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  • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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  • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
  • B01D2321/281—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by applying a special coating to the membrane or to any module element
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  • B01D2323/081—Heating
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  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
  • B01D61/025—Reverse osmosis; Hyperfiltration
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  • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
  • B01D65/08—Prevention of membrane fouling or of concentration polarisation
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  • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

• the present embodiments are related to crosslinked graphene oxide membranes and provide membranes with anti-microbial properties.
• microbes in today's society can present serious issues in applications where the level of microbes must be controlled. In applications such as health industry and in water delivery, treatment, and filtration, the growth of microbes to unhealthy levels can result in widespread sickness. Additionally, the growth of microbes in water filtration and delivery apparatuses can also result in biological fouling, reducing the effective lifespan of the equipment. In Heating, Ventilation, and Air Conditioning (HVAC) systems, microbes multiplying in the moist air ducts can lead to foul odor and health problems if left untreated. Also, for vessels in water, unchecked growth of microbes on the vessel's wetted area can reduce the hydrodynamic efficiency of the hull by disrupting the hull shape and creating drag thereby reducing fuel efficiency.
• HVAC Heating, Ventilation, and Air Conditioning
• a crosslinked GO membrane may reduce the presence of microbes.
• an anti-microbial membrane can be described as comprising: (1 ) a support, and (2) a composite coating the support comprising a crosslinked optionally substituted graphene oxide compound, where the graphene was crosslinked by a crosslinker selected form the group consisting of an optionally substituted biphenyl of Formula 1 , an optionally substituted triphenylmethane of Formula 2, an optionally substituted diphenylamine or optionally substituted 9H-carbazole represented by Formula 3A or 3B, and an optionally substituted bishydroxy methyl propanediol compound of Formula 4:
• Ri and R 2 are independently NH 2 or OH; and R 3 and R 4 are independently OH, S0 3 H, S0 3 Na, or S0 3 K;
• R 5 is H, CH 3 , or C 2 H 5 ;
• R 6 is H, CH 3 , -C0 2 H, -C0 2 Li, -C0 2 Na, -C0 2 K, -S0 3 H, - S0 3 Li, -S0 3 Na, or -S0 3 K; and n is 0, 1 , 2, 3, 4, or 5;
• Ri and R 2 can be independently be NH 2 , or OH;
• R 7 and R 8 are independently H, CH 3 , C0 2 H, C0 2 Li, C0 2 Na, C0 2 K, S0 3 H, S0 3 Li, S0 3 Na, or S0 3 K;
• k is 0 or 1 ;
• m is 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
• p is 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10;
• R 9 , Ri 0 , R-n , and Ri 2 can be independently:
• R 13 is independently OH, NH 2 , C0 2 H, C0 2 Na, C0 2 K, S0 3 H, S0 3 Na, or S0 3 K and r is 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10; whereby the membrane kills microbes as determined by having an antibacterial effectiveness of 2.0 or more.
• the optionally substituted biphenyl can be selected from:
• the optionally substituted biphenyl can be selected from:
• the optionally substituted graphene oxide comprises platelets.
• the platelets may be between about 0.05 ⁇ and about 50 ⁇ .
• the mass ratio of graphene oxide to crosslinker in the composite can be a value ranging from 1 :1000 to 50:1.
• the support can be the article to be protected from microbial growth.
• a method of preventing microbial growth comprising: (1) providing the aforedescribed membrane and (2) exposing the membrane to a working fluid containing microbes, wherein the membrane can kill microbes as a result of exposure to the working fluid as determined by having an antibacterial effectiveness of 2.0 or more.
• providing the aforedescribed membrane can comprise coating said membrane on the surface to be protected from microbes.
• the mass ratio of graphene oxide to crosslinker in the composite can be a value ranging from 1 :1000 to 50: 1.
• the support can comprise the article to be protected from microbes.
• FIG. 1 is a diagram showing the dimensions of a graphene platelet.
• FIG. 2 is a depiction of one possible embodiment of an anti-microbial membrane that may be used in anti-microbial applications.
• FIG. 3 is another possible embodiment of an anti-microbial membrane where the support as part of the object protected; the support being the hull of a boat.
• FIG. 4 is yet another possible embodiment of an anti-microbial membrane where the support as part of the object protected; the support being a reverse osmosis membrane.
• FIG. 5 is a depiction of possible method embodiment(s) for preventing microbial growth and/or microbial fouling.
• the solid lines indicate a possible embodiment and the dashed lines indicate a more specific possible embodiment of the method for preventing microbial growth.
• killing microbes can be measured by the methods used in JIS Z 2801 :2012 (English Version pub. Sep. 2012) where successful killing of microbes by an object can be defined as that object having an antibacterial activity of 2.0 or higher.
• selective permeability refers to a membrane that is relatively permeable for one material and relatively impermeable for another material.
• a membrane may be relatively permeable to water vapor and relatively impermeable to oxygen and/or nitrogen.
• the ratio of permeabilities of the different materials may be useful in describing the selective permeability.
• the term “rest,” “resting,” or “rested” refers to the act of leaving a solution stand undisturbed at room temperature and atmospheric pressure for a specific duration of time.
• molecular weight is used with respect to a moiety or part of a molecule to indicate the sum of the atomic masses of the atoms in the moiety or part of a molecule, even though it may not be a complete molecule.
• phenylene has the broadest meaning generally understood in the art, and may include a cyclic ring or ring system comprising six carbon atoms where there are at least two ring hydrogen substitutions.
