RETROFITTABLE FLEXIBLE FABRIC LINERS WITH SURFACE-FUNCTIONALIZED ELECTROLESS NICKEL COATINGS FOR MIDSTREAM TRANSPORTATION OF BITUMEN

Abstract

Omniphobic compositions and methods of fabricating the same are provided. An omniphobic (or superomniphobic) coating can be fabricated on a fabric (e.g., cotton fabric) substrate. The multiscale textured surface can be achieved using a polymer (e.g., polytetrafluoroethylene (PTFE)) electroless nickel coating, and the surface energy can be further reduced with the binding of a fluorinated monolayer. Once rendered repellant to both water and oil, the fabric substrates retain their repellency even after being contorted.

Claims

1. A method of fabricating an omniphobic composition, the method comprising: performing a first surface functionalization on a substrate using a first moiety; and after performing the first surface functionalization, performing electroless nickel deposition together with a texturization component on the substrate, wherein the omniphobic composition is hydrophobic and oleophobic.

2. The method according to claim 1, further comprising, after performing the first surface functionalization and before performing the electroless nickel deposition, performing a second surface functionalization on the substrate using a second moiety different from the first moiety.

3. The method according to claim 2, wherein the second moiety is PdCl.sub.2.

4. The method according to claim 1, further comprising, after performing the electroless nickel deposition, performing a third surface functionalization using a third moiety different from the first moiety and the second moiety, wherein the third moiety is a fluorinated monolayer.

5. The method according to claim 4, wherein the third moiety is 1H, 1H,2H,2H-perfluorooctanephosphonic acid (PFOPA).

6. The method according to claim 4, wherein the third surface functionalization is performed for at least 10 hours.

7. The method according to claim 1, wherein the texturization component is polytetrafluoroethylene (PTFE).

8. The method according to claim 1, wherein the texturization component comprises beads of a polymer.

9. The method according to claim 1, wherein the performing of the electroless nickel deposition comprises using a nickel alloy, and wherein the nickel alloy is a nickel phosphorous alloy.

10. The method according to claim 1, wherein the first moiety is 3-aminopropyltrimethoxysilane (APTMS).

11. The method according to claim 1, wherein the substrate is a fabric substrate.

12. The method according to claim 1, wherein the electroless nickel deposition is performed for at least 30 seconds.

13. The method according to claim 1, wherein a coating formed by the electroless nickel deposition is disposed directly on the substrate.

14. An omniphobic composition, comprising: a substrate; and an electroless nickel coating together with a texturization component disposed on the substrate, wherein the omniphobic composition is hydrophobic and oleophobic.

15. The omniphobic composition according to claim 14, wherein the electroless nickel coating is surface functionalized with a fluorinated monolayer.

16. The omniphobic composition according to claim 15, wherein the fluorinated monolayer is 1H,1H,2H,2H-perfluorooctanephosphonic acid (PFOPA).

17. The omniphobic composition according to claim 14, wherein the texturization component is polytetrafluoroethylene (PTFE), and wherein the substrate is surface functionalized with at least one of 3-aminopropyltrimethoxysilane (APTMS) and PdCl.sub.2.

18. The omniphobic composition according to claim 14, wherein the electroless nickel coating comprises a nickel alloy, and wherein the nickel alloy is a nickel phosphorous alloy.

19. The omniphobic composition according to claim 14, wherein the substrate is a fabric substrate.

20. The omniphobic composition according to claim 14, wherein the omniphobic composition is flexible and remains hydrophobic and oleophobic after being contorted, and wherein the omniphobic composition remains hydrophobic and oleophobic up to a temperature of at least 220 C.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0007] FIG. 1 shows a schematic illustration of a method for fabricating omniphobic fabric substrates, according to an embodiment of the subject invention. The method can include surface activation using 3-aminopropyltrimethoxysilane (APTMS) and PdCl.sub.2, followed by electroless co-deposition of nickel and polytetrafluoroethylene (PTFE) beads, and further surface functionalization of the nickel coating with perfluorooctanephoshonic acid (PFOPA).

[0008] FIG. 2A shows a scanning electron microscope (SEM) image of bare cotton fabric. The scale bar is 1 millimeter (mm).

[0009] FIG. 2B shows an SEM image of bare cotton fabric. The scale bar is 500 micrometers (m).

[0010] FIG. 2C shows an SEM image of bare cotton fabric. The scale bar is 100 m.

[0011] FIG. 2D shows an SEM image of a PTFE electroless nickel coating after 1-minute of deposition. The scale bar is 500 m.

[0012] FIG. 2E shows an SEM image of a PTFE electroless nickel coating after 1-minute of deposition. The scale bar is 30 m.

[0013] FIG. 2F shows an SEM image of a PTFE electroless nickel coating after 1-minute of deposition. The scale bar is 1 m.

[0014] FIG. 2G shows an energy dispersive X-ray spectroscopy (EDX) graph of Ni K map for a PTFE electroless nickel coating after 1-minute of deposition. The scale bar is 500 m.

[0015] FIG. 2H shows an EDX graph of P K map for a PTFE electroless nickel coating after 1-minute of deposition. The scale bar is 500 m.

[0016] FIG. 2I shows an EDX graph of F K map for a PTFE electroless nickel coating after 1-minute of deposition. The scale bar is 500 m.

[0017] FIG. 2J shows an EDX graph of Ni K map for a PTFE electroless nickel coating (after 1-minute of deposition) functionalized with 27 millimolar (mM) PFOPA for 24 hours. The scale bar is 500 m.

[0018] FIG. 2K shows an EDX graph of P K map for a PTFE electroless nickel coating (after 1-minute of deposition) functionalized with 27 mM PFOPA for 24 hours. The scale bar is 500 m.

[0019] FIG. 2L shows an EDX graph of F K map for a PTFE electroless nickel coating (after 1-minute of deposition) functionalized with 27 mM PFOPA for 24 hours. The scale bar is 500 m.

[0020] FIG. 3A shows a plot of intensity (in arbitrary units (a.u.)) versus 2 (in degrees, with =0.15418 nanometers (nm)), showing an XRD plot of cotton fabric (the (black) curve with the lower intensity values) and a fabric with PTFE electroless nickel (after 1-minute of deposition) functionalized with 27 mM PFOPA for 24 hours (the (blue) curve with the higher intensity values).

[0021] FIG. 3B shows a plot of absorbance (in a.u.) versus wavenumber (in per centimeter (cm1)), showing Fourier-transform infrared (FTIR) spectroscopy of cotton fabric (the (black) curve with the lowest absorbance values), cotton fabric with PTFE electroless nickel after 1-minute of deposition (the (red) curve with the second-lowest absorbance values), and fully functionalized fabric (i.e, cotton fabric with PTFE electroless nickel (after 1-minute of deposition) functionalized with 27 mM PFOPA for 24 hours; the (blue) curve with the highest absorbance values).

[0022] FIG. 3C shows a plot of weight percentage (in %) versus temperature (in C.) and derivative of the weight percentage (in %/ C.) versus temperature (in C.), showing a thermogravimetric analysis (TGA) for fully functionalized fabric (i.e, cotton fabric with PTFE electroless nickel (after 1-minute of deposition) functionalized with 27 mM PFOPA for 24 hours). The curve with the highest value at a temperature of 0 C. is for the weight percentage, and the curve with the lowest value at a temperature of 0 C. is for the derivative of the weight percentage.

[0023] FIG. 3D shows a plot of viscosity (in centipoise (cP)) versus temperature (in C.) for heavy oil used to measure oleophobicity at elevated temperatures.

[0024] FIG. 4A shows a series of timelapse images (from 0 seconds(s) to 0.27 s) of a champion formulation with a PTFE electroless nickel (after 1-minute of deposition) coating functionalized with 27 mM PFOPA for 24 hours, showing the rapid removal of water.

[0025] FIG. 4B shows a series of timelapse images (from 0 s to 4.56 s) of the champion formulation with a PTFE electroless nickel (after 1-minute of deposition) coating functionalized with 27 mM PFOPA for 24 hours, showing the rapid removal of heavy oil where both the heavy oil and the substrate were at a temperature of 150 C.

[0026] FIG. 5 shows an illustration of fabric and oil. The fabric that can be used with embodiments of the subject invention can be, for example, cotton fabric of the same type that may be found in shirts or other common items of clothing. After activation, deposition, and/or functionalization, the fabric can repel the oil.

[0027] FIG. 6A shows an SEM image of A36 low-alloy steel. The scale bar is 20 m.

[0028] FIG. 6B shows an SEM image of an electroless nickel coating on low-alloy steel (coating thickness of about 12 m). The scale bar is 100 m.

