, preferably at least 20%, preferably at least 25% relative to a glass surface that is not immersed, exposed, or both.

(61) As used herein, surface roughness (roughness) is a component of surface texture. It is quantified by the deviations in the direction of the normal vector of a real surface from its ideal form. If these deviations are large, the surface is rough; if they are small, the surface is smooth. Roughness is often considered to be the high-frequency, short-wavelength component of a measured surface. In one embodiment, roughness can be measured by manual comparison against a sample of known surface roughness, alternatively a surface profile measurement may be made with a profilometer that can be contact and/or optical.

(62) In one embodiment, the textured glass surface has a roughness root mean square taken over a 5 m scale value in the range of 100-500 nm, preferably 110-450 nm, preferably 120-400 nm, preferably 140-375 nm, preferably 160-350 nm, preferably 180-325 nm, preferably 200-300 nm, preferably 210-290 nm, preferably 220-280 nm, preferably 230-270 nm. In one embodiment, the method increases the roughness root mean square value of the textured glass surface by at least 25%, preferably at least 50%, preferably at least 75%, preferably at least 100%, preferably at least 150%, preferably at least 200%, preferably at least 250%, preferably at least 300% relative to a glass surface that is not immersed, exposed, or both.

(63) As used herein, the coefficient of friction is a dimensionless scalar value which describes the ratio of the force of friction between two bodies and the force pressing them together. In general, coefficients of friction range from near zero to greater than one. In one embodiment, the textured polycarbonate surface has a coefficient of friction in the range of 0.025-0.75, preferably 0.05-0.50, preferably 0.10-0.45, preferably 0.20-0.40, preferably 0.25-0.35. In a preferred embodiment, the method of the present disclosure decreases the coefficient of friction of the textured polycarbonate glass surface relative to a treated/immersed polycarbonate glass surface and/or an untreated polycarbonate glass surface that is not exposed to the vapor phase polar aprotic solvent of the present method described herein, the coefficient of friction of the textured polycarbonate glass surface is less than the coefficient of friction of a treated/immersed polycarbonate glass surface and/or an untreated polycarbonate glass surface that is not exposed to the vapor phase polar aprotic solvent.

(64) As used herein, transmittance of the surface of a material is its effectiveness in transmitting radiant energy. It is the fraction of incident electromagnetic power that is transmitted through a sample. Internal transmittance refers to energy loss by absorption, whereas total transmittance refers to that which is due to absorption, scattering, reflection, etc. As used herein, optical light transmittance or visible transmittance refers to the amount of light in the UV-visible portion of the spectrum that passes through the material, preferably light having a wavelength of 400-800 nm, preferably 450-750 nm, preferably 500-600 nm.

(65) In a preferred embodiment, the treated glass surface has an optical light transmittance of greater than 85%, preferably greater than 86%, preferably greater than 87%, preferably greater than 88%, preferably greater than 89%, preferably greater than 90%, preferably greater than 92% and the textured glass surface has an optical light transmittance of greater than 75%, preferably greater than 76%, preferably greater than 77%, preferably greater than 78%, preferably greater than 79%, preferably greater than 80%, preferably greater than 82%, preferably greater than 84%, preferably greater than 86%, preferably greater than 88%, preferably greater than 90%. In a preferred embodiment, the textured glass surface has an optical light transmittance that is reduced by no more than 25 percentage points relative to the optical light transmittance of the polycarbonate glass surface prior to the immersing, the exposing, or both, preferably no more than 20 percentage points, preferably no more than 18 percentage points, preferably no more than 16 percentage points, preferably no more than 14 percentage points, preferably no more than 12 percentage points, preferably no more than 10 percentage points, preferably no more than 8 percentage points, preferably no more than 5 percentage points.

(66) In a preferred embodiment, the method further comprises dip coating the textured glass surface in a sol gel comprising a silane and an orthosilicate compound to form a coated textured glass surface. In a preferred embodiment the formed sol gel coating covers (in terms of % surface area) greater than 50% of the textured glass surface, preferably greater than 60%, preferably greater than 70%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 98%, preferably greater than 99/c %.