• biphenyl has the broadest meaning generally understood in the art, and may refer to the cyclic ring or ring system comprising 12 carbon atoms which includes: where there is at least one hydrogen substitution.
• triphenylmethane has the broadest meaning generally understood in the art, and may refer to the cyclic ring or ring system comprising 20 carbon atoms which includes:
• diphenylamine has the broadest meaning generally understood in the art, and may include a heterocyclic ring or ring system
• C X -C Y or "C X . Y” refers to a carbon chain having from X to Y carbon atoms.
• C1-12 alkyl or C1-C12 alkyl includes fully saturated hydrocarbon containing 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , or 12 carbon atoms.
• Layered GO membranes with lamellar structure can be fabricated from a GO aqueous solution, but may be highly susceptible to be dispersed in environments under high flux or with transient shear forces. To solve this issue, the GO sheets can be cross-linked firmly to withstand the shear forces while keeping the lamellar structure.
• an anti-microbial membrane is described.
• the membrane can comprise a composite coating.
• the membrane can comprise a support and a composite coating on the support material.
• the anti-microbial membrane may be selectively permeable.
• the membrane is not selectively permeable.
• the membrane is not permeable.
• the membrane can have high water vapor permeability.
• the membrane may have low water vapor permeability.
• the support may be porous. In other embodiments, the support can be non-porous.
• the composite coating may comprise a graphene material and a crosslinker material.
• the graphene material may be arranged amongst a polymer material.
• the crosslinker material can also be a polymer.
• the graphene material and the crosslinker material are covalently linked to one another.
• the crosslinker material can be the same material as the polymer material.
• the graphene material may be arranged amongst other materials in the composite coating in such a manner as to create an exfoliated nanocomposite, an intercalated nanocomposite, or a phase-separated microcomposite.
• a phase-separated microcomposite phase may be when, although mixed, the graphene material exists as separate and distinct phases apart from the other materials.
• An intercalated nanocomposite may be when the other compounds begin to intermingle amongst or between the graphene platelets but the graphene material may not be distributed throughout the polymer.
• the individual graphene platelets may be distributed within or throughout the other materials.
• An exfoliated nanocomposite phase may be achieved by chemically exfoliating the graphene material by a modified Hummer's method, a process well known to persons of ordinary skill.
• the majority of the graphene material may be staggered to create an exfoliated nanocomposite as a dominant material phase.
• the graphene material may be separated by about 10 nm, 50 nm, 100 nm to about 500 nm, to about 1 micron.
• the graphene material may be in the form of sheets, planes or flakes. In some embodiments, the graphene material may be in the form of platelets. In some embodiments, the graphene may have a platelet size of about 0.05 ⁇ to about 100 ⁇ . In some embodiments, the graphene material may have a surface area of between about 100 m 2 /g to about 5000 m 2 /g. In some embodiments, the graphene material may have a surface area of about 150 m 2 /g to about 4000 m 2 /g. In some embodiments the graphene material may have a surface area of about 200 m 2 /g to about 1000 m 2 /g, e.g. , about 400 m 2 /g to about 500 m 2 /g.
• the graphene oxide may be platelets having one or more dimensions in the nanometer to micron range.
• the platelets may have dimensions in the x, y and/or z dimension.
• the platelets may have: an average x dimension between about 0.05 um to about 50 um, or any value in a range bounded by, or between, any of these lengths; an average y dimension of 0.05 um to about 50 um, or any value in a range bounded by, or between, any of these lengths.
• the graphene oxide comprises GO platelets, the platelets defining an average size of about 0.05 ⁇ to about 50 ⁇ .
• the graphene material may not be modified and may comprise of a non-functionalized graphene base.
• the graphene material may comprise a modified graphene.
• the modified graphene can comprise an optionally substituted graphene material.
• the optionally substituted graphene material may comprise a functionalized graphene. In some embodiments, more than about 90%, about 80%, about 70%, about 60% about 50%, about 40%, about 30%, about 20%, about 10% of the graphene may be functionalized. In other embodiments, the majority of graphene material may be functionalized. In still other embodiments, substantially all the graphene material may be functionalized.
• the functionalized graphene may comprise a graphene base and functional compound.
• a graphene may be "functionalized,” becoming functionalized graphene when there is one or more types of functional compounds not naturally occurring on GO are substituted instead of hydroxide in the acetic acid groups of one or more hydroxide locations in the graphene matrix.
• the graphene base may be selected from reduced graphene oxide and/or graphene oxide.
• the graphene base may be selected from:
• multiple types of functional compounds are used to functionalize the graphene material in addition to comprising at least one epoxide group. In other embodiments, only one type of functional compound can be utilized to functionalize the graphene material. In some embodiments, the functional compounds comprise an epoxide group.
• the epoxide group may comprise a epoxide- based compound having the functional group:
• the epoxide groups can be the by-product of oxidation of the graphene to create graphene oxide.
• the epoxide groups are formed on the surface of the graphene base by additional chemical reactions.
• the epoxide groups are a mix of those formed during oxidation and those formed by additional chemical reactions.
• the graphene material may be a crosslinked graphene, where the graphene material may be crosslinked with at least one other graphene base by a crosslinker material/bridge.
• the graphene material may comprise crosslinked graphene material where at the graphene bases are crosslinked such that at least about 1 %, about 5 %, about 10 %, about 20 %, about 30 %, about 40 % about 50 %, about 60 %, about 70 %, about 80 %, about 90 %, about 95 %, or all of the graphene material may be crosslinked.