[0029] 20 FIG. 6C shows an SEM image of a PTFE electroless nickel coating on low-alloy steel (coating thickness of about 12 m). The scale bar is 5 m.

[0030] FIG. 7A shows a plot of absorbance (in a.u.) versus wavenumber (in cm.sup.1), showing FTIR spectroscopy for cotton fabric and for the cotton fabric after subsequent steps for PTFE electroless nickel deposition and functionalization. The (black) curve with the lowest absorbance values is for the cotton fabric; the (purple) fabric with the second-lowest absorbance values is for the cotton fabric after activation with APTMS; the (orange) curve with the second-highest absorbance values is for the cotton fabric after activation with APTMS and PdCl.sub.2; and the (red) curve with the highest absorbance values is for the cotton fabric with the electroless nickel coating.

[0031] 30 FIG. 7B shows a plot of absorbance (in a.u.) versus wavenumber (in cm.sup.1), showing FTIR spectroscopy for cotton fabric and for the cotton fabric after subsequent steps for PTFE electroless nickel deposition and functionalization. The (black) curve with the lowest absorbance values is for the cotton fabric; the (red) fabric with the second-lowest absorbance values is for the cotton fabric with the electroless nickel coating; the (blue) curve with the second-highest absorbance values is for the cotton fabric after activation with the electroless nickel coating functionalized with PFOPA; and the (green) curve with the highest absorbance values is for PFOPA.

[0032] FIG. 7C shows a plot of intensity (in a.u)) versus 2 (in degrees, with =0.15418 nm), showing an XRD plot of cotton fabric and for the cotton fabric after subsequent steps for PTFE electroless nickel deposition and functionalization. The (black) curve with the lowest intensity values is for the cotton fabric; the (purple) fabric with the second-lowest intensity values is for the cotton fabric after activation with APTMS; the (orange) curve with the third-lowest intensity values is for the cotton fabric after activation with APTMS and PdCl2; the (red) curve with the second-highest intensity values is for the cotton fabric with the electroless nickel coating; and the (blue) curve with the highest intensity values is for the cotton fabric after activation with the electroless nickel coating functionalized with PFOPA.

[0033] FIG. 8A shows a plot of weight percentage (in %) versus temperature (in C.) and derivative of the weight percentage (in %/ C.) versus temperature (in C.), showing a TGA for bare cotton fabric. The curve with the highest value at a temperature of 0 C. is for the weight percentage, and the curve with the lowest value at a temperature of 0 C. is for the derivative of the weight percentage.

[0034] FIG. 8B shows a plot of weight percentage (in %) versus temperature (in C.) and derivative of the weight percentage (in %/ C.) versus temperature (in C.), showing a TGA plot for cotton fabric with PTFE electroless nickel coating (after 1-minute of deposition). The curve with the highest value at a temperature of 0 C. is for the weight percentage, and the curve with the lowest value at a temperature of 0 C. is for the derivative of the weight percentage.

[0035] FIG. 9 shows a plot of viscosity (in cP) versus temperature (in C.) for two types of crude oil. The (purple) curve with the lower viscosity values is for C. Bitumen; and the (pink) curve with the higher viscosity values is for P. Bitumen.

[0036] FIG. 10 shows a table of contact angles of treated cotton fabric substrates with various thicknesses of PTFE electroless nickel deposited with water and heavy oil.

[0037] FIG. 11 shows a plot of thicknesses of PTFE electroless nickel coatings applied at various length of times.

[0038] FIG. 12 shows a table of wettability of functionalized fabric coatings with heavy oil.

[0039] FIG. 13 shows a workflow for integrating an electroless nickel composite coating onto cotton fabric, according to an embodiment of the subject invention. Electroless nickel electrodeposition embedding PTFE beads yields a conformal surface coating on fibers of a woven cotton fabric. The nickel composite coating can further be functionalized with PFOPA to imbue oleophobic properties.

[0040] FIGS. 14A-14O show the surface texturization of electroless nickel PTFE (EN-PTFE) coated cotton fabrics with PFOPA functionalization. FIGS. 14A-14C show SEM images of different scales of texturization of fibers of a woven cotton fabric after 1 minute of EN-PTFE coating. The scale bars for FIGS. 14A-14C are 500 m, 50 m, and 10 m, respectively. FIGS. 14D-14F shows energy-dispersive X-ray spectroscopy (EDS) maps, corresponding to FIGS. 14A-14C, respectively, where purple represents phosphorus, blue represents nickel, and green color represents fluorine. FIGS. 14G-14I show SEM images illustrating how complex PTFE texturization can arise from integration of PTFE beads along fibers. The scale bars for FIGS. 14G-14I are 50 m, 50 m, and 10 m, respectively. FIGS. 14J-14L are higher magnification SEM images of the beads on the fibers. The scale bar is 10 m for each of FIGS. 14J-14L. FIG. 14M shows an SEM image (scale bar of 50 m) depicting dense PTFE beads discernible for thicker 10 minute EN-PTFE coatings (with PFOPA functionalization), as corroborated by the EDS map in FIG. 22D. FIGS. 14N and 14O show SEM images of texturizing features after 45 minutes of EN-PTFE coating and PFOPA functionalization. The scale bars for FIGS. 14N and 14O are 50 m and 10 m, respectively.

[0041] FIG. 15A shows a plot of thickness (in m) versus coating time (in minutes), showing evolution of EN-PTFE coating thickness as a function of electroless deposition reaction time. The curve with the higher thickness values is for thread thickness, and the other curve is for coating thickness.

[0042] FIG. 15B shows a plot of weight (in %; left vertical axis) and derivative weight (in % / C.; right vertical axis) versus temperature (in C.), showing a thermogravimetric analysis of EN-PTFE PFOPA functionalized coatings deposited onto cotton fabrics for 10 minutes.

[0043] FIG. 15C shows a plot of stress (in megapascal (MPa)) versus strain (in %), showing representative stress-strain curves acquired for bare cotton and EN-PTFE-coated samples at 1 minute, 10 minutes, and 60 minutes of electroless deposition time. The curve with the highest stress value at a strain of 17% is for 10 minutes of EN-PTFE; the curve with the second-highest stress value at a strain of 17% is for 60 minutes of EN-PTFE; the curve with the second-lowest stress value at a astrain of 17% is for 1 minute of EN-PTFE; and the curve with the lowest stress value at a astrain of 17% is for cotton.

[0044] FIG. 15D shows a bar chart of break force (in kilonewtons (kN); left vertical axis) and break strain (in %; right vertical axis) versus coating time (in minutes (min)), showing measured break force and break strain of bare cotton and EN-PTFE-coated cotton fabric samples after 1 minute, 10 minutes, and 60 minutes of electroless deposition time. All error bars correspond to standard deviations from measurements. At each coating time, the left bar is for break force and the right bar is for break strain.

[0045] FIG. 16A shows a plot of transmittance versus wavenumber (in centimeters.sup.1 (cm.sup.1)), showing Fourier transform infrared spectroscopy (FTIR) transmission spectra before and after EN-PTFE deposition and after PFOPA functionalization. An FTIR spectrum acquired for PFOPA is plotted alongside for comparison. The curve with the highest transmittance values is for PFOPA; the curve with the second-highest transmittance values is for 10 minutes EN-PTFE PFOPA; the curve with the second-lowest transmittance values is for 10 minutes EN-PTFE; and the curve with the lowest transmittance values is for cotton.

[0046] FIG. 16B shows a plot of transmittance versus wavenumber (in cm.sup.1), showing the evolution of FTIR transmission spectra as a function of EN-PTFE deposition time. The curve with the lowest transmittance values is for cotton, and then the curves have higher transmittance values for higher deposition time (i.e, the curve with the second-lowest transmittance values is for 1 minute EN-PTFE, the curve with the third-lowest transmittance values is for 2 minutes EN-PTFE, etc.).

[0047] FIG. 16C shows a plot of intensity (in counts per second (cps)) versus binding energy (in electron Volts (eV)), showing core-level carbon Is X-ray photoelectron spectroscopy (XPS) spectrum obtained for a cotton substrate coated with EN-PTFE for 10 min and subsequently functionalized with PFOPA.

[0048] FIG. 16D shows a plot of intensity (in cp)) versus binding energy (in eV), showing (D) Core-level Ni 2p spectrum obtained for the same sample from FIG. 16C.

