Patent Description:
Conventional electrospray is effective in creating small charged drops for ionization, atomization and aerosol applications, but inefficient at forming uniform and/or thin coatings and films, particularly at high throughput production rates.

<CIT> discloses a system for electrospray ionization of discrete samples, the system comprising: an electrospray ionization emitter nozzle; a one-dimensional segmented sample array directly coupled to the electrospray ionization emitter nozzle, the array comprising a plurality of sample plugs including a first medium, the sample plugs separated by spacer plugs including a second medium; a pumping means operable to advance the array to the electrospray ionization emitter nozzle; and a power supply electrically coupled to a sample plug within or proximate to the electrospray ionization emitter nozzle and electrically coupled to a spray receiver. <CIT> discloses a process for preparing a nanofiber, the process comprising: electrospinning a liquid polymer with a high velocity gas stream; wherein: (a) the liquid polymer surrounds the high velocity gas; (b) the high velocity gas surrounds the liquid polymer; (c) the liquid polymer is electrospun through a high temperature nozzle; (d) the liquid polymer is electrospun and the liquid polymer is provided along the same longitudinal axis; or (f) any combination thereof. <CIT> discloses a method for depositing an electro-active material over a flexible conductive substrate, comprising: transferring a flexible conductive substrate over a first heated roller while simultaneously spraying a first electro-active material over the flexible conductive substrate; and transferring the flexible conductive substrate over a second heated roller while simultaneously spraying a second electro-active over the flexible conductive substrate, wherein the first and second electro-active material each comprise a cathodically active material or an anodically active material.

According to the invention, there is provided a process for manufacturing a film or coating (<NUM>), the process comprising generating a plume or aerosol by providing a fluid stock to a first inlet of a first conduit of an electrospray nozzle, the fluid stock comprising a liquid and an inclusion comprising graphene, graphene oxide, or reduced graphene oxide; the plume or aerosol being generated by providing a voltage to the nozzle and electrospraying the fluid stock in the presence of a high velocity gas (<NUM>), wherein the high velocity gas is provided by providing a pressurized gas to a second inlet of a second conduit of the electrospray nozzle thereby providing the high velocity gas with a velocity of <NUM>/s or more at a second outlet of the second conduit; the high velocity gas (<NUM>) and the plume or aerosol having a directional mean within <NUM> degrees of one another; and the film or coating (<NUM>) having a thickness of about <NUM> to about <NUM>.

Disclosed in certain instances herein are processes for manufacturing films or coatings, such as thin layer films or coatings. The coatings themselves are not according to the invention. The processes of the invention are as described in the paragraph above. In some instances, processes disclosed herein are suitable for and configured to manufacture uniform depositions, such as having uniform thickness. In further or alternative instances, processes disclosed herein are exceptionally suitable for and configured to manufacture two (or more) component systems, or one component systems, wherein distribution of the components is highly uniform.

In certain instances, disclosed herein is a process for manufacturing a film or coating, the process comprising generating a plume or aerosol from a fluid stock. The fluid stock comprises a liquid and an inclusion. The plume or aerosol is generated using an electrospray technique. The process further comprises generating the plume or aerosol in the presence of a high velocity gas. In specific instances, the high velocity gas facilitates the fine dispersion of the plume or aerosol particulates, which, in turn, facilitates the controlled and uniform deposition of the liquid and/or inclusion parts on a substrate surface. The direction of the flow of the gas and the plume/aerosol are in the same general direction and have a directional mean within <NUM> degrees of one another).