• the majority of the graphene material may be crosslinked.
• some of the graphene material may be crosslinked such that at least 5 % of the graphene material may be crosslinked with other graphene material.
• the amount of crosslinking may be estimated by the wt% of the crosslinker/precursor as compared with the total amount of polymer present.
• one or more of the graphene base(s) that are crosslinked may also be functionalized.
• the graphene material may comprise both crosslinked graphene and non-crosslinked, functionalized graphene.
• the adjacent graphene oxide material can be covalently bonded to each other by one or more crosslinks.
• the graphene oxide material can be bonded to the support covalently and/or by Van der Waals forces.
• the crosslinks can be a product of a crosslinker compound (CLC).
• the crosslinker can comprise a crosslinker selected from the group:
• Link can be the body of the crosslinker.
• the resulting linkage can be represented as:
• GO represents an optionally substituted graphene oxide and Link can be the body of the crosslinker.
• the cross-link can be made by a crosslinker to create a covalent linkage that links two or more optionally substituted graphene oxides.
• the crosslinker compound (CLC) containing nucleophilic groups can comprise an optionally substituted biphenyl, optionally substituted triphenylmethane, optionally substituted diphenylamine, optionally substituted 9H-carbazole, or optionally substituted 2,2-bis(hydroxymethyl)propane-1 ,3- diol. While not wanting to be bound by theory the presence of a nucleophilic group may increase the reactivity of the corresponding position to an epoxide group on the graphene platelet.
• the crosslinker can crosslink at least one of the -NH and/or -OH substituents at Ri , R 2 , R3 and/or R 4 , for example, two adjacent graphene oxides, three adjacent graphene oxides, or four adjacent graphene oxides. In some embodiments, the crosslinker can crosslink at least one of the -NH and/or -OH substituents at Ri and/or R 2 , for example, two adjacent graphene oxides. In some embodiments, Ri and R 2 are independently NH 2 or OH. In some embodiments, Ri and R 2 are both NH 2 . In some embodiments, Ri and R 2 are both OH.
• suitable crosslinkers include potassium tetraborate (“KBO”), a benzoic acid derivate (e.g., 3,5-diaminobenzoic acid (“DABA”)), and 2,5-dihydroxyterephthalic acid (“DHTA”), which can be used individually or in combination with each other or other crosslinkers.
• KBO potassium tetraborate
• DABA 3,5-diaminobenzoic acid
• DHTA 2,5-dihydroxyterephthalic acid
• the crosslinker can be an optionally substituted biphenyl represented by Formula 1.
• R 3 and R 4 can be independently H, OH, NH 2 , CH 3 , -C0 2 H, -C0 2 Li, -C0 2 Na, - C0 2 K, -SO 3 H, -SO 3 U, -S0 3 Na, or -SO 3 K.
• at least two of Ri , R 2 , R 3 , and R 4 can be a nucleophilic group.
• the site of the nucleophilic group can be the location of the covalent linkage with the epoxide.
• Ri and R 2 can be independently a nucleophilic group, for example, NH 2 or OH.
• R 3 and R 4 can be independently OH, S0 3 H, S0 3 Na, or S0 3 K. In some embodiments, R 3 and R 4 can be independently OH, S0 3 Na, or S0 3 K. In some embodiments, the substituted biphenyl can comprise:
• the crosslinker can be an optionally substituted triphenylmethane represented by Formula 2:
• R 5 can be H, CH 3 , or C 2 H 5 ;
• R 6 can be H, CH 3 , -C0 2 H, -C0 2 Li, -C0 2 Na, - C0 2 K, -S0 3 H, -S0 3 Li, -S0 3 Na, or -S0 3 K; and n can be 0, 1 , 2, 3, 4, or 5.
• R 5 can be H, CH 3 , or C 2 H 5 .
• R 5 can be CH 3 .
• R 6 can be independently H, CH 3 , OH, or an organic acid group or a salt thereof, such as -C0 2 H, -C0 2 Na, -C0 2 Li, -C0 2 K, -S0 3 H, -S0 3 Na, -S0 3 Li, or -S0 3 K.
• R 6 can be S0 3 Na.
• n can be 4.
• at least two of Ri, R 2 , R 5 , and R 6 can be a nucleophilic group.
• the site of the nucleophilic group can be the location of the covalent linkage with the epoxide.
• Ri and R 2 can be independently a nucleophilic group, for example, NH 2 or OH.
• R 5 can be an alkyl group.
• the optionally substituted triphenylmethane can comprise:
• the crosslinker is an optionally substituted diphenylamine or optionally substituted 9H-carbazole represented by formula 3A or 3B:
• R 7 and R 8 can be independently H, CH 3 , C0 2 H, C0 2 Li, C0 2 Na, C0 2 K, S0 3 H, S0 3 Li, S0 3 Na, or S0 3 K; k can be 0 or 1 ; m can be 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10; and p can be 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10.
• a dashed line represents the presence or absence of a bond.
• compounds represented by Formulas 3B-1 and 3B-2 as shown below are included.
• Ri, R 2 , R 6 , and R 7 can be a nucleophilic group.
• the site of the nucleophilic group can be the location of the covalent linkage with the epoxide.
• Ri and R 2 can be independently a nucleophilic group, for example, NH 2 or OH.