(67) As used herein, a sol gel refers to a process or a method for producing solid materials from small molecules. The process involves conversion of monomers into a colloidal solution (or sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers. One of the largest application areas of sol gels is in thin films and protective coatings which can be produced on a piece of substrate (i.e. the textured polycarbonate glass surface) by spin coating or dip coating. Generally deposition grade silanes comprise alkoxysilanes and/or their predecessors such as chlorosilane. Transformations of the alkoxysilanes during the processing proceed through a series of subsequent hydrolysis, condensation and thermal treatment steps. Exemplary silanes and their precursors include, but are not limited to, allyltrimethoxysilane, butyltrichlorosilane, ethyltrichlorosilane, isobutyl(trimethoxy)silane, [3-(diethylamino)propyl]trimethoxysilane, methyltrichlorosilane, N-propyltriethoxysilane, pentyltrichlorosilane, tetramethyl orthosilicate, tetrapropyl orthosilicate, triethoxy(octyl)silane, triethoxyphenylsilane, triethoxyvinylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, 1,1,1,3,3,3-hexamethyl disilazane (HMDS) and the like. In a preferred embodiment, the silane is 1,1,1,3,3,3-hexamethyl disilazane (HMDS). In a preferred embodiment, the organosilicon compound is an orthosilicate. Exemplary orthosilicates include, but are not limited to, tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, tetraallyl orthosilicate, tetrakis(dimethylsilyl) orthosilicate, tetraamyl orthosilicate and the like. In a preferred embodiment the organosilicaon compound is tetraethyl orthosilicate (TEOS). In a preferred embodiment the ratio of HMDS:TEOS is 0.5-5, preferably 1-4, preferably 1.5-3, preferably 1.75-2.5, or about 2.

(68) In one embodiment, the coated textured glass surface has an average water droplet contact angle of greater than 130, preferably greater than 131, preferably greater than 132, preferably greater than 133, preferably greater than 134, preferably greater than 135, preferably greater than 136, preferably greater than 137, preferably greater than 138, preferably greater than 139, preferably greater than 140, preferably greater than 145, preferably greater than 150, preferably greater than 155, preferably greater than 160. For example, the textured glass surface has an average water droplet contact angle in the range of 130-160, preferably 131-155, preferably 132-150, preferably 133-145, preferably 134-142, preferably 135-140. In one embodiment, the method increases the surface hydrophobicity as measured by an average water droplet contact angle of the coated textured glass surface by at least 10%, preferably at least 15%, preferably at least 20%, preferably at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 100% relative to a textured glass surface that is not coated (i.e. the percent increase in water droplet contact angle from the textured glass surface to the coated textured glass surface).

(69) In one embodiment, the coated textured glass surface has an average glycerol droplet contact angle in the range of 110-170, preferably 130-160, preferably 131-155, preferably 132-150, preferably 133-145, preferably 134-142, preferably 135-140. In one embodiment, the method increases the surface hydrophobicity as measured by an average glycerol droplet contact angle of the coated textured glass surface by at least by at least 10%, preferably at least 15%, preferably at least 20%, preferably at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 100% relative to a textured glass surface that is not coated. In one embodiment, the coated textured glass surface has an average diiodomethane droplet contact angle in the range of 110-170, preferably 130-160, preferably 131-155, preferably 132-150, preferably 133-145, preferably 134-142, preferably 135-140. In one embodiment, the method increases the surface hydrophobicity as measured by an average diiodomethane droplet contact angle of the textured glass surface by at least 15%, preferably at least 20%, preferably at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 100% relative to a textured glass surface that is not coated.

(70) In one embodiment, the coated textured glass surface has a roughness root mean square taken over a 5 m scale value in the range of 100-500 nm, preferably 150-475 nm, preferably 200-450 nm, preferably 250-425 nm, preferably 300-400 nm, preferably 310-390 nm, preferably 320-380 nm, preferably 325-375 nm, preferably 340-370 nm, preferably 350-368 nm. In one embodiment, the method increases the roughness root mean square value of the textured glass surface by at least 25%, preferably at least 50%, preferably at least 75%, preferably at least 100%, preferably at least 150%, preferably at least 200%, preferably at least 250%, preferably at least 300% relative to a textured glass surface that is not coated.

(71) In one embodiment, the coated textured polycarbonate surface has a coefficient of friction in the range of 0.01-0.80, preferably 0.025-0.75, preferably 0.05-0.50, preferably 0.10-0.45, preferably 0.20-0.40, preferably 0.25-0.35. In a preferred embodiment, the method of the present disclosure decreases the coefficient of friction of the textured polycarbonate glass surface relative to a textured/treated/immersed polycarbonate glass surface and/or an untreated polycarbonate glass surface that is not coated by the present method described herein, the coefficient of friction of the coated textured polycarbonate glass surface is less than the coefficient of friction of a textured/treated/immersed polycarbonate glass surface and/or an untreated polycarbonate glass surface that is not coated.

(72) In a preferred embodiment, the coated textured glass surface has an optical light transmittance of greater than 45%, preferably greater than 46%, preferably greater than 47%, preferably greater than 48%, preferably greater than 49%, preferably greater than 50%, preferably greater than 55%, preferably greater than 60%, preferably greater than 65%, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 82%, preferably greater than 85%. In a preferred embodiment, the coated textured glass surface has an optical light transmittance that is reduced by no more than 60 percentage points relative to the optical light transmittance of the textured glass surface prior to the coating, preferably no more than 50 percentage points, preferably no more than 45 percentage points, preferably no more than 40 percentage points, preferably no more than 35 percentage points, preferably no more than 30 percentage points, preferably no more than 25 percentage points, preferably no more than 20 percentage points, preferably no more than 15 percentage points, preferably no more than 10 percentage points, preferably no more than 5 percentage points.