[0049] FIGS. 17A-17P show wettability as evaluated by contact angle measurements, including digital photographs of water and bitumen droplets on a cotton fabric substrate under blacklight with and without nickel coating and PFOPA functionalization. FIGS. 17A-17H show water contact angles, and FIGS. 17I-17P show bitumen contact angles. FIGS. 17A-17D and FIGS. 17I-17L show unfunctionalized coatings, and FIGS. 17E-17H and FIGS. 17M-17P show PFOPA-functionalized coatings. The columns from left to right show the bare cotton fabric substate, EN-PTFE coatings deposited for 1 min, EN-PTFE coatings deposited for 10 min, and EN-PTFE coatings deposited for 60 min.

[0050] FIGS. 18A-18I show wettability as evaluated by dynamic contact angle measurements, including digital images of water droplets dispensed and retracted on uncoated and coated cotton fabric substrates under blacklight. FIGS. 18A-18C show dispensation of a water droplet onto a bare cotton fabric and ensuing wetting of the substrate. FIGS. 18D-18F show dispensation of a water droplet onto a cotton fabric directly functionalized with PFOPA but without a EN-PTFE coating, which results in delayed but eventual wetting. FIGS. 18G-18I show dispensation of a water droplet onto a EN-PTFE-coated fabric with an electroless deposition time of 10 min subsequently functionalized with PFOPA; the substrate strongly repels water droplets, which are retracted into the dispenser. In each case, the right column shows advancing contact angles, the middle column shows receding contact angles, and the left column shows the wetting after the test. Scale bars represent 1 mm.

[0051] FIGS. 19A-19H show the examination of bulk bitumen wettability, including still digital images contrasting the wettability of EN-PTFE-coated coated fabric subsequently functionalized with PFOPA (FIGS. 19A, 19B, 19E, and 19F) and bare cotton (FIGS. 19C, 19D, 19G, and 19H) towards bitumen. FIGS. 19A and 19B show heavy crude oil poured on EN-PTFE-coated fabric subsequently functionalized with PFOPA. FIGS. 19C and 19D show heavy crude oil poured onto a bare cotton fabric. FIGS. 19E and 19F show EN-PTFE-coated fabric subsequently functionalized with PFOPA being immersed in heavy crude oil. FIGS. 19G and 19H show bare cotton fabric being immersed in heavy crude oil.

[0052] FIGS. 20A-20C show SEM images of EN-PTFE coatings on flat steel substrates. FIG. 20A shows the surface of A36 low-alloy steel; the scale bar is 20 m. FIG. 20B shows the low alloy steel substrate after deposition of (about 12 m thick) electroless nickel/phosphorus composite coating; the scale bar is 100 m. FIG. 20C shows the surface of the low alloy steel substrate after deposition of (about 12 m thick) electroless nickel/phosphorus composite coating embedding PTFE beads; the scale bar is 5 m.

[0053] FIGS. 21A-21C show SEM images of uncoated cotton substrates displaying intricate woven patterns. The scale bars for FIGS. 21A-21C are 500 m, 50 m, and 10 m, respectively.

[0054] FIGS. 22A-22D show EDS maps of coated substrates (i.e, SEM images of EN-PTFE coated fabric functionalized with PFOPA with EDS mapping, where purple corresponds to phosphorus, blue corresponds to nickel, and green corresponds to fluorine). FIGS. 22A and 22B show the case where EN-PTFE coating was deposited on woven cotton for 1 min; the scale bars for FIGS. 22A and 22B are 50 m and 10 m, respectively. FIG. 22C shows the case where the EN-PTFE coating was deposited on woven cotton for 10 min; an agglomeration of PTFE beads is observed next to a nickel-alloy-coated fiber. The scale bar for FIG. 22C is 10 m. FIG. 22D shows the case where the EN-PTFE coating was deposited on woven cotton for 45 min. The scale bar for FIG. 22D is 10 m.

[0055] FIGS. 23A-23C show plots of intensity (in counts) versus binding energy (in kilo-electron Volts (keV)), showing labeled EDS plots corresponding to EDS maps shown in FIGS. 14D-14F, respectively.

[0056] FIGS. 24A-24C show plots of intensity (in counts) versus binding energy (in keV), showing labeled EDS spectra corresponding to the EDS maps shown in FIGS. 22A-22D, respectively.

[0057] FIG. 25 shows a plot of intensity (in cps) versus binding energy (in eV), showing the core-level fluorine 1s XPS spectra of EN-PTFE-coated cotton fabric with PFOPA functionalization.

[0058] FIG. 26 shows a plot of viscosity (in centipoise (cP)) versus temperature (in C.), showing the viscosity profile for heavy crude oil used as a probe liquid.

[0059] FIGS. 27A and 27B show images of an experimental setup for a 45-day bitumen breakthrough test. Cotton fabric with EN-PTFE coating and PFOPA functionalization was suspended in a boat shape filled with bitumen and held at 175 C. No bitumen was observed to permeate the fabric over the test period.

[0060] FIG. 28 shows a table of characterization of wettability, including water, heavy oil (Puma Energy), and sweet light oil static contact angles measured for different thicknesses of EN-PTFE films with surface functionalization with PFOPA (values measured prior to PFOPA surface functionalization are listed in the table in FIG. 30). Dynamic water contact angles (advancing, receding, hysteresis) are also shown. The rightmost two columns list water roll-off angles. Deposition times from 1 min to 60 min noted in the first column correspond to EN-PTFE thin film thicknesses from about 2 m to about 14 m. Values reported are the mean of at least 3 measurements and error bars represent standard deviation. Dynamic and hysteresis values are advancing angles minus receding angles and thus errors reflect standard deviations in measurement of initial angles.

[0061] FIG. 29 shows a table of p-values from t-tests comparing the breaking force and elongation at maximum force of PTFE electroless nickel-coated samples (deposited for 1 min, 10 min, and 60 min) on bare cotton fabric.

[0062] FIG. 30 shows a table of characterization of wettability, including water, heavy oil, and sweet light oil static contact angles measured for different thicknesses of EN-PTFE films without PFOPA surface functionalization. Dynamic water contact angles (advancing, receding, hysteresis) are also shown. The rightmost two columns list water roll-off angles of the substrates. Deposition times from 1 min to 60 min noted in the first column correspond to EN thin film thicknesses from about 2 m to about 14 m. The table in FIG. 28 shows values for PFOPA functionalized samples.

[0063] FIG. 31 shows a table of water and heavy oil static contact angles measured for different thicknesses and surface functionalization of EN-PTFE films. Deposition times from 1 min to 60 min noted in the first column correspond to EN film thicknesses from about 2 m to about 14 m. Strong superhydrophobic character was retained across all of the modes of functionalization. Superoleophobic character was retained in the 27 millimolar (mM) PFOA samples, but only oleophobic character was observed for EN-PTFE coatings functionalized with 2.7 mM PFOPA. The table in FIG. 28 shows values for 27 mM PFOPA functionalized samples.

[0064] FIG. 32 shows a schematic illustration of a method for fabricating omniphobic fabric substrates, according to an embodiment of the subject invention.

DETAILED DESCRIPTION

[0065] Embodiments of the subject invention provide novel and advantageous compositions that are omniphobic (or superomniphobic), as well as methods of fabricating the same. An omniphobic (or superomniphobic) coating can be fabricated on (e.g., directly on with no other elements therebetween) a fabric (e.g., cotton fabric) substrate. The multiscale textured surface can be achieved using a polytetrafluoroethylene (PTFE) electroless nickel coating, and the surface energy can be further reduced with the binding of a fluorinated monolayer. Once rendered repellant to both water and oil, the fabric substrates retain their repellency even after being contorted.

[0066] Increasing global energy needs, improved access, and favorable geopolitical considerations have spurred a surge in the worldwide reliance on unconventional deposits such as heavy crude oil and bitumen, which have emerged as major contributors to the fuel mix of modern economies. The handling and transportation of hydrocarbons from unconventional deposits is plagued by a distinctive set of challenges traceable to their complex rheological properties and high sulfur content. Transportation of viscous oils oftentimes entails dilution with light hydrocarbons and/or heating with an extensive thermal jacketing infrastructure to enable transportation through conduits such as pipelines, trucks, rail cars, and tankers. By geopolitical happenstance, the richest geological deposits for bitumen are located at a considerable distance (e.g., in the Athabasca region of Canada or Venezuela) from the refineries that are best equipped (in the Houston Gulf Coast area in the United States of America) to effectively convert these hydrocarbons into a diverse slate of products. Substantial viscosity modification is required to facilitate midstream transportation of heavy oil, which can have viscosities exceeding 300,000 centipoise (cP), American Petroleum Institute (API) gravity of less than 22.3, and specific gravity of greater than 920 kilograms per cubic meter (kg/m.sup.3) (see also, e.g., FIG. 3D). The addition of diluents, typically light condensates, reduces the transportation volume efficiency by approximately 30%, incurs considerable cost, and requires additional energy-intensive separation steps upon arrival at refineries to return the oil to its original composition. Other challenges attributable to the complex rheological properties of viscous oil include difficulties in maintenance and cleaning of various transportation vessels as well as the loss of substantial product volume (estimated to be as much as 10% in some cases) as a result of surface fouling.