• R 7 and R 8 can be independently H, CH 3 , or an organic acid group or a salt thereof, such as -C0 2 H, -C0 2 Na, -C0 2 Li, -C0 2 K, -S0 3 H, -S0 3 Na, -S0 3 Li, or -S0 3 K.
• R 6 and R 7 can be independently -S0 3 K. In some embodiments, R 7 and R 8 can be both -S0 3 K. In some embodiments, k can be 0. In some embodiments, k can be 1 . In some embodiments, m can be 0. In some embodiments, m can be 3. In some embodiments, p can be 0. In some embodiments, p can be 3. In some embodiments, m and p can be both 0. In some embodiments, m and p can be both 3.
• the optionally substituted diphenylamine or optionally substituted 9H-carbazole can be:
• the optionally substituted bishydroxy methyl propanediol compound can be described by formula 4:
• R 9 , Ri 0 , R-n, and Ri 2 can be independently:
• each Ri 3 can independently be a nudeophilic group.
• the site of the nudeophilic group can be the location of the covalent linkage with the epoxide.
• Ri 3 can be independently OH, NH 2 , C0 2 H, C0 2 Na, C0 2 K, S0 3 H, S0 3 Na, or S0 3 K. While not wanting to be bound by theory the presence of a nudeophilic group may increase the reactivity of the corresponding position to an epoxide group on the graphene platelet.
• r can be 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10.
• the optionally substituted bishydroxy methyl propanediol compound can comprise:
• the resulting linkage can be created by a substitution reaction, wherein an epoxide functional group of the functionalized graphene oxide can be opened. While not wanting to be limited by theory, opening the epoxide ring and may result in a carbon becoming covalently bonded to the crosslinker, taking the place of a hydrogen atom in the NH 2 group or hydrogen in an OH group.
• C-N bonding to the epoxide functional groups instead of forming amide bonds will result in higher incidences of crosslinking between vertically stacked graphene oxide (i.e., crosslinks normal to the graphene's surface) because amide bonds may depend on the presence of a carboxyl groups that are predominantly on the edge of the graphene instead of in the body or planar interior of the graphene and may provide in-plane bonding between adjacent graphene materials.
• the reaction for the crosslinker and the optionally substituted graphene oxide can form a crosslink vertically between stacked optionally substituted graphene oxides.
• one of many potential mechanisms for killing microbes can be the presence of active sites on the graphene platelets and that the crosslinker can be chosen such that active sites on the graphene are not completely consumed by the crosslinking process, thus allowing for the generation of reactive species.
• the amount or reactivity of the crosslinker can be chosen so as to ensure the existence of graphene active sites.
• a non-limiting example can be represented as:
• the crosslinker material comprises an aqueous solution of about 2 wt% to about 50 wt% crosslinker. In some embodiments, the crosslinker material comprises an aqueous solution of about 2.5 wt% to about 30 wt% crosslinker. In some embodiments, the crosslinker material comprises an aqueous solution of about 5 wt% to about 15 wt% crosslinker.
• the weight ratio of optionally substituted graphene oxide to substituted biphenyl can be from about 1 : 1000 to about 50: 1 . In some embodiments, the weight ratio of optionally substituted graphene oxide to substituted biphenyl can be from about 1 : 100 to about 15: 1 . In some embodiments, the weight ratio of optionally substituted graphene oxide to substituted biphenyl can be about 1 : 15 to about 1 : 1 . In some embodiments, the weight ratio of optionally substituted graphene oxide to substituted biphenyl can be about 1 1 to about 1 : 1 .
• the crosslinker can crosslink a first interior carbon atom on a face of a first optionally substituted graphene oxide platelet to a second interior carbon atom on a face of a second optionally substituted graphene oxide platelet.
• An interior carbon atom on a face of an optionally substituted graphene oxide platelet is a carbon atom that is not on an outer border of the optionally substituted graphene oxide platelet.
• the interior carbon atoms are shown in bold. It should be noted that the structure below is depicted only to illustrate the principle of an interior carbon atom, and does not limit the structure of graphene oxide.
• the support can be a part of the membrane.
• Non limiting examples of such supports include reverse osmosis membranes, tapes, or anything that can be used as a substrate, either flexible or non-flexible.
• the support material may be polymeric.
• the support material can comprise hollow fibers.
• the support can be the article to be protected from microbial growth.
• the article to be protected can be any item where biological growth is undesirable. Examples include but are not limited to ship hull's, treatment basins, pipes, desalination filters, air filters, HVAC system components, hospital equipment and furnishings, counter-tops, lavatory furnishings, and the like.
• the support may comprise a porous material.
• the support can comprise a non-porous material.
• the material may be polymeric.
• the polymer may be polyamide, polyvinylidene fluoride, polyethylene terephthalate, polysulfone, polyether sulfone, and/or mixtures thereof.
• the porous support can comprise a polyamide (e.g. Nylon).
• the porous material may be a polysulfone based ultrafiltration membrane.
• the porous material can be polyvinylidene fluoride.
• the porous material may comprise hollow fibers.
• the hollow fibers may be cast or extruded.
• the hollow fibers may be made, for example, as described in United States Patent Nos., 4,900,626 and 6,805,730 and United States Patent Publication No. 2015/0165,389, which are all incorporated by reference in their entireties.
• the gas permeability of the membrane may be less than 0.100 cc/m 2 -day, 0.010 cc/m 2 -day, and/or 0.005 cc/m 2 -day.