(73) In one embodiment, the method described herein in any of its embodiments may further comprise coating the treated glass surface, the textured glass surface, and/or the coated textured glass surface with a hydrophobic layer to form a more hydrophobic and/or superhydrophobic glass surface. It is envisaged that adding one or more hydrophobic layers to an already treated/textured/coated surface as defined herein may increase the surface contact angle, and therefore the hydrophobicity of the surface. The hydrophobic layer may be in addition to or in lieu of the sol gel coating.

(74) In one embodiment, the hydrophobic layer comprises at least one selected from the group consisting of a fluorocarbon, a perfluorocarbon, a resin, a hydrophobic fatty acid and a hydrophobic self-assembled monolayer. Exemplary fluorocarbons and perfluorocarbons include, but are not limited to, i) fluoroalkanes such as carbon tetrafluoride, perfluoroocatane, perfluoro-2-methylpentane, perfluorooctanoic acid, perfluoro-1,3-dimethylcyclohexane, perfluorodecalin, hexafluoroethane, perfluoropentane, pefluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoromethyldecalin, ii) fluoroalkenes/fluoralkynes such as perfluoroisobutene, tetrafluoroethylene, hexafluoropropylene, hexafluorobutyne, iii) perfluoroaromatic compounds such as hexafluorobenzene, octafluorotoluene, and octafluoronaphthalene and iv) fluoropolymers such as polyvinylfluoride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, fluorinated ethylene-propylene, perfluropolyether, perfluoropolyoxetane, pefluoroalkoxy polymer, polyethylenetetrafluoroethylen, polyethylenechlorotrifluoroethylene, and the like.

(75) Exemplary resins and/or films include, but are not limited to, films or resins made from carbon layers or carbon sheets, phenolic resins, epoxy resins (e.g. bisphenol A and F epoxy resins, glycidylamine epoxy resin, aliphatic epoxy resin, etc.), polystyrene (PS), poly(methylmethacralate), manganese oxide polystyrene (MnO.sub.2/PS) nanocomposite, zinc oxide polystyrene (ZnO/PS) nanocomposite, precipitated calcium carbonate, carbon nanotube structures, silica nanocoating, nanopin film, and the like.

(76) The hydrophobic fatty acid that may be used to coat the treated glass surface, the textured glass surface, and/or the coated textured glass surface may be selected from the group including, but not limited to propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic and, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid, henatriacontanoic acid, dotriacontanoic acid, tritriacontanoic acid, tetratriacontanoic acid, pentatriacontanoic acid, hexatriacontanoic acid and combinations thereof.

(77) As used herein, self-assembled monolayers (SAM) refer to molecular assemblies formed spontaneously on a surface by adsorption and are essentially organized into ordered domains. In some cases the molecules that form the monolayer may not interact strongly with the substrate. In other cases the molecules may possess a head group that has a strong affinity for the substrate and may anchor the molecule to it. In one embodiment, the treated glass surface, the textured glass surface, and/or the coated textured glass surface is coated with a hydrophobic layer comprising a self-assembled monolayer. Exemplary self-assembled monolayers include, but are not limited to, (11-mercatoundecyl)tetra(ethylene glycol), [11-(methylcarbonylthio)undecyl]-tetra-(ethylene glycol), tetra(ethylene glycol) dithiol, 1-hexadecanethiol and the like.

(78) According to a second aspect, the present disclosure relates to a textured bisphenol A polycarbonate glass surface comprising a hierarchical patterned nanoporous structure comprising pores with an average diameter of 200-1000 nm, preferably 250-990 nm, preferably 300-980 nm, preferably 350-970 nm, preferably 400-950 nm, preferably 450-900 nm, preferably 500-800 nm and an average depth of 20-150 nm, preferably 30-130 nm, preferably 40-120 nm, preferably 50-100 nm, preferably 60-90 nm which has a water droplet contact angle of greater than 75, preferably greater than 76, preferably greater than 77, preferably greater than 78, preferably greater than 79, preferably greater than 80, preferably greater than 81, preferably greater than 82, preferably greater than 84, preferably greater than 86, preferably greater than 88, preferably greater than 90, preferably greater than 95, preferably greater than 100, preferably greater than 105, an optical light transmittance of greater than 75%, preferably greater than 76%, preferably greater than 77%, preferably greater than 78%, preferably greater than 79%, preferably greater than 80%, preferably greater than 82%, preferably greater than 84%, preferably greater than 86%, preferably greater than 88%, preferably greater than 90%, and a roughness root mean square value in the range of 100-500 nm, preferably 110-450 nm, preferably 120-400 nm, preferably 140-375 nm, preferably 160-350 nm, preferably 180-325 nm, preferably 200-300 nm, preferably 210-290 nm, preferably 220-280 nm, preferably 230-270 nm.

(79) According to a third aspect, the present disclosure relates to a photovoltaic or solar cell comprising the textured bisphenol A polycarbonate glass surface. In a preferred embodiment, the textured bisphenol A polycarbonate glass surface would serve as a transparent solar glass panel or array.