[0067] In addition, much of the midstream infrastructure is constructed from base metals such as low alloy steels, which are prone to corrosion as a result of the high concentration of sulfur compounds, abrasive particles, and other highly corrosive species present in viscous crude oil. Corrosion-related failures can have a devastating impact on vulnerable ecosystems. As such, the inventors have recognized that there is a need for multifunctional coatings that mitigate surface fouling and facilitate ready transfer of viscous liquids. Given the complex form factors of transportation vessels spanning the range from bitutainers to containers in shipping barges, and the difficulties in on-field/on-board application of complex coatings, the design of flexible fabric liners represents an attractive solution for retrofitting current midstream infrastructure. Embodiments of the subject invention address the problems discussed above by providing oleophobic coatings on fabric surfaces that can be used in retrofitting applications across different forms of midstream conduits.

[0068] Fabricating surfaces that glide and are not wetted by oil streams represents a considerably greater challenge as compared to the design of surfaces repellant to water as a result of the much lower cohesive forces (primarily, van der Waals' interactions) and thus much lower surface tension of oil streams. Indeed, hydrophobic surfaces are reasonably abundant in nature, spanning the range from lotus leaves to shark skin and cuticles of insects, whereas oleophobic surfaces are not observed in nature. Three key aspects to controlling the behavior of liquid droplets and flow streams on a surface through modulation of interfacial interactions include: texturization across length scales, spanning the range from nanoscale and micron-sized topographies to define a landscape of trapped air bubbles; geometrical features that define reentrant curvature; and surface energy as governed by the chemical moieties that are available for interaction with an impinging liquid. Under an appropriate set of conditions, a liquid can be suspended in the metastable Cassie-Baxter regime, where it resides atop micro-and nano-textured surfaces and the air pockets embedded by the topographic features, which are known as plastrons. Superhydrophobic and superolcophobic behavior can be demonstrated utilizing ZnO tetrapods on metal meshes as textural elements, and by using the low-temperature sintering of TiO.sub.2 nanoparticles arrayed onto solid steel coupons by colloidal crystal templating (see also, e.g.; Douglas et al., Three-Dimensional Inverse Opal TiO.sub.2 Coatings to Enable the Gliding of Viscous Oils, Energy & Fuels 2020, 34 (11), 13606-13613; and O'Loughlin et al., Biomimetic plastronic surfaces for handling of viscous oil, Energy & Fuels 2017, 31 (9), 9337-9344; both of which are incorporated herein by reference in their entireties). However, the integration of these coatings with current transportation vessels is constrained by challenges in adhesion and durability of the coatings, and difficulties with field application, which have limited the viability of using such coatings in retrofitting existing infrastructure. Embodiments of the subject invention address this by providing superhydrophobic and superoleophobic electroless nickel composite coatings on a fabric surface (e.g., a cotton fabric surface) that allows for facile integration within existing transportation vessels and that can be readily fitted to adopt various form factors.

[0069] Electroless plating has found extensive industrial applications on planar metal surfaces (see also, e.g., Brenner and Riddell, Electroless plating on metals by chemical reduction, Proc Am Electropl Soc 1946, 33, 4-12; which is hereby incorporated herein by reference in its entirety). Electroless nickel coatings exhibit excellent corrosion as well as wear and abrasion resistance, homogeneous thickness across extended length scales, excellent adhesion to a variety of substrates, and applicability across a diverse range of form factors. Electroless nickel formulations typically contain a source of nickel ions, a reducing agent, complexing agents, and stabilizers. The autocatalytic reaction for electroless nickel deposition proceeds through the following half reactions:

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The overall equation can be written as:

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[0070] The versatility of electroless nickel coatings allows for the coating to be fine-tuned to suit particular environments and to incorporate various additives. Electroless nickel coatings are amenable to alloying, as well as the inclusion of bulk and surface precipitates. Nickel alloys can be deposited through the incorporation of phosphorous or boron from a reducing agent, and the volume of incorporated phosphorus influences the level of crystallinity of the electroless coatings. The incorporation of nanoparticles facilitates the formation of composite coatings with tailorable properties. For example, the inclusion of hard particles such as diamond or soft particles such as fluorinated salts can alter the lubricity of the coating. Guglielimi's theory describes the mechanism by which particles can be incorporated during electroless deposition. Adsorption occurs in two sequential steps, which establishes a relationship between the ultimate particle concentration embedded within the coating and particle concentration in the bath dispersion.

[0071] Embodiments of the subject invention include methods for electroless deposition to coat a fabric (e.g., a cotton fabric) substrate with nickel or a nickel alloy (e.g., nickel phosphorous alloy) incorporating polymer (e.g., PTFE) beads. The coating can be functionalized with a fluorinated monolayer (e.g., 1H,1H,2H,2H-perfluorooctanephosphonic acid (PFOPA)). The composite textured and low-surface-energy coating enables the rapid removal of heavy oil and water and retains superhydrophobic and superoleophobic properties even after mechanical deformation. The ability to fabricate large-area fabric substrates to exhibit robust omniphobicity provides an innovative retrofittable solution to challenges with viscous oil handling in the midstream sector. FIG. 5 shows an illustration of fabric and oil. The fabric that can be used with embodiments of the subject invention can be, for example, cotton fabric of the same type that may be found in shirts and other common items of clothing. After activation, deposition, and/or functionalization, the fabric can repel the oil.

[0072] Each of FIGS. 1 and 32 shows a schematic illustration of a method for fabricating omniphobic fabric substrates, according to an embodiment of the subject invention. Referring to FIGS. 1 and 32, the method can include surface activation (e.g., using 3-aminopropyltrimethoxysilane (APTMS) and/or PdCl.sub.2) of the fabric substrate, followed by electroless co-deposition of nickel (or a nickel alloy) and polymer (e.g., PTFE) beads. The method can also include further surface functionalization of the nickel coating (e.g., with PFOPA). Though FIG. 1 lists some specific materials (e.g., APTMS, PdCl.sub.2, PTFE, and PFOPA), these are for exemplary purposes and should not be construed as limiting.

[0073] Embodiments of the subject invention also include omniphobic (e.g., hydrophobic and oleophobic; such as superomniphobic (e.g., superhydrophobic and superoleophobic) compositions or coatings that can be applied to fabrics (e.g., cotton fabrics), as well as the coated fabrics. The composition or coating can comprise an electroless nickel (e.g., nickel alloy) coating with a polymer (e.g., PTFE). The composition or coating can further comprise a fluorinated monolayer (e.g., PFOPA) or surface-grafted fluorinated macromolecules bound to the nickel, the polymer, and/or the fabric. The fabric with the coating can be flexible and can retain its omniphobic (or superomniphobic) properties even after being contorted. The fabric with the coating can also retain its omniphobic (or superomniphobic) properties even at a temperature of, for example, at least 220 C. (e.g., at least 230 C., at least 240 C., at least 250 C., or at least 260 C.).

[0074] Embodiments of the subject invention also include methods of using an omniphobic composition as disclosed herein for midstream transport of bitumen or other oil products or byproducts. Embodiments also include a vehicle comprising an omniphobic composition as disclosed herein lining a transport section of the vehicle.

[0075] Embodiments of the subject invention represent a major advance in internal coatings of pipelines (gathering, transmission, and distribution), bitutainers, railcars, and Supermax tankers by providing an omniphobic flexible coating enabling rapid removal of heavy oil. Methods and compositions of embodiments of the subject invention allow for retrofittable application of omniphobic liners to enable rapid removal of rheologically challenging liquids such as heavy oil and bitumen. The liners can be incorporated directly as internal coatings of pipelines or vessels without the need for on-site coating application, which is exceedingly challenging under dry dock conditions given the large volumes and constraints on application of complex coatings. No related art coatings exist for the specific applications in handling of heavy oil.

[0076] Embodiments of the subject invention provide electroless deposition to coat a fabric (e.g., a cotton fabric) with an alloy (e.g., a nickel phosphorous alloy) incorporating beads (e.g., PTFE beads). The coating can be functionalized (e.g., with PFOPA). The composite textured and low-surface-energy coating enables the rapid removal of heavy oil and water and retains super-hydrophobic and superoleophobic properties after mechanical deformation. The ability to fabricate thermally robust and mechanically resilient large-area fabric substrates to exhibit robust omniphobicity provides an innovative retrofittable solution to challenges with viscous oil handling in the midstream sector.