• a suitable method for determining gas permeability is disclosed in United States Patent Publication US2014/0272.350, ASTM D3985, ASTM F1307, ASTM 1249, ASTM F2622, and/or ASTM F1927, which are incorporated by reference in their entireties for their disclosure of determining gas (oxygen) permeability %, e.g., oxygen transfer rate (OTR).
• OTR oxygen transfer rate
• the moisture permeability of the membrane may be greater than 10.0 gm/m 2 -day, 5.0 gm/m 2 -day, 3.0 gm/m 2 -day, 2.5 gm/m 2 -day, 2.25 gm/m 2 -day and/or 2.0 gm/m 2 -day.
• the moisture permeability may be a measure of water vapor permeability/transfer rate at the above described levels. Suitable methods for determining moisture (water vapor) permeability are disclosed in Caria, P.
• the selective permeability of the membrane may be reflected in a ratio of permeabilities of water vapor and at least one selected gas, e.g., oxygen and/or nitrogen, permeabilities.
• the membrane may exhibit a water-vapor permeability to gas permeability ratio, e.g., WVTR/OTR, of greater than 50, greater than 100, greater than 200, and/or greater than 400.
• the selective permeability may be a measure of water vapor: gas permeability/transfer rate ratios at the above described levels. Suitable methods for determining water vapor permeability and/or gas permeability have been disclosed herein.
• the membrane can have anti-microbial properties, or kill microbes in a working fluid.
• the microbes killed can comprise escherichia coli (ATCC® 8739, American Type Culture Collection (ATCC), Manassas, VA USA).
• the membrane can have an antibacterial effectiveness of 2.0 or more. The antibacterial effectiveness can be determined by standard JIS Z 2801 (2010).
• the working fluid can be either liquid, gas, or a combination thereof (e.g., saturated air).
• Non-limiting examples of a liquid working fluid can be the brine/salt water or fresh water in a desalination plant, water in a waste treatment plant, ocean water for a ship, air in a HVAC system, or air in an enclosed space.
• the anti-microbial membrane may be disposed between an object to be protected and a fluid reservoir.
• the fluid reservoir can contain microbes.
• the membrane can kill microbes on the membrane.
• solvents may also be present in the antimicrobial element.
• solvents used in manufacture of material layers, solvents include, but are not limited to, water, a lower alkanol such as but not limited to ethanol, methanol, isopropyl alcohol, xylenes, cyclohexanone, acetone, toluene and methyl ethyl ketone, and mixtures thereof.
• a lower alkanol such as but not limited to ethanol, methanol, isopropyl alcohol, xylenes, cyclohexanone, acetone, toluene and methyl ethyl ketone, and mixtures thereof.
• Some embodiments can use water as a solvent.
• the anti-microbial membrane, 100 may comprise at least a substrate element, 120, and the aforementioned composite coating, 110. The coating is exposed to the working fluid, 130.
• the substrate, 120 can comprise the article to be protected from microbes.
• the article to be protected is a reverse osmosis membrane and the membrane is on the surface of the membrane.
• the article to be protected is the hull of a ship and the membrane is a coating on the hull.
• a material may be included in the antimicrobial membrane 100 to increase or improve the interaction membrane 100 has with the working fluid 130.
• the added material or spacer material may improve the flux or movement of the working fluid over or through membrane 100.
• the added material creates space or volume within the anti-microbial membrane 100.
• the added material creates or increases the roughness or irregularity of the surface of the anti-microbial membrane 100.
• the added material is silica, such as silica nanoparticles, or another suitable material that creates the desired fluid flux or surface texture.
• the size of the particles can be between 1 nm and 500 nm, between 40 nm and 300 nm, or between 70 nm and 250 nm. In some embodiments, the particle size is 5 nm, 7 nm, 10 nm, 20 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, or 220 nm. In addition, other nanoparticles having similar size and behavioral characteristics include nanoparticles of Fe 3 0 4 , ⁇ 2, Zr0 2 , or AI2O3.
• the spacer material has a weight percentage of about 1 % to about 10% relative to the total weight of composite coating 110. In some embodiments, the spacer material has a weight percentage of about 6% or about 6.6% relative to the total weight of composite coating 110.
• composite coating 110 has a thickness ranging from about 10 nm to about 10 ⁇ .
• Composite coating 110 can have a thickness of 50 nm, 100 nm, 1 10 nm, 150 nm, 180 nm, 200 nm, 220 nm, 300 nm, 400 nm, 500 nm, 600 nm, 1 ⁇ , 1 .4 ⁇ , 5 ⁇ , or any value close to or between these values.
• the thickness is less than about 20 ⁇ , less than about 15 ⁇ , less than 10, or less than about 5 ⁇ .
• composite coating 110 is not thick enough to be self-supported. In other words, in some embodiments, composite coating 110 must be applied to or adhered to a support structure or surface, such as substrate element 120.
• membrane 100 is prepared by applying composite coating 110 to substrate element 120 and then exposing the resulting membrane to an elevated temperature for a period time. In some embodiments, this process cures membrane 100. In some embodiments, after being applied to substrate element 120 composite coating 110 is allowed to air dry for a period of time before being exposed to an elevated temperature. In some embodiments, the elevated temperature ranges from about 30 °C to about 300 °C, from about 60 °C to about 200 °C, or from about 70 °C to about 150 °C. In some embodiments, the elevated temperature is about 70 °C, about 85 °C, about 90 °C, about 130 °C, about 140 °C, or any value close to or between these values.