(80) As used herein, a solar cell or photovoltaic cell refers to an electrical device that converts the energy of light directly into electricity by the photovoltaic effect. Exemplary types of solar cells or photovoltaic cells include, but are not limited to, amorphous silicon solar cells, biohybrid solar cells, buried contact solar cells, cadmium telluride solar cells, concentrated PV solar cells, copper indium gallium selenide solar cells, dye-sensitized solar cells, gallium arsenide germanium solar cells, hybrid solar cells, luminescent solar concentrator cells, micromorph cells, monocrystalline solar cells, multi-junction solar cells, nanocrystal solar cells, organic solar cells, perovskite solar cells, photoelectrochemical cells, plasmonic solar cells, plastic solar cells, polycrystalline solar cells, polymer solar cells, quantum dot solar cells, solid-state solar cells, thin-film solar cells, and wafer solar cells.

(81) According to a fourth aspect, the present disclosure relates to a coated textured glass surface, comprising i) a bisphenol A polycarbonate glass surface with a hierarchical patterned nanoporous structure and ii) a sol gel coating layer comprising 1,1,1,3,3,3-hexamethyl disilazane (HMDS) and tetraethyl orthosilicate (TEOS), wherein the sol gel coating layer is disposed on and in continuous contact with the glass surface, wherein the hierarchical patterned nanoporous structure comprises pores with an average diameter of 200-1000 nm, preferably 250-990 nm, preferably 300-980 nm, preferably 350-970 nm, preferably 400-950 nm, preferably 450-900 nm, preferably 500-800 nm and an average depth of 20-150 nm, preferably 30-130 nm, preferably 40-120 nm, preferably 50-100 nm, preferably 60-90 nm, and wherein the coated textured glass surface has a water droplet contact angle of greater than 130, preferably greater than 131, preferably greater than 132, preferably greater than 133, preferably greater than 134, preferably greater than 135, preferably greater than 136, preferably greater than 137, preferably greater than 138, preferably greater than 139, preferably greater than 140, preferably greater than 145, preferably greater than 150, preferably greater than 155, preferably greater than 160, an optical light transmittance of greater than 45%, preferably greater than 46%, preferably greater than 47%, preferably greater than 48%, preferably greater than 49%, preferably greater than 50%, preferably greater than 55%, preferably greater than 60%, preferably greater than 65%, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 82%, preferably greater than 85%, and a roughness root mean square value in the range of 100-500 nm, 100-500 nm, preferably 150-475 nm, preferably 200-450 nm, preferably 250-425 nm, preferably 300-400 nm, preferably 310-390 nm, preferably 320-380 nm, preferably 325-375 nm, preferably 340-370 nm, preferably 350-368 nm. According to a fifth aspect, the present disclosure relates to a photovoltaic or solar cell comprising the coated textured glass surface.

(82) The examples below are intended to further illustrate methods and protocols for treating and characterizing the textured glass surfaces or coated textured glass surfaces comprising a polycarbonate of the present disclosure. Further, they are intended to illustrate assessing the properties of these hierarchical patterned nanoporous structured surfaces. They are not intended to limit the scope of the claims.

EXAMPLE 1

(83) General Materials and Methods of Characterization for Prepared Superhydrophobic Surfaces

(84) Bisphenol A polycarbonate sheets [2,2-bis(p-hydroxyphenyl) propane] of 3 mm thickness made by Juliet Company were used. Solvents used were reagent grade and acquired from Sigma-Aldrich. Dichloromethane puriss. p.a., ACS reagent reag. ISO, 99.9% (GS) (Sigma-Aldrich) was used to initiate the nanopores. Acetone solvent from Sigma-Aldrich (purity 99.5% b.p.: 56 C., MW: 58.08, and v.p.: 184 mmHg at 20 C.) was used for the vapor induced crystallization process. Tetraethoxysilane (TEOS) and 1,1,1,3,3,3-hexamethyldisilazane (HMDS) were purchased from Sigma-Aldrich and used in the sol gel method to generate a superhydrophobic coating on polycarbonate glass.

(85) Several characterization techniques were utilized in order to study the different effects of changing the experimental parameters within the study of the chemical and physical properties of the textured surfaces. Atomic force microscopy (AFM) molecular imaging (PicoSPM LE5100, Agilent Technologies) was used to scan, determine, and characterize surface topography and roughness profile in contact. Image analysis was performed using WSxM v5.0 Develop 6.2. Silicon nitride probes tips manufactured by Bruker AFM Probes Co. were used with a radius in the range of 20-60 nm and a specified force constant (k) of 0.12 N/m. Fourier-Transform Infrared (FTIR) spectroscopy (model 6700 from Thermo Electron Corporation) was utilized to carry out the identification of different functional groups that are present on the surface before and after the texturing process. A UV-Vis spectrophotometer (Lambda EZ 210 from PerkinElmer Company) was utilized to measure the transmittance of the polycarbonate sheet before and after the patterning process. A Goniometer (KYOWA DM-701) is used to determine the degree of both the hydrophilicity and the hydrophobicity of the surface by measuring the static contact angles between a deionized water droplet (of 0.4-5 L volume, preferably of 2 L volume) and the surface.