[0077] When ranges are used herein, combinations and subcombinations of ranges (including any value or subrange contained therein) are intended to be explicitly included. When the term about is used herein, in conjunction with a numerical value, it is understood that the value can be in a range of 95% of the value to 105% of the value, i.e. the value can be +/5% of the stated value. For example, about 1 kg means from 0.95 kg to 1.05 kg.

[0078] A greater understanding of the embodiments of the subject invention and of their many advantages may be had from the following examples, given by way of illustration. The following examples are illustrative of some of the methods, applications, embodiments, and variants of the present invention. They are, of course, not to be considered as limiting the invention. Numerous changes and modifications can be made with respect to embodiments of the invention.

Example 1

Coating Fabrication

[0079] The initial fabric activation step was performed by adapting a known procedure (see Guo et al., Electroless nickel deposition of a palladium-activated self-assembled monolayer on polyester fabric, Journal of applied polymer science 2013, 127 (5), 4186-4193; which is hereby incorporated herein by reference in its entirety). A 1-inch by 1-inch cotton fabric substrate (JOANN Fabrics and Crafts) was submerged in a 1 wt. % ethanol solution of APTMS (Sigma) at room temperature for 24 hours (h). Next, the substrate was removed from the solution, annealed at 70 C. for 30 minutes (min) in a muffle furnace, and rinsed with deionized water (p=18.2 megaohms per centimeter (M/cm). Subsequently, the sample was immersed in a 0.05 wt. % aqueous solution of PdCl.sub.2 containing 2 vol. % of an aqueous solution of 37 wt. % HCl at room temperature for 10 min, followed by rinsing with deionized water (about 2-5 milliliters (mL) per square inch). Next, a PTFE electroless nickel (EN-P) coating (Caswell, Inc. Lyons, NY, USA) was deposited onto the activated substrate. Briefly, the activated fabric was submerged in the EN-P precursor solution at approximately 100 C. for various lengths of time ranging from 1 min to 60 min. Upon removal from the EN-P bath the coated fabric was rinsed with water (about 2-5 mL per square inch). Next, the coating was immersed in a 27 millimolar (mM) solution of PFOPA (Sigma) in tetrahydrofuran (THF) (Fisher Chemical) for 24 h. The workflow for coating fabrication is schematically illustrated in FIG. 1.

Coating Characterization

[0080] Wettability of the coated substrates was evaluated by measuring contact angles with a goniometer (Attension Theta Lite). The values reported are an average of a minimum of three measurements taken in unique areas across the substrate. Water droplets of approximately 5 microliters (L) were dispensed prior to recording a digital image. Heavy oil (Puma Energy) droplets with a viscosity of about 140 cP at 150 C., as measured using rotational rheometer with 40 millimeter (mm) parallel Peltier plate (Discovery Hybrid DHR-2 rheometer, TA instruments), were measured by manually placing oil droplets of about 10-15 L onto the substrate and analyzing the droplet using the Attension Theta Lite software. Where specified, heavy oil contact angles were recorded at temperatures of 150 C.-200 C., by heating the heavy oil to the target temperature and placing the substrate on a hot plate set to the same temperature. All other measurements were acquired at room temperature unless otherwise denoted.

[0081] The surface morphology of the coated substrates was examined using field-emission scanning electron microscopy (FE-SEM) (JEOL JSM-7500F) with an emission current of 10 microamps (A), probe current of 8 A, accelerating voltage of 5 kilovolts (kV), and 15 mm working distance. Bare fabric substrates were coated with 3-4 nanometers (nm) of platinum (Pt) using a 208 HR High-Resolution Sputter Coater. Energy dispersive X-ray spectroscopy (EDX or EDS) measurements were recorded using the Oxford system with an accelerating voltage of either 5 kV, emission current of 20 A, probe current of 12 A, and working distance of 8 mm.

[0082] X-ray diffraction (XRD) patterns were collected on a copper (Cu)-source (Cu K, =1.5418 Angstroms ()) Bruker-ENDEAVOR powder instrument with a Lynxeye XTE Detector. Samples were cut into strips of approximately 1 centimeter (cm) by 2 cm, and secured to steel sample power XRD (PXRD) holders with carbon tape, with layers of carbon tape added to make each sample flush with the holder surface. Scans were taken from 5-702 with a step size of 0.015 degrees per step (/step) and a dwell time of 1 second(s).

[0083] A Bruker Vertex-70 with PIKE MIRacle single-reflection horizontal attenuated total reflectance (ATR) accessory was used to collect Fourier-transform infrared (FTIR) spectroscopy data.

[0084] Thermogravimetric Analysis (TGA) data was collected using a TA Instruments TGA 5500 at a ramp rate of 10 C. per minute (C/min)-20 C./min up to 900 C. In a typical experiment, a 3 milligram (mg)-7 mg sample was placed in a platinum pan under an inert atmosphere.

[0085] FIG. 1 schematically depicts the coating fabrication process beginning with surface activation using APTMS and PdCl.sub.2, electroless deposition of a nickel composite coating embedding PTFE beads, and surface functionalization with PFOPA. From analogous experiments on flat low-alloy steel substrates, it was determined that electroless nickel coatings provide smooth homogenous deposition. The addition of PTFE beads to the electroless deposition bath results in agglomerates of PTFE beads of about 200 nanometers (nm) in diameter being agglomerated across the surface (see also FIGS. 6A-6C). Referring to FIGS. 2D-2F, high-resolution scanning electron microscope (SEM) images show the intricate woven pattern of the cotton fabric and delineate the incorporation of a conformal electroless nickel thin coating and PTFE beads on each individual thread of the substrate. Contrasting the bare cotton fabric at varying magnifications from FIGS. 2A-2C with the coated substrates, PTFE nanobeads are embedded along each strand and also observed in clusters at the intersections of the woven pattern. FIGS. 2G-2I are EDX maps showing the distribution of Ni, P, and F, respectively, across the functionalized substrate without the PFOPA monolayer. FIGS. 2J-2L show EDX maps showing the distribution of Ni, P, and F, respectively, across the functionalized substrate with the PFOPA monolayer.

[0086] FIG. 3A shows XRD patterns acquired after electroless Ni/PTFE deposition contrasted to the bare cotton substrate. The curve depicting the functionalized cotton fabric (after 1 minute of PTFE electroless nickel deposition and immersion in a 27 mM PFOPA solution for 24 hours) shows broad reflections assigned to metallic nickel (JCPDS #88-2326) indicating the deposition of Ni.sub.xP.sub.y thin films; another reflection assigned at 2=18 can be indexed to crystalline PTFE (JCPDS #47-2217), in addition to unique cellulose reflections that are still apparent. FTIR spectroscopy was performed to evaluate the role of PFOPA functionalization. FIG. 3B contrasts the distinctive vibrational bands of the pristine cotton substrate, cotton after EN-P deposition, and the EN-P substrate after functionalization with PFOPA. FIGS. 7A-7C contrast the cotton fabric after initial surface activation with APTMS, PdCl.sub.2, and neat PFOPA to further understanding the structural changes occurring after each activation step. The appearance of characteristic fluoroalkyl PFOPA bands in the functionalized fabric sample confirm PFOPA functionalization of the nickel (Ni) surface. Specifically, the bands at 1142 cm.sup.1, 1184 cm.sup.1, and 1207 cm.sup.1 are assigned to symmetric CF.sub.2, asymmetric CF.sub.3, and asymmetric CF.sub.2 stretches, respectively. The 1232 cm.sup.1 band is derived from overlapping symmetrical CF.sub.2 and PO stretches. A slight blue shift is observed for the PO and PO bands from 952 cm.sup.1, 935 cm.sup.1, and 920 cm.sup.1 for the free molecule to 995 cm.sup.1, 977 cm.sup.1, and 962 cm.sup.1 in the surface-bound species. Similar changes in PFOPA vibrational modes can be ascribed to formation of a fluorocarbon helix on the surface.

[0087] TGA was performed to evaluate the thermal robustness of the architected coatings. As shown in FIG. 3C, the derivative curve indicates two separate thermal degradation processes. The first process is operational in the temperature range of 265 C.-360 C. corresponding to decomposition of the surface bound PFOPA layer, whereas the second process corresponds beyond 420 C. to decomposition of the cotton substrate. The latter assignment was verified based on control TGA experiments performed on untreated cotton fabric and the fabric with EN-Ni/PTFE (but without PFOPA functionalization) as shown in FIGS. 8A and 8B. Because degradation occurs well beyond 220 C., the highest handling temperature of bitumen, the functionalized fabrics plainly have the thermal robustness needed for midstream applications.