• the period of exposure is from about 1 minute to about 180 minutes, from about 2 minutes to about 150 minutes, from about 3 minutes to about 120 minutes. In some embodiments, the period of exposure is about 3 minutes, about 6 minutes, about 8 minutes, about 20 minutes, about 30 minutes, about 60 minutes, about 90 minutes, about 120 minutes, or any value close to or between these values.
• a method for killing microbes on a surface can be described, as shown in Figure 5.
• the method can comprise providing any of aforedescribed antimicrobial membranes.
• providing any of the aforedescribed membranes can comprise coating the surface to be protected with any of the said membranes.
• the membrane can comprise a composite coating.
• the membrane can comprise a support and a composite coating on the support material.
• the composite coating can comprise graphene oxide and a crosslinker.
• the crosslinker can comprise potassium tetraborate, 3,5-diaminobenzoic acid, 2,5-dihydroxyterephthalic acid, an optionally substituted biphenyl, optionally substituted triphenylmethane, optionally substituted diphenylamine, optionally substituted 9H-carbazole, or optionally substituted 2,2-bis(hydroxymethyl)propane-1 ,3- diol as described elsewhere in this application.
• the substituted biphenyl can be described by Formula 1 :
• the substituted biphenyl can comprise:
• the crosslinker can be an optionally substituted triphenylmethane represented by Formula 2:
• the optionally substituted triphenylmethane can comprise:
• the crosslinker is an optionally substituted diphenylamine or optionally substituted 9H-carbazole represented by Formula 3A or 3B:
• the optionally substituted diphenylamine can comprise:
• the optionally substituted bishydroxy methyl propanediol compound can be described by Formula 4:
• R 9 , Ri 0 , Rn , and Ri 2 can be independently:
• the optionally substituted bishydroxy methyl propanediol compound can comprise:
• the mass ratio of graphene oxide to crosslinker can be from 1 : 1000 to 50:1 . In some embodiments, the mass ratio of graphene material to crosslinker can range from about 1 : 100 to about 15:1. In some embodiments, the mass ratio of graphene material to crosslinker can range from about 1 :15 to about 1 :1.
• the support can be porous. In other embodiments, the support can be non-porous. In some embodiments, the support can be part of the coating. In other embodiments, the support can be separate from the coating. In some embodiments, where the support is separate from the coating, the support can comprise the article to be protected from microbes. Examples include but are not limited to ship hull's, treatment basins, pipes, desalination filters, air filters, HVAC system components, hospital equipment and furnishings, counter-tops, lavatory furnishings, and the like.
• the method further comprises exposing the membrane to a working fluid.
• the working fluid can contain microbes, whereby the membrane kills microbes as a result of exposure to the working fluid.
• the microbes controlled can comprise escherichia coli (ATCC® 8739, ATCC).
• the membrane can have an antibacterial effectiveness of 2.0 or more. The antibacterial effectiveness can be determined by standard JIS Z 2801 (2012).
• the working fluid can comprise air.
• the working fluid can comprise water.
• the working fluid can comprise a mixture of air and water vapor.
• the mixture of air and water vapor can have a relative humidity ranging from about 100 % to about 0 %. In some embodiments, the relative humidity can range from 0 %, 20 %, 50 %, 60 %, 78 %, 80 %, to 90 %, to 93 % to 100%, or any combination thereof.
• GO was prepared from graphite using modified Hummers method. Graphite flake (2.0g, Aldrich, 100 mesh) was oxidized in a mixture of NaN0 3 (2.0g), KMn0 4 (10g) and concentrated 98% H 2 S0 4 (96 mL) at 50 °C for 15 hours. The resulting pasty mixture was then poured into ice (400g) followed by the addition of 30% hydrogen peroxide (20 mL). The resulting solution was stirred for 2 hours to reduce the manganese dioxide, filtered through filter paper, and washed with deionized (Dl) water.
• Dl deionized
• the solid was collected and dispersed in Dl water by stirring, centrifuged at 6300 rpm for 40 minutes, and demayted the aqueous layer. The remaining solid was dispersed in Dl water, and washing process repeated 4 times. The purified GO was then dispersed in Dl water under sonication (20 W) for 2.5 hours for a GO dispersion (0.4% wt).
• CLC-2.1 Sodium 4-(4-(1,1-bis(4-hydroxyphenyl)ethyl)phenoxy)butane-1- sulfonate (CLC-2.1) Preparation: To a stirring quantity of tert-butanol (90 mL) (Aldrich) at room temperature, 4,4',4"-(ethane-1 ,1 ,1-triyl)triphenol (5 g, 16 mmol) (Aldrich) was added followed by sodium tert-butoxide (1.57g, 16 mmol) (Aldrich). The mixture was then stirred at 1 10 °C for 15 minutes.
• N1, N3-bis(4-nitrophenyl)benzene-1,3-diamine (CLC-3.1) Preparation: A mixture of 4-fluoro-1 -nitrobenzene (10.6 mL, 100 mmol) (Aldrich), meta- phenylenediamine (5.4g, 50 mmol) (Aldrich) and potassium carbonate (16.6g, 120 mmol) (Aldrich) in anhydrous dimethyl sulfoxide (DMSO) (80 mL) (Aldrich) was heated to 105 °C for 20 hours. The resulting mixture was poured into water (250 mL) slowly and then extracted with dichloromethane (500 mL) (Aldrich).