EXAMPLE 2

(86) Preparation of Textured Polycarbonate Surfaces

(87) Bisphenol A polycarbonate plates [2,2-bis(p-hydroxyphenyl) propane] of 3 mm thickness made by Juliet Company were used. The bisphenol A 2,2-bis(p-hydroxyphenyl) based polycarbonate plates were cleaned with soap and then sonicated for 15 minutes in a mixture of isopropyl alcohol and deionized water. The cleaned samples were left to dry at ambient conditions for three hours and then immersed in dichloromethane solvent for a few seconds (2 seconds) at room temperature. This is important as at longer immersions (>3 seconds) the glass will become opaque. The samples were then removed from the solvent and immediately exposed to acetone vapor for 1, 2, and 4 minutes at 33 C. In some embodiments, after removal from dichloromethane the samples are immediately immersed in water and subsequently exposed to acetone vapor. The acetone vapor may pass through a 1 cm1 cm squared outlet, for 1, 2, and 4 minutes where the liquid acetone temperature is maintained at 33 C. A 25 mL cylindrical glass is used in the setup which evolves and/or evaporates acetone in the vertical direction towards the polycarbonate surface. After exposure to the acetone vapor the polycarbonate sheet is removed, cleaned with water, and left to dry at ambient room temperature. The exposure time plays a crucial role in the polycarbonate crystallization process. Thus, polycarbonate sheets are exposed to acetone vapor for different periods of time in order to investigate the effect of time on the surface texture characteristics, such as size, density and distance of the generated spherules and gaps. Table 1 is a summary of the experimental parameters of the solid-vapor interface method of the present disclosure in the preparation of textured polycarbonate glass by immersion (2 seconds) in pure liquid CH.sub.2Cl.sub.2, and exposure to acetone vapor.

(88) TABLE-US-00001 TABLE 1 Experimental parameter of solid-vapor interface method of preparing textured polycarbonate surfaces Designation Acetone Exposure Time B1 1 minute B2 2 minutes B4 4 minutes

EXAMPLE 3

(89) Preparation of Tetraethyl Orthosilicate (TEOS) and 1,1,1,3,3,3-Hexamethyldisilazane (HMDS) Sol Gel and Coated Textured Polycarbonate Surfaces

(90) After texturing of the polycarbonate sheets, a hydrophobic and transparent TEOS/HMDS sol gel was dip coated onto the top of the polycarbonate glass textured surface. The pH value for deionized water was adjusted to 0.5 by adding 4-5 drops of HCl solution. Tetraethyl orthosilicate (TEOS) was hydrolyzed with acidic deionized water at a fixed molar ratio of TEOS:C.sub.2H.sub.5OH:H.sub.2O of 1:48:4 (pH=0.5) at 70 C. with vigorous stirring for 2 h, followed by the addition of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) at a HMDS/TEOS ratio equal to 2 in 20 parts (1 drop at a time). The sequential addition of HMDS proceeded for 3 hours, optionally under sonication, with each successive addition being placed into the sol at different positions.

(91) In some embodiments, upon the fourth or fifth addition of HMDS and the sonication of the sol, part of the sol was transformed into a transparent jelly. In this instance, the addition of HMDS is halted and the transparent jelly is retransformed into transparent sol when additional C.sub.2H.sub.5OH (C.sub.2H.sub.5OH/TEOS=24) is added over 1-2 hours. In addition to the fixed 3 hours, this period of 1-2 hours was required to break up the transparent jelly. Subsequently, HMDS continued to be added until the end of the procedure and the transparent jelly was found to no longer be present. In some embodiments, to obtain an ideal superhydrophobic sol gel, while maintaining transparency as high as possible, further C.sub.2H.sub.5OH (C.sub.2H.sub.5OH/TEOS=6) was added to the sol gel at the end of the addition of HMDS. The prepared sol gels were then aged in a refrigerator at 20 C. for 72 hours. The prepared sol gel was subsequently dip coated onto the polycarbonate glass substrates for 5 seconds. Heat treatment at 100-200 C. for 2 hours was used to repel the excess ethanol and stabilize the film.

EXAMPLE 4

(92) Atomic Force Microscopy (AFM) Studies of Polycarbonate Textured Surfaces

(93) Atomic force microscopy (AFM) scans were taken for smooth polycarbonate glass surfaces at a 20 m scale. FIG. 1 shows the 3D AFM topography image of smooth polycarbonate glass surfaces. FIG. 2 presents the 2D second order flattened topography micrograph of the smooth untreated polycarbonate surface. FIG. 3 shows the 2D AFM line profile of the smooth untreated polycarbonate surfaces. FIG. 4 shows the 3D AFM topography image of untreated polycarbonate glass after ultrasonication for 15 minutes in isopropyl alcohol on a 1 m scale demonstrating a smooth surface with very low surface roughness, as can be noted from the z-scale (8.1 nm). In all instances, the untreated surface appears slightly curved without any kind of texture on the surface of the polycarbonate sheet.