[0088] Coating wettability and flexibility were evaluated as a function of electroless nickel/PTFE deposition time (which controls the thickness) and PFOPA concentration. Both of these variables are essential to controlling wettability as they allow for precise control of the multiscale texturization, reentrant curvature, and surface energy reduction. As depicted by the contact angle values shown in the table in FIG. 10, without functionalization with PFOPA, the fabric with EN-P/PTFE exhibits superhydrophilic behavior characterized by the flash spreading of water. The increased surface area resulting from the electrodeposited Ni and additional PTFE nanobeads amplify the intrinsic wettability of the cotton fabric (which has a water contact angle of) 0, enabling the system to rapidly access the Wenzel wetting regime. Similarly, oil droplets completely wet the cotton fabrics with EN-P/PTFE without PFOPA functionalization with the flash spreading of the heavy oil when both are at a temperature of 150 C. There is a direct correlation between the time the fabric substrates were immersed in the PTFE electroless nickel bath and the coating deposition thickness. Upon varying the deposition rate from 1 min-60 min, the deposition thickness as deposited on the strands of thread varied from about 2 micrometers (m) to 14 m (see also the table in FIG. 11). Superhydrophobicity and superoleophobicity was achieved with just 1 min of the EN-P/PTFE deposition, corresponding to a thickness of 2.7 m3.8 m upon surface functionalization of the Ni coating with PFOPA at a concentration of 27 mM in THF. In general, a decrease in oleophobicity was observed with increasing thickness of the PTFE electroless nickel deposition, as Ni deposits into crevices and reduces the asperities between the individual threads of the fabric substrate, which brings about an overall reduction in the different scales of texture. An optimal combination of hydrophobic and oleophobic behavior was observed for the 1 minute sample, which shows contact angles of 1511 for water, 1563 for heavy oil at 150 C., and 1534 for heavy oil at 200 C. The table in FIG. 12 details the water contact angles as a function of coating deposition time and PFOPA concentration in addition to wettability performance with heavy oil #2, which has a different viscosity as contrasted in FIG. 9.

[0089] In summary, upon deposition of the electroless nickel composite coating embedding PTFE beads and surface functionalization with a PFOPA monolayer, the cotton fabric was rendered both superhydropobic and superoleophobic. The functionalized fabric was flexible, could be fashioned into different forms as required to adapt to the geometries of different receptacles and pipelines, and glided both water and heavy oil. A coating thickness of about 2 um of electroless nickel/PTFE was found to be optimal for fully utilizing the hierarchical texturization of the cotton substrate while retaining its flexibility and enabling reduction in surface energy upon surface functionalization with PFOPA. The coatings were thermally robust and resisted degradation up to temperatures of 265 C., well beyond the 220 C. operational temperature limit considered to be the upper limits of operational temperatures for conventional midstream infrastructure. These results indicate a solution for the integration of treated fabric as liners in midstream transportation vessels, thereby mitigating the challenges of on-board coating, and bringing about substantial benefits in reducing product loss, minimizing the use of diluents and thermal jacketing, and greatly simplifying maintenance and cleaning operations.

Example 2

[0090] FIG. 4 depicts sequenced images demonstrating the superhydrophobic and superoleophobic behavior of the fabricated coatings (from Example 1). The cotton substrate was fashioned into an open-faced cubic receptacle, and filled with deionized water and heavy oil. The wettability was observed at room temperature for water and at 150 C. for the heavy oil. In both instances, the liquid was rapidly removed from the receptable and the coated fabric was readily recovered without residual contamination from oil. The omniphobicity of the coatings was maintained for over 6 months. The open-faced cube was further filled with water and was allowed to stand for 1 h. No outflows or leaks of water were observed, and the receptacle fully retained its ability to repel water. This indicates the robustness of the plastrons that are stabilized from the multiscale texture, reentrant curvature, and reduced surface energy.

Example 3

[0091] Coatings were prepared similarly to those for Examples 1 and 2.

Coating Fabrication

[0092] Parchment-colored 100% utility cotton (JOANN Fabrics & Crafts) was chosen as the substrate for coatings. A cotton fabric substrate was submerged in a 1 wt. % ethanol (96%, Fisher Chemical) solution of APTMS (97%, Sigma) at room temperature for 24 h. Next, the substrate was removed from the solution, annealed at 70 C. for 1 h in a muffle furnace (Thermo Scientific Thermolyne FD1540M), and rinsed with deionized (DI) water (Thermo Scientific Barnstead GenPure filtration system, p=18.2 M.Math.cm.sup.1) using a spray bottle. Subsequently, the sample was immersed in a 0.05 wt. % PdCl.sub.2 aqueous solution with 0.2 M HCl at room temperature for 10 min, followed by rinsing with deionized water (about 2 mL to about 5 mL per square inch). Next, the activated substrate was submerged in Caswell electroless nickel plating (EN) solutions at 85 C. to 90 C. (Caswell, Inc. Lyons, NY, USA) for various lengths of time ranging from 1 min to 60 min. The solution was replenished every 5 min to 10 min; PTFE beads were added as needed to obtain thicker coatings. Upon removal from the EN-PTFE bath the coated fabric was rinsed with DI water with a spray bottle until the runoff was clear. Next, the coating was immersed in a 27 mM solution of PFOPA (95%, Sigma) in ethanol for 24 h. The final coating is schematically illustrated in FIG. 13.

Coating Characterization

[0093] Wettability of the coated substrates was evaluated by measuring contact angles using a goniometer (Attension Theta Lite). The values reported are an average of a minimum of measurements taken across three distinct areas across the substrate. Approximately 20 L of deionized water and light sweet crude oil (obtained from Permian Basin, specific gravity 0.8050 g/mL) 25 were dispensed onto substrate manually prior to recording a digital image. Heavy oil (Puma Energy) droplet contact angles, with a viscosity of ca. 140 cP at 150 C. as measured using rotational rheometer with 40 mm parallel Peltier plate (Discovery Hybrid DHR-2 rheometer, TA instruments), were measured by manually placing oil droplets of about 20 L onto the substrate and analyzing the droplet using the Attension Theta Lite software. Heavy oil contact angles were recorded at temperatures of 175 C., by heating the heavy oil to the target temperature and placing the substrate on a hot plate (VWR VMSC4) set to the same temperature. All other measurements were acquired at room temperature unless otherwise denoted. Dynamic contact angles were measured with the same goniometer with a changing drop size of 0 L to 20 L at a rate-of-change 0.5 L/s (40 s advancing measurement and 40 s receding measurement).

[0094] Roll-off angles were obtained with 20 L droplets based on two methods. In the first approach, the tilting plate method, droplets were dispensed onto a flat fabric surface and the surface angle changed at approximately 1/s until translational motion of the droplet is initiated with reference to a marked location on the fabric to ensure objectivity. Multiple droplets were tested at different fabric surfaces. In the second approach, labeled as centimeter drop, droplets were also dispensed about 1 cm above a fabric substrate angled at 15 and the angle decreased at approximately 1 per droplet until the drop did not roll off on contact.

[0095] The surface morphology of the coated substrates was examined using field-emission scanning electron microscopy (FE-SEM) (JEOL JSM-7500F) with an emission current of 10 A, probe current of 8 A, accelerating voltage of 5 kV, and 15 mm working distance to the pole piece. Bare fabric substrates were mounted on Cu tape and coated with 5 nm of Pt using a 208HR high-resolution sputter coater. EDS measurements were recorded using the Oxford system with an accelerating voltage of 5 kV, emission current of 20 A, probe current of 12 A, and a working distance of 8 mm.

[0096] To determine the thickness of the coatings, cross-sectional samples were prepared for SEM. Fabric pieces were embedded in Epoxicure 2 resin and hardener (4:1 ratio) and left at room temperature to harden for 24 h. A cut through the embedded fabric was made with a Buchler IsoMet diamond precision saw and the cut surface was then ground with a Buchler EcoMet 30 grinding and polishing wheel using 1200 grit P600 silicon carbide sandpaper followed by 4000 grit P1200 silicon carbide sandpaper. Polishing was then done with an Electron Microscopy Sciences 1 m diamond polishing paste and 200 mm Struers MD-Floc polishing pads. The polishing paste was diluted with Falcon Tool Company water-based polishing lubricant and diamond thinner. The samples were sputter coated with 5 nm of Pt and examined under FE-SEM and EDS. A minimum of three coating replicates were examined at three different locations to determine the thickness of the deposited nickel coating.