• DMSO dimethyl sulfoxide
• IC-1 Dimethyl 4,4'-((2,2-bis((4-(methoxycarbonyl)phenoxy)methyl)- propane-1 ,3-diyl)bis(oxy))dibenzoate (IC-1): Into ⁇ /, ⁇ /'-dimethylformamide (100 mL) (Aldrich) at room temperature, pentaerythritol tetrabromide (6 g, 15.5 mmol, Aldrich) was added with stirring followed by methyl 4-hydroxybenzoate (9.42 g, 61.9 mmol, Aldrich), and then potassium carbonate (27.80 g, 201.5 mmol, Aldrich). The resulting mixture was heated to 150 °C overnight.
• Crosslinked GO membrane (AM-1) Preparation: 4 mg/mL of a graphene oxide (GO) aqueous dispersion prepared as described in Example 1.1 was diluted to 0.1 wt% by de-ionized water. Second, a 0.1 wt% CLC-1.1 aqueous solution was created by dissolving appropriate amounts of CLC-1.1 in Dl water. Then, a coating mixture was created by mixing a mixture consisting of 0.1 wt% CLC-1.1 aqueous solution and a mixture consisting of 0.1 wt% graphene oxide aqueous dispersion at a weight ratio of 3: 1. The resulting solution was then was stirred at room temperature for 10 minutes.
• the resulting solution was cast onto a Reverse Osmosis (RO) membrane (ESPA Membrane, Hydranautics) by dropping the solution on membrane surface using a die caster (Taku-Die 200, Die-Gate Co., Ltd., Tokyo, Japan), set to coat 0.6 g of mixture per 90 cm 2 . After drying in air, the membrane was put in an oven (DX400, Yamato Scientific Co., Ltd. Tokyo, Japan) at 85 °C for 30 minutes in order to remove water and crosslink the membrane, resulting in a membrane that was 1 .4 ⁇ thick with 1 :3 mass ratio GO/CLC-1.1 membrane, or AM-1.
• RO Reverse Osmosis
• Example 1 .2.2 additional anti-microbial elements were constructed. The methods used were similar to the one in Example 1.2.1 with the exception that parameters were varied for the specific elements as identified in Table 1.
• CM-1 Comparative Element/Hydranautics Membrane
• RO reverse osmosis
• Example 2.1 Measurement of Anti-Microbial Properties.
• example AM-1 was measured using a procedure that conformed to Japanese Industrial Standard (JIS) Z 2801 :2012 (English Version pub. Sep. 2012) for testing anti-microbial product efficacy, which is incorporated herein in its entirety.
• JIS Japanese Industrial Standard
• the organisms used in the verification of antimicrobial capabilities were escherichia coli. (ATCC® 8739, ATCC).
• a broth was prepared by suspending 8 g of the nutrient powder (DifcoTM Nutrient Broth, Becton, Dickinson and Company, Franklin Lakes, NJ USA) in 1 L of filtered, sterile water, mixing thoroughly and then heating with frequent agitation. To dissolve the powder the mixture was boiled for 1 minute and then autoclaved at 121 °C for 15 minutes. The night before testing, the escherichia coli. were added to 2-3 mL of the prepared broth and grown overnight.
• the nutrient powder DifcoTM Nutrient Broth, Becton, Dickinson and Company, Franklin Lakes, NJ USA
• the resulting culture was diluted in fresh media and then let grow to a density of 10 8 CFU/mL (or approximately diluting 1 mL of culture into 9 mL of fresh nutrient broth). The resulting solution was then left to re-grow for 2 hours. The re-growth was then diluted by 50 times in sterile saline (NaCI 8.5 g (Aldrich) in 1 L of distilled water) to achieve an expected density of about 2 x 10 6 CFU/mL. 50 ⁇ of the dilute provides the inoculation number.
• test specimens and cover film were transferred with sterile forceps into 50 mL conical tubes with 20 mL of saline and the bacteria for each sample was washed off each sample by mixing them for at least 30 seconds in a vortex mixer (120V, VWR Arlington Heights, IL USA).
• bacteria cells in each solution were then individually transferred using a pump (MXPPUMP01 , EMD Millipore, Billerica, MA USA) combined with a filter (Millflex-100, 100 mL, 0.45 ⁇ , white gridded, MXHAWG124, EMD Millipore) into individual cassettes prefilled with tryptic soy agar (MXSMCTS48, EMD Millipore).
• a pump MXPPUMP01
• EMD Millipore Billerica, MA USA
• a filter Millflex-100, 100 mL, 0.45 ⁇ , white gridded, MXHAWG124, EMD Millipore
• the cassettes were then invented and then placed in an incubator at 37 °C for 18 hours. After 18 hours, the number of colonies on the cassettes was counted. If there were no colonies a zero was recorded. For untreated pieces, after 24 hours the number of colonies was not less than 1 x 10 3 colonies. The tests were run three times for each sample type to assure validity and repeatability of the data. Similar experiments were run for samples AM-2 thru AM-23, with the results shown in Table 2. Even assuming that the TNTC samples had counts equivalent to the approximate maximum count value of around 4000 colonies, the antibacterial activity can be estimated at 3.8. Thus, the antibacterial activity is at least 3.8, which supports an antibacterial activity of 2.0 or higher. As a result, it was determined that the crosslinked GO coatings disclosed herein are an effective biocide that could help prevent microbe buildup on surfaces.