(94) AFM scans were carried out on polycarbonate surfaces immersed in dichloromethane (CH.sub.2Cl.sub.2) for 2 seconds up to 5 seconds. FIG. 5 shows the 3D AFM topography image of polycarbonate glass after immersing in dichloromethane for 2 seconds. It can be noted that the surface shows a nonuniform nanoporous morphology with unaffected areas in between. FIG. 6 shows a line profile taken through FIG. 5 across pores allowing one to obtain quantitative information of the topographical details. The line profile demonstrates main pores with depth in the range of 10-12 nm and maximum surface width of 2 m. The distance between the pores is in the range of 4 m. The line profile also shows the initiation of infant pores with smaller widths of 183-600 nm and shallower depths that do not exceed 5 nm. FIG. 7 shows the 3D AFM micrograph at 20 m scale of polycarbonate glass after immersing in dichloromethane for 2 seconds. FIG. 8 shows the 2D AFM micrograph at 20 m scale of polycarbonate glass after immersing in dichloromethane for 2 seconds. FIG. 9 shows the 3D AFM topography image of polycarbonate glass after immersing in dichloromethane for 5 seconds. It is noted that beyond 2 seconds large micropores begin to develop as shown in the AFM image and likely significantly decreasing the polycarbonate transmittance.

(95) FIG. 10, FIG. 11A, and FIG. 11B show the 3D topography AFM image of the polycarbonate after immersion for 2 seconds in dichloromethane and exposure for 1 minute to acetone vapors at 10 m scale, 20 m scale, and 5 m scale respectively. FIG. 12 is the 2D topography AFM micrograph at 20 m scale. FIG. 13 is the line profile texture micrograph taken through FIG. 12. FIG. 14 is the 2D topography AFM micrograph at 5 m scale. FIG. 15 is the line profile texture micrograph taken through FIG. 14. At this first stage (1 minute exposure) the spherules are still small and have not expanded vertically significantly yet. The AFM data at the 20 m scale scan exhibits a uniformly textured surface comprising pores of sizes ranging from 370-971 nm in diameter and a maximum depth of 103 nm. Upon magnification to the 5 m scale, the pores appear patterned with a hill-like structure as the surface between them.

(96) However, after 2 minutes of exposure complete micrometer size spherules are observed in the 3D AFM topographic image. The surface morphology further reveals the presence of areas of high posts follow by relatively unaffected void areas which close up after the 2 minute exposure limit. Voids between the spherules may be necessary to allow the surface to maintain sufficient optical transmittance.

(97) Several AFM images are scanned at different areas on the textured polycarbonate glass surface after 2 seconds immersed in dichloromethane and 4 minute exposure to acetone vapor. FIG. 16A, and FIG. 16B show the 3D topography AFM image of the polycarbonate after immersion for 2 seconds in dichloromethane and exposure for 4 minutes to acetone vapors at 20 m scale and 5 m scale respectively. FIG. 17 is the 2D topography AFM micrograph at 20 m scale. FIG. 18 is the line profile texture micrograph taken through FIG. 17. FIG. 19 is the 2D topography AFM micrograph at 5 m scale. FIG. 20 is the line profile texture micrograph taken through FIG. 19. Increasing exposure time of the polycarbonate glass for the acetone vapors will cause a further increase in the size of the spherules, and hence reduce the path for light transmittance. It can be noticed that the spherules are closing up while no significant change in spherule height is observed as compared to the 2 minute exposure. The micrographs show clearly that there is texture over the surface of the polycarbonate after chemical treatment. In the 20 m micrograph, complete coverage of the surface with large spherules of 13 m in width and 1.4 m in height are observed with fine nanaostructures on top as noted in the line profile (FIG. 18). The spherules' surface is textured and covered with fibers. At the 5 m scale the micrograph reveals the fibers having a diameter of 459 nm and a height of 157 nm.

EXAMPLE 5

(98) Light Transmittance of Polycarbonate Textured Surfaces

(99) Polycarbonate sheets as received and those treated are scanned between 400 nm to 800 nm (visible region) by UV-Vis to measure its transmittance. FIG. 21 shows all the transmittance curves for the four treated samples. The descending arrangement of the samples according to exposure time to the acetone vapor is B.sub.4>B.sub.2>B.sub.1>untreated sample. The descending arrangement of the transmittance values for the samples is untreated sample>B.sub.1>B.sub.2>B.sub.4. It can be inferred that the transmittance value is inversely proportional to the exposure time to acetone vapor. FIG. 22 depicts that by increasing the exposure time to the acetone vapor, the transmittance of the patterned surface decreases. The average transmittance of the untreated polycarbonate glass in the visible region was found to be 90.20%. The optical transmittance was 80% for the 1 minute exposure to acetone vapors versus 26% for the 2 minute exposure to acetone vapors. After 4 minutes of treatment with acetone vapors the optical transmittance was reduced to just a few percent.