In some instances, disclosed herein is a system or process for manufacturing a thin layer film or coating having a thickness of about <NUM> to about <NUM>, e.g., about <NUM> micron to about <NUM>), although the systems themselves are not according to the claimed invention. In some instances, thicker depositions (e.g., films or coatings) are also contemplated (e.g., about <NUM> to about <NUM>), although these depositions are not produced by the process of the invention. The system is configured to or the process comprises injecting a fluid stock into a gas stream. In specific instances, the fluid stock is injected into the gas stream in a substantially parallel direction (e.g., within about <NUM> degrees, about <NUM> degrees, about <NUM> degrees, or the like of parallel). In specific instances, the process comprises producing an electrostatically charged plume. In more specific instances, the plume comprises a plurality of nanoscale particles and/or droplets (e.g., < <NUM> micron in average dimension or diameter). The particles or droplets (e.g., nanoscale droplets (e.g., the droplets comprising solutions, suspensions, solution-suspensions, and/or solid particles)) comprise an additive and a liquid medium. In certain instances, micro-scale droplets are present in the plume, such as when larger additive inclusions are utilized, larger droplets are produced by processes herein. In some instances, plumes described herein comprise micro-scale particles or droplets, such as having an average dimension or diameter of at least <NUM> micron (e.g., about <NUM> micron to about <NUM> micron, about <NUM> micron to about <NUM> micron, or the like).

The plume is generated by: providing a fluid stock to a first inlet of a first conduit of an electrospray nozzle. In specific instances, the first conduit being enclosed along the length of the conduit by a wall having an interior surface and an exterior surface, the first conduit having a first outlet. The fluid stock comprises a liquid medium and an additive. The process comprises providing a (e.g., direct current) voltage to the nozzle (e.g., wall of the first conduit). In some instances, the voltage provides an electric field (e.g., at the first outlet) (e.g., which field at least partially drives the electrospraying process). The process further comprises providing a pressurized gas (e.g., provided from a gas supply, such as a pump, a pressurized reservoir, or the like) (e.g., a system being configured to provide a pressurized gas) to a second inlet of a second conduit of the nozzle, e.g., thereby providing high velocity gas at a second outlet of the second conduit (the high velocity gas having a velocity of <NUM>/s or more, such as about <NUM>/s or more, about <NUM>/s or more, or the like). In some instances, the second conduit is enclosed along the length of the conduit by a second wall having an interior surface. The second conduit has a second inlet and a second outlet. Generally, the second conduit has a second diameter, and the first conduit is positioned inside the second conduit. In specific instances, the exterior surface of the first wall and the interior surface of the second wall are separated by a conduit gap (e.g., the ratio of the conduit overlap length to the first diameter being about <NUM> to <NUM>). In specific instances, the droplets (e.g., partially or wholly dried in the plume) are collected on a substrate (e.g., as a dry or semi-wet deposition (e.g., a coherent film) on the substrate). In some instances, the substrate is a grounded collector. In other instances, the substrate is configured between a grounded collector and the nozzle.

Ejecting of a charged fluid stock from an electrospray nozzle produces a fluid jet, which is disrupted to form a plume comprising a plurality of droplets (or plume particulates). In certain instances, such droplets are in varying states of dryness (e.g., wherein more dry droplets comprise less fluid medium relative to solid inclusion materials) as they move toward a collector, with the droplets near the collector being dryer (i.e., comprising less fluid medium) (or even completely dry) than those droplets near the nozzle. In some instances, the plume comprises (e.g., especially in closest proximity to the collector substrate) droplets wherein all fluid medium has been evaporated. In preferred instances, plume droplets (particularly in proximity to the collector substrate surface) are disrupted and small enough to reduce or minimize the number and/or amount of inclusions included within each droplet. In certain instances, reducing and/or minimizing the number and/or amount of inclusions in each droplets facilitates good distribution of inclusion throughout the plume, particularly in proximity to the collector. In some instances, good distribution of inclusions within the plume facilitates good distribution of inclusions as collected on the collector substrate. In particular, films and coatings suffer from poor performance characteristics due to lack of uniformity of the film or coating (e.g., due to variations in dispersion and/or concentration of inclusions/additives, variations in film/coating thickness, etc.).

Typical spray techniques are insufficient to adequately disrupt and break apart the droplets of the plume and are insufficient to provide good distribution of the inclusion materials in the plume and on the collector substrate so as to provide dispersions with good uniformity, particularly in systems comprising multiple inclusion types. Instead, typical spray techniques have been observed to produce particle agglomerations, including co-agglomerations with poor dispersion uniformity and control, without which resultant materials exhibit poor or insufficient performance characteristics.