• TNTC denotes too numerous to count.
• a number of antimicrobial elements were prepared in a manner similar to AM-1 using different crosslinkers in varying ratios and deposited in varying thicknesses. In some samples, additional crosslinkers or other materials were used to test the effect of those materials on the performance. The details of each antimicrobial element and the results obtained for each are shown in Table 3 below.
• silica nanoparticles in this sample have a size of 80 nm. The same is true for samples 7, 8, and 9.
• Embodiment 1 An anti-microbial membrane comprising:
• a composite coating the support comprising a crosslinked optionally substituted graphene oxide compound, where the graphene was crosslinked by a crosslinker selected form the group consisting of a benzoic acid derivative, an optionally substituted biphenyl of Formula 1 , an optionally substituted triphenylmethane of Formula 2, an optionally substituted diphenylamine or an optionally substituted 9H- carbazole represented by Formula 3A or 3B, and an optionally substituted bishydroxymethyl propanedi 4:
• Ri and R 2 are independently NH 2 or OH; and R 3 and R 4 are independently OH, S0 3 H, S0 3 Na, or S0 3 K;
• R 5 is H, CH 3 , or C 2 H 5 ;
• R 6 is H, CH 3 , -C0 2 H, -C0 2 Li, -C0 2 Na, - C0 2 K, -S0 3 H, -S0 3 Li, -S0 3 Na, or -S0 3 K; and n is 0, 1 , 2, 3, 4, or 5;
• R 7 and R 8 are independently H, CH 3 , C0 2 H, C0 2 Li, C0 2 Na, C0 2 K, SO 3 H, SO 3 L1, S0 3 Na, or S0 3 K; k is 0 or 1 ; m is 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10; and p is O, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10;
• R 9 , Ri 0 , Rn , and Ri 2 can be independently: wherein R13 is independently OH, NH 2 , C0 2 H, C0 2 Na, C0 2 K, SO3H , S0 3 Na, or SO3K and r is 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10; whereby the membrane kills microbes as determined by having an antibacterial effectiveness of 2.0 or more.
• Embodiment 2 The membrane of embodiment 1 , wherein the optionally substituted biphenyl is:
• Embodiment 3 The membrane of embodiment 1 , wherein the optionally substituted triphenylmethane is:
• Embodiment 4 The membrane of embodiment 1 , wherein the optionally substituted diphenylamine or optionally substituted 9H-carbazole is:
• Embodiment 5 The membrane of embodiment 1 , wherein the optionally substituted bishydroxymethyl propanediol compound is:
• Embodiment 6 The membrane of embodiment 1 , wherein the benzoic acid derivative is 3,5-diaminobenzoic acid.
• Embodiment 7 The membrane of embodiment 1 or 6, wherein the composite further comprises at least one of potassium tetraborate and 2,5- dihydroxyterephthalic acid.
• Embodiment s. The membrane of embodiment 1 , 2, 3, 4, 5, 6, or 7, wherein the optionally substituted graphene oxide comprises platelets.
• Embodiment 9 The membrane of embodiment 8, wherein the platelets are between about 0.05 ⁇ and about 50 ⁇ .
• Embodiment 10 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, or 9, wherein the mass ratio of graphene oxide to crosslinker in the composite is a value ranging from 1 : 1000 to 50: 1.
• Embodiment 11 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, or 9, wherein the mass ratio of graphene oxide to crosslinker in the composite is a value ranging from 1 :4 to 12: 1.
• Embodiment 12 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, or 9, wherein the mass ratio of graphene oxide to crosslinker in the composite is a value ranging from 1 :4 to 1 : 1.
• Embodiment 13 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, or 9, wherein the mass ratio of graphene oxide to crosslinker in the composite is a value ranging from 4: 1 to 1 1 : 1.
• Embodiment 14 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, or 13, wherein the composite further comprises a spacer material.
• Embodiment 15 The membrane of embodiment 14, wherein the spacer material comprises silica nanoparticles.
• Embodiment 16 The membrane of embodiment 15, wherein the silica nanoparticles have a size of about 3 nm to about 20 nm.
• Embodiment 17 The membrane of embodiment 15, wherein the silica nanoparticles have a size of about 50 nm to about 250 nm.
• Embodiment 18 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, or 17, wherein the composite coating on the support has a thickness of about 0.9 ⁇ to about 3 ⁇ .
• Embodiment 19 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, or 17, wherein the composite coating on the support has a thickness of about 10 nm to about 500 nm.
• Embodiment 20 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, or 17, wherein the composite coating on the support has a thickness of about 100 nm to about 300 nm.
• Embodiment 21 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, or 20, wherein the membrane is prepared by applying the composite to the support and exposing the resulting membrane to a temperature of about 70 °C to about 200 °C for a period of about 2 minutes to about 60 minutes.
• Embodiment 22 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, or 20, wherein the membrane is prepared by applying the composite to the support and exposing the resulting membrane to a temperature of about 80 °C to about 150 °C for a period of about 3 minutes to about 30 minutes.
• Embodiment 23 The membrane of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , or 22, wherein the support is the article to be protected from microbial growth.
• Embodiment 24 A method of killing microbes, the method comprising:
• the membrane kills microbes as a result of exposure to the working fluid as determined by having an antibacterial effectiveness of 2.0 or more.

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• 2017
  • 2017-09-08 JP JP2019517954A patent/JP6770639B2/ja active Active
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