EXAMPLE 6

(100) Contact Angle Studies of Textured Polycarbonate Surfaces

(101) The contact angle of the untreated polycarbonate surface is measured by dropping a deionized water droplet over the surface and is measured using a goniometer. Different areas of the surface were taken into consideration during the measurements. FIG. 23 shows that it was found that the average contact angle is 77.6; indicating the slight hydrophilicity of the smooth polycarbonate surface. FIG. 24 shows that the contact angle after immersion of polycarbonate glass in dichloromethane the resulting contact angle was 91.8 compared to 77.6 for the untreated polycarbonate glass. Table 2 presents the determined contact angles for prepared treated samples.

(102) TABLE-US-00002 TABLE 2 Average contact angles of different prepared textured polycarbonate surface samples Acetone Contact Average Exposure Angle Contact Sample Time (min) (deg.) Angle (deg.) B.sub.1 (area 1) 1 80.3 79 B.sub.1 (area 2) 77.5 B.sub.1 (area 3) 79.2 B.sub.2 (area 1) 2 82.1 79.93 B.sub.2 (area 2) 79.3 B.sub.2 (area 3) 78.4 B.sub.3 (area 1) 4 100.9 102.8 B.sub.3 (area 2) 103.2 B.sub.3 (area 3) 104.4

(103) FIG. 25, FIG. 26, and FIG. 27 show the measurement of the contact angle for textured polycarbonate samples after immersion in dichloromethane for 2 seconds and subsequent exposure to pure acetone vapors for 1 minute, 2 minutes, and 4 minutes, respectively. From the above data, it can be extracted that by increasing the treatment time of the polycarbonate sample with the acetone vapor, the contact angle increases. Secondly, the average contact angle value increase slightly from 1 minute (80.3) to 2 minute (82.1) treatments with acetone vapor and then increased rapidly for the 4 minute treatment (>98).

EXAMPLE 7

(104) Fourier-Transform Infrared (FT-IR) Analysis and Roughness Root Mean Square (RMS) Values of Polycarbonate Textured Surfaces

(105) Fourier-transform Infrared (FT-IR) technique is used for the identification of the presence of chemical groups, functional, side and terminal groups. FT-IR technique is used to study the chemical structure of the polycarbonate surface before and after the treatment process. In addition, the technique gives an indication on the degree of crystallization of the surface after the treatment process through the peaks intensities values. The amorphous form of the polymer gives a relatively higher degree of freedom to the polymers tail motion. This permits the absorption of larger amounts of energy, and consequently, the performance of stronger vibrations, in the case of molecules or groups that have a dipole moment (asymmetric chemical structure) [Liang, G. G., et al., Diallyl orthophthalate as a reactive plasticizer for polycarbonate. Part 1: Uncured system. European Polymer Journal, 2008. 44(2): p. 366-375; and Atkins, P., Paula J. Atkins' physical chemistry. 2012, Oxford, N.Y.: Oxford University Presseach incorporated herein by reference in its entirety].

(106) FT-IR was carried out on all textured surfaces. FIG. 28 presents the FT-IR spectra of all the textured surfaces and the untreated polycarbonate surface. The analysis focuses on the wavelength at which the peak of the carbonyl, CO, stretching mode appears. Before the exposure to acetone, the peak of the carbonyl stretching mode appears at 1766 cm.sup.1 (1766.8 cm.sup.1 for B.sub.1, 1762.9 cm.sup.1 for B.sub.2, and 1767.1 cm.sup.1 for B.sub.4. The spectra are identical except for the decrease of the carbonyl peak intensities around 1766 cm.sup.1 indicating the phase transformation of the polymer from the amorphous phase, which allows a higher degree of freedom to the chains motion and bonds vibrations, to the crystalline phase, in which the molecules are tightly packed and consequently the vibrations and motions are restricted. Further, it indicates that the acetone interaction with the polycarbonate is a physical process as there is no new peak that emerges after the treatment process [de Oliveira, F. L. O., et al., Study on bisphenol-A polycarbonates samples crystallized by acetone vapor induction. Polymer bulletin, 2011. 67(6): p. 1045-1057; and Liu, C. K., C. T. Hu, and S. Lee, Effect of compression and thickness on acetone transport in polycarbonate. Polymer Engineering & Science, 2005. 45(5): p. 687-693; and Dybal, J., et al., Ordered structures in polycarbonate studied by infrared and Raman spectroscopy, wide-angle X-ray scattering, and differential scanning calorimetry. Macromolecules, 1998. 31(19): p. 6611-6619; and Paragkumar N, T., D. Edith, and J.-L. Six, Surface characteristics of PLA and PLGA films. Applied Surface Science, 2006. 253(5): p. 2758-2764each incorporated herein by reference in its entirety].