[0097] X-ray photoelectron spectroscopy (XPS) was recorded with an Omicron DAR 400 XPS/UPS system with a 128 micro-channel Argus detector. A 1253.6 eV Mg X-ray source at 15 kV and 20 mA emission current were utilized with a CN10 electron source to minimize charging. Spectra were calibrated to a carbon Is feature from adventitious carbon at 248.8 eV. Fabric samples were kept in an Across International model AT19 vacuum oven at 100 C. for 2 days prior to measurement.

[0098] A Bruker Vertex-70 with PIKE MIRacle single-reflection horizontal attenuated total reflectance (ATR) accessory was used to acquire Fourier-transform infrared (FTIR) spectroscopy data. Sample substrates were pinched underneath the sample head above a diamond ATR crystal. Thermogravimetric analysis (TGA) data were collected using a TA Instruments TGA 5500 at a ramp rate of 20 C./min up to 900 C. In a typical experiment, a 3 mg to 7 mg sample was placed in a platinum pan under an inert atmosphere.

[0099] Tensile testing was performed following ASTM D5035 to evaluate the mechanical properties of textile fabrics after coatings were applied for 1 min, 10 min, and 60 min, alongside uncoated control samples. Testing parameters were selected based on the results of textured fabric tensile studies reported in the literature. Specimens were precisely cut using a rotary cutter to prevent edge distortion and conditioned at room temperature (22 C.) before testing. A 1 kN Instron 5943 tensile tester with pneumatic side-action grips was used, applying a displacement rate of 100 mm/min. The gauge length between grips was set at 70 mm, and samples were stretched to rupture, recording breaking force (in N) and elongation at maximum force. At least fifteen replicates were tested per sample type to ensure statistical robustness. Data were analyzed for statistical significance, with results reported as mean values and standard deviations.

[0100] FIG. 13 schematically illustrates the deposition of an alloyed Ni composite coating onto woven cotton fabric. Initial surface activation is achieved using APTMS and PdCl.sub.2, followed by electroless deposition of a nickel composite coating embedding PTFE beads for various times (as denoted in sample labels), followed subsequently by surface functionalization with PFOPA. Based on analogous experiments performed on flat low-alloy steel substrates, electroless nickel coatings are observed to provide smooth conformal deposition; the addition of about 200 nm PTFE beads yields agglomerated beads dispersed across the surface (FIGS. 20A-20C).

[0101] High-resolution scanning electron micrographs in FIGS. 14A-14O show the intricate woven pattern of the cotton fabric (bare cotton fibers are shown in FIGS. 21A-21C) and attest to the incorporation of electroless nickel and PTFE on each individual thread of the substrate. Contrasting the bare cotton fabric at varying magnifications with the coated substrates, PTFE nanobeads are embedded along each strand. Some agglomeration of the PTFE beads in clusters is observed at the intersections of the woven pattern (FIG. 14I). PTFE nanobeads are observed to agglomerate into complex texturizing elements at lower deposition times, as seen in FIGS. 14A-14L. The corresponding EDS maps are shown in FIGS. 14E-14F. After 10 minutes of electroless deposition, larger PTFE agglomerations are observed, as exhibited in FIG. 14M. With coating thickness increases, it becomes more difficult to retain the PTFE bead texturization as it is over-coated by the electroless Ni alloy (FIGS. 14N and 14O). This smoothening effect is especially pronounced for reaction times more than 45 min. EDS maps of texturizing elements in FIGS. 14A-14O are shown in FIGS. 22A-22D, whereas the corresponding EDS spectra are plotted in FIGS. 23A-23C and 24A-24D.

[0102] The evolution of coating thickness as a function of electroless deposition reaction time is plotted in FIG. 15A. After an initial rapid deposition of about 2 m of the composite, the coating thickness increases at a steady rate of 0.2 m/min. The rapid initial growth in thickness is consistent with the electroless reduction, nucleation, and deposition of nickel alloy particles mediated by sur-face activation of the cotton fibers by reaction with APTES and PdCl.sub.2. Beyond the initial nucleation and deposition step, which proceeds until conformal coverage is achieved across the surface-functionalized cotton fibers, there is a direct correlation between the time the cotton fabric substrates are immersed in the PTFE electroless nickel bath and the coating thickness. During deposition times from 1 min to 60 min, the deposition thickness steadily increases from about 2 m to about 14 m (FIG. 15A).

[0103] To evaluate the thermal stability of the engineered substrates, TGA was performed. As shown in FIG. 15B, the derivative curve indicates three separate thermal degradation processes. Control TGA experiments were performed on untreated cotton fabric, cotton fabric with an electroless nickel coating without PTFE beads, cotton fabric with EN-PTFE (but without PFOPA functionalization), and finally cotton fabric with EN-PTFE coating and PFOPA functionalization. Based on these control experiments, the first process in the temperature range of 20 C. to 50 C. corresponds to a small mass loss arising from loss of volatile species from the cotton substrate. The second mass loss regime in the temperature range of 260 C. to 360 C. corresponds to the degradation of the cotton substrate. The third mass loss regime in the temperature range of 360 C. to 460 C. corresponds to the gradual decomposition of the PTFE beads. Because the bulk of the degradation occurs well beyond 220 C., the highest handling temperature of bitumen, the functionalized fabrics are observed to exhibit the desired thermal robustness needed for midstream applications.

[0104] The mechanical resilience of the coatings were evaluated using the tensile testing experiments shown in FIGS. 15C and 15D. The results indicate that the EN-PTFE coating increases the breaking force of fabric samples; a progressive increase in breaking force is observed with an increase in coating time. Statistical analyses confirm that all coated samples exhibited significantly higher breaking force as compared to plain cotton (p<0.05), demonstrating improved mechanical strength (see the table in FIG. 29). However, this increase in strength comes at the expense of reduced breaking strain, as coated samples exhibited progressively lower flexibility with longer coating durations. T-test results in the table in FIG. 29 confirmed that the reduction in elongation was also statistically significant (p<0.05), which indicates a trade-off between strength and flexibility. These findings suggest that while the coating reinforces the fabric, it also makes it less deformable, a factor that will need to be considered in designing liners for bitumen vessels with different form factors and geometries.

[0105] FIGS. 16A-16D present spectroscopic characterization of the functionalized fabrics. FIG. 16A contrasts the distinctive vibrational modes of the uncoated cotton substrate, cotton substrate after EN-PTFE deposition, and the EN-PTFE coated substrate after functionalization with PFOPA. An FTIR spectrum acquired for PFOPA is also shown for comparison. The appearance of characteristic fluoroalkyl modes observed in the functionalized fabric sample corroborates PFOPA functionalization of the Ni surface. Specifically, bands at 1142, 1184, and 1207 cm.sup.1 are assigned to symmetric CF2, asymmetric CF3, and asymmetric CF2 stretches, respectively. The 1232 cm.sup.1 band is derived from overlapping symmetrical CF2 and PO stretches. A blue shift is observed for the PO and PO bands from 952 cm.sup.1, 935 cm.sup.1, and 920 cm.sup.1 for the free molecule to 995 cm.sup.1, 977 cm.sup.1, and 962 cm.sup.1 in the surface-bound species, which corroborates the grafting of PFOPA to Ni surfaces through phosphonate head groups. Similar changes in PFOPA vibrational modes have been ascribed to formation of a fluorocarbon helix on the surface. FIG. 16B plots the evolution of ATR-IR absorbance with varying EN-PTFE deposition times. Notably, the water IR bands at 1350 cm.sup.1 and 3700 cm.sup.1 are greatly diminished after 2 min of coating and the cotton bands (such as at 1000 cm.sup.1, 2900 cm.sup.1, and 3300 cm.sup.1) are no longer discernible after 10 min of coating. The latter reflects the complete coverage of the cotton fibers by the composite Ni alloy coating.

[0106] FIGS. 16C, 16D, and 25 show core-level XPS spectra of 10 min EN-PTFE coated cotton fabric. The peaks have been assigned based on compiled library values for elements and in comparison to XPS spectra acquired for nickel oxide. The surface of the coated fabric shows pendant fluorocarbon moieties derived from the PTFE beads and PFOPA monolayer with a smaller contribution of ether, carbonyl, and alkyl moieties as shown in FIG. 16C. As can be seen in FIG. 16D, the surface comprises Ni.sup.2+ and Ni.sup.3+ contributions atop the metallic Ni alloy layer. FIG. 25 plots core-level F 1s XPS spectra, which support these ideas by demonstrating the presence of distinctive CF.sub.2 and CF.sub.3 features.

Example 4

[0107] The wettability of the coated cotton fabrics (from Example 3) towards water and bitumen was evaluated as a function of electroless nickel/PTFE deposition time (which governs the coating thickness and texture) and PFOPA functionalization. The former is important to precise control of the multiscale texturization and reentrant curvature that defines plastronic architectures and mediates the surface topographies that interact with liquids, whereas the latter governs the surface energy at the solid/liquid interface. Coatings to facilitate bitumen midstream transportation are required to have high contact angles, low roll-off angles, and low contact angle hysteresis. Three different probe liquids were used-deionized water, sweet light crude oil, and bitumen. FIG. 26 plots the temperature-dependent viscosity of a heavy oil sourced from Puma Energy. The table in FIG. 30 lists these values for EN-PTFE coatings on cotton fabrics for varying electroless deposition times, whereas The table in FIG. 28 lists values for EN-PTFE coatings on cotton fabrics after PFOPA functionalization. Ni alloy composite coatings embedding PTFE beads imbue superhydrophobicity even before functionalization with PFOPA (FIG. 29). Indeed, even the thinnest EN-PTFE coated fabrics show water contact angles >150. EN-PTFE coatings further demonstrate promising normal oleophobicity towards bitumen at 175 C., but do flash wet sweet light crude oil, which has a lower viscosity. Notably, the contact angle hysteresis is halved for EN-PTFE coatings as compared to bare cotton and cotton functionalized with PFOPA, which indicates that the combination of 3D texturization and low-surface-energy PTFE inclusions visible in FIGS. 14A-14O greatly reduce the interactions between water droplets and the substrate.

[0108] Next, turning to FIGS. 28 and 17A-17P, PFOPA functionalization halves the water contact angle hysteresis again, which reflects a further reduction in surface energy at the liquid/solid interface that decreases interactions between fluid droplets and the coated cotton fabric substrates. FIG. 28 illustrates that EN-PTFE coatings with PFOPA functionalization glide water droplets at roll off angles between 35 and 50 for coating less than 20 min. As the coating exceeds thicknesses of 5 m, water droplets no longer roll off quite so easily because of the loss of PTFE-nanobead-derived texturization. Notably, with diminution of geometric texturization as a result of Ni overdeposition around PTFE beads and between individual threads of the woven fibers, the contact angles of water and bitumen are reduced by about 10 to 20. As such, coating thicknesses of less than 10 m corresponding to deposition times less than 45 min yield optimal EN-PTFE texturization.

[0109] Examining the wettability metrics listed in FIG. 28, superhydrophobicity and superoleophobicity is achieved even for the thinnest 1 min EN-PTFE electroless deposition time, which corresponds to a thickness of 2.70.6 m upon surface functionalization with PFOPA at a concentration of 27 mM in ethanol. FIGS. 17A-17P depict bitumen and deionized water droplets placed on top of coated cotton substrates under blacklight. The untreated fabric is hydrophobic and oleophilic to bitumen. The EN-PTFE coating or direct PFOPA functionalization of the cotton substrate achieves superhydrophobicity and bitumen oleophobicity; however, both coating with EN-PTFE and subsequent functionalization with PFOPA are required to achieve bitumen superoleophobocity and light crude oil oleophobicity (FIG. 17N). In general, a decrease in oleophobicity is observed beyond coating times of 45 min with increasing thickness of the coatings, as Ni deposits into intervening crevices and smooths the asperities between the individual threads of the woven fabric substrate, thereby bringing about an overall reduction in the different scales of texture (as evidenced in FIGS. 14N and 14O). An optimal combination of water and oil repellence is observed for EN-PTFE samples less than 5 m (corresponding to deposition times <5 min), which show contact angles of 1625 for water, 1534 for heavy oil at 175 C., and 1242 for light sweet crude oil.

[0110] Perfluorooctanoic acid (PFOA) and an order of magnitude smaller concentration (2.7 mM) of PFOPA were also tested as functionalizing procedures of the EN-PTFE coatings (see the table in FIG. 31). These coatings also achieved superhydrophobicity and superoleophobicity in very similar fashion to the 27 mM PFOPA coatings shown in FIG. 28. However, the 2.7 mM PFOPA functionalized samples suffered a loss of 10 in heavy contact angles as compared to the best performing 27 mM PFOPA functionalized samples, which is likely indicative of sub-monolayer PFOPA coverage of surfaces contacted by oil droplets.

[0111] Dynamic contact angle measurements provide a glimpse of the evolution of substrate wettability upon liquid contact. When measuring dynamic contact angles of the substrates, wetting over time is observed for all fabric samples not coated with EN-PTFE. Bare cotton wets in less than a minute despite initially exhibiting a non-zero contact angle; direct PFOPA functionalization of the substrate delays water wetting, which is nevertheless observed after about 5 min of placement of a water droplet. This wetting is particularly notable in measurements of receding contact angles, as shown in FIGS. 18A-18I. In stark contrast, a PFOPA-functionalized EN-PTFE coating is so water repellent that the water droplet is pulled completely off the substrate by the pipette.

[0112] Next, beyond individual droplets, the wettability of coated substrates was examined upon immersion in water and bitumen, as relevant to the midstream transportation of bitumen. The EN-PTFE-coated fabric with PFOPA functionalization was subjected to several tests involving immersion within water or bitumen, or where these liquids were flowed across the substrates. Images contrasting the wettability of bare cotton and the EN-PTFE-coated fabric with PFOPA functionalization are shown in FIGS. 19A-19H. In all cases, water and bitumen were removed from the latter substrate within 30 s with remnants being pinned that still do not wet the substrate.

[0113] A cotton substrate with an EN-PTFE coating and PFOPA functionalization was fashioned into an open-faced cubic receptacle and filled with deionized water and heavy oil as a scale model for a bitutainer. The wettability towards water at 25 C. and heavy oil at 150 C. is examined for these scale models. In both instances, the liquids are rapidly removed from the receptacle and the coated fabric is readily recovered in near pristine condition. The coated receptacle is further filled with water and was allowed to stand for 1 h. No outflows or leaks of water are observed, and the receptacle fully preserved its ability to repel water. These results indicate the robustness of the plastrons that are stabilized from the multiscale texture, reentrant curvature, and reduced surface energy resulting from embedding PTFE beads and PFOPA functionalization. Indeed, the hydrophobic and oleophobic characteristics of the coatings is maintained for over 6 months under ambient conditions. These results further indicate that ultrathin EN-PTFE coatings remain flexible and readily glide heavy oil even after being shaped into different configurations, which attests to their suitability for application as liners for retrofit-ting midstream transportation vessels.

[0114] To validate the ability of these coatings to retain heavy oil without leaks over an extended period of time, a 45-day study was conducted with bitumen at 175 C. Three EN-PTFE-PFOPA-coated cotton fabrics with dimensions of 2 inches4.375 inches were folded to create a boat shape as shown in FIGS. 27A and 27B. The boats were suspended in a 600 ml beaker using paperclips attached to the edges. Next, 4 g of bitumen was placed in each boat. The material was then placed in a forced air convection oven at 175 C. Bitumen melted inside the boats but did not break through the treated fabric. No bitumen breakthrough was observed after 45 days. The bitumen was observed to slowly harden and solidify as volatile components evaporated, however. This test further attests to the long-term thermal stability and mechanical resilience of coated fabric substrates to retain bitumen without plastron collapse and leakage.

[0115] Overall, upon deposition of an electroless nickel composite coating embedding PTFE beads and subsequent surface functionalization with a PFOPA monolayer, cotton fabric was rendered both superhydrophobic and superoleophobic to bitumen. The coated substrate demonstrated low roll-off angles and low contact angle hysteresis in dynamic contact angle measurements, which attest to minimal interfacial interactions with common fluids and enable facile gliding of both water and oil flow streams. Electroless nickel deposition reinforces the cotton fabric and increases its strength but preserves sufficient flexibility such that the fabrics can be fashioned into free-standing receptacles or adjusted to follow the contours of vessels different forms. A coating thickness of about 2 m to about 4 m of electroless nickel/PTFE was found to be optimal for fully utilizing the hierarchical texturization of the cotton substrate while retaining its flexibility and enabling reduction in surface energy upon surface functionalization with PFOPA. The coatings are thermally robust and resist degradation up to temperatures of 265 C., well beyond the 220 C. operational temperature limit common to midstream transportation of bitumen. These results indicate an excellent solution for the integration of treated fabric as liners in midstream transportation vessels, thereby mitigating the challenges of on-board coating, and bringing about substantial benefits in reducing product loss, minimizing the use of diluents and thermal jacketing, and greatly simplifying maintenance and cleaning operations.

[0116] 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.

[0117] All patents, patent applications, provisional applications, and publications referred to or cited herein (including in the References section, if present) 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.

REFERENCES

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