(107) Table 3 exhibits the roughness root mean square (RMS) values taken at a 5 m scale for the prepared textured polycarbonate samples. The data shows that the RMS values calculated at the 5 m scale illustrate that the sample treated with acetone vapor for 4 minutes has the highest surface roughness. By increasing the exposure time with acetone vapor, the polycarbonate surface gets more crystallized, pore depths increase, the compositions of the air-pockets begins, and the RMS values inversely increase with the decrease in the transmittance.

(108) TABLE-US-00003 TABLE 3 Roughness root mean square (RMS) values of different prepared textured polycarbonate surface samples RMS values, nm Scale Smooth (m) Polycarbonate B.sub.1 B.sub.2 B.sub.4 5 112 213 260 639.2 Avg. T % 90.20 81.33 23.67 0.60

EXAMPLE 8

(109) Effect of Sol Gel Coating on Polycarbonate Textured Surfaces

(110) Sol gel coating is well known to improve the surface properties of many different materials. Surface modification by the deposition of a transparent hydrophobic material on the rough surface to increase hydrophobicity has shown promise. In the case of photovoltaic cell applications the interest is in developing a superhydrophobic coating while maintaining high optical transmittance. FIG. 29 is the equation for the hydrolysis of tetraethyl orthosilicate (TEOS). FIG. 30 is the equation for the reaction between a SiOH functionality and 1,1,1,3,3,3-hexamethyldisilazane (HMDS) to form the hydrophobic bond. With this aim, textured polycarbonate samples formed by treatment with dichloromethane and acetone vapor for 1 minute (B.sub.1) and 2 minutes (B.sub.2) were dip coated in a TEOS/HMDS sol gel.

(111) Table 4 exhibits the effect of a sol gel coating upon the contact angles of the treated polycarbonates samples. FIG. 31 and FIG. 35 show the measurement of the contact angle for textured polycarbonate samples after immersion in dichloromethane for 2 seconds, subsequent exposure to pure acetone vapors for 1 minute and 2 minutes followed by coating with a TEOS/HMDS sol gel respectively. FIG. 32 shows the 2D topography AFM image of the polycarbonate after immersion for 2 seconds in dichloromethane, exposure for 1 minute to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale. FIG. 33 is the 3D topography AFM micrograph at 5 m scale. FIG. 34 is the line profile texture micrograph taken through FIG. 33. FIG. 36 shows the 2D topography AFM image of the polycarbonate after immersion for 2 seconds in dichloromethane, exposure for 2 minutes to acetone vapors and coating with a TEOS/HMDS sol gel at 5 m scale. FIG. 37 is the 3D topography AFM micrograph at 5 m scale. FIG. 38 is the line profile texture micrograph taken through FIG. 37.

(112) TABLE-US-00004 TABLE 4 Experimental parameter of solid-vapor interface method of preparing textured polycarbonate surfaces Average Average Contact Angle Contact Angle Sample Before Coating After Coating B.sub.1 79 135.8 B.sub.2 79.9 133.1

(113) The contact angles of the uncoated textured polycarbonate samples are increased significantly upon applying the hydrophobic TEOS/HMDS sol gel coating (135.8 for the B.sub.1 coated sample). Furthermore, AFM micrographs show texturing on the surface and a tremendous increase in the RMS value (179 nm) compared to counterpart uncoated polycarbonate B samples leading to an enhancement of hydrophobicity and a minor reduction in transmittance. The optical transmittance of the dichloromethane/acetone vapor/sol gel coated polycarbonate glass sample treated with acetone for 1 minute (B.sub.1) was found to be approximately 40-70% (FIG. 39). Similarly for the B.sub.2 sample the RMS value rose to 364 nm and lead to a high contact angle of 133.1 and only a slight reduction in transmittance from 23.67% to 16.85%. In conclusion, a facile two step method has been demonstrated by immersing polycarbonate materials in dichloromethane for 2 s followed by exposure to acetone vapor at 33 C. for 1 minute and then sol gel coating. This resulted in a hierarchical superhydrophobic TEOS/HMDS gel coated surface having a contact angle of 135.8 and a transmittance of 50-70%. Hence, proper optimization of the spherules growth, dimensions, and interspherule distances and then sol gel coating resulted in a significantly hydrophobic polycarbonate surface. This approach is promising in developing future superhydrophobic, economic, and less technologically demanding surfaces for application as photovoltaic panels.

(114) Thus, the foregoing discussion discloses and describes merely exemplary embodiments of the present invention. As will be understood by those skilled in the art, the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Accordingly, the disclosure of the present invention is intended to be illustrative, but not limiting of the scope of the invention, as well as other claims. The disclosure, including any readily discernible variants of the teachings herein, defines, in part, the scope of the foregoing claim terminology such that no inventive subject matter is dedicated to the public.