Processes herein comprise generating a plume or aerosol with a high velocity gas with a velocity of ≥ <NUM>/s. An electrostatically charged fluid stock is injected into a stream of high velocity gas. In certain instances, the high velocity gas facilitates further disruption (e.g., breaking apart) of the droplets formed during electrospray of the fluid stock. In some instances, droplets of the plume comprise (e.g., on average) less than <NUM> inclusions (e.g., sum of inclusion(s) in the droplets), less than <NUM> inclusions, less than <NUM> inclusions, less than <NUM> inclusions or the like. In specific instances, the collector is a distance d away from the nozzle and the droplets of the plume within d/<NUM>, d/<NUM>, or d/<NUM> away from the collector comprise (e.g., on average) about <NUM> inclusions or less, about <NUM> inclusions or less, about <NUM> inclusions or less, about <NUM> inclusions or less, about <NUM> inclusions or less, about <NUM> inclusions or less, or the like. In some instances, the good dispersion of the droplets and the low concentration of inclusions per droplets facilitates the formation of a well-dispersed and well-controlled systems (e.g., multicomponent systems), such as described herein.

In specific instances, electrospraying of the fluid stock or producing an electrostatically charged plume of the fluid stock comprises (i) providing a fluid stock to a first inlet of a first conduit of an electrospray nozzle, the first conduit being enclosed along the length of the conduit by a wall having an interior surface and an exterior surface, the first conduit having a first outlet; and (ii) providing a voltage to the electrospray nozzle (e.g., thereby providing an electric field). The fluid stock comprises a plurality (i.e., more than one) of inclusion particles and fluid medium (e.g., an aqueous medium, such as comprising water). In specific instances, the inclusion particles have at least one average dimension (e.g., overall average dimension or average smallest dimension) of less than <NUM> micron (µm) (e.g., about <NUM> to about <NUM> micron) (e.g., less than <NUM> micron, less than <NUM> micron, less than <NUM> micron, <NUM> micron to <NUM> micron, or less than <NUM> micron (<NUM>)) (e.g., the smallest dimension).

In certain instances, processes described herein are suitable for high throughput of heavily loaded fluid stocks. Where electrospray processes occur with a gas stream, higher loading of particles and/or inclusions are possible. In addition, in some instances, high concentrations of inclusion components are preferred in order to facilitate good coverage of a surface (of a collector or substrate), good uniformity of films (e.g., thickness, dispersion, etc.), and/or the like. In certain instances, the fluid stock provided herein comprises at least <NUM> wt. %, at least <NUM> wt. %, or at least <NUM> wt. % inclusion component, e.g., at least <NUM> wt. % inclusion component, at least <NUM> wt. % inclusion component, at least <NUM> wt. % inclusion component, at least <NUM> wt. % inclusion component, or the like (e.g., up to <NUM> wt. %, up to <NUM> wt. %, up to <NUM> wt. %, up to <NUM> wt. %, up to <NUM> wt. %, or the like). In certain instances, the fluid stock comprises about <NUM> wt. % to about <NUM> wt. % (e.g., about <NUM> wt. % to about <NUM> wt. %) inclusion component.

In certain instances, processes disclosed herein further comprise collecting a film (e.g., a film being a layer of material, prepared by a deposition technique described herein) resulting from the spraying of a fluid stock as described herein) on a substrate. The film comprises a plurality inclusions, as described in the fluid stock herein. In certain instances, the fluid of the fluid stock is partially or completely removed (e.g., by evaporation during the electrospray process).

Any suitable substrate is optionally utilized. In some instances, the substrate is a grounded substrate or positioned between a plume generating nozzle and a grounded surface. In certain instances, the substrate has a surface that is positioned in opposing relation to a plume generating nozzle outlet (e.g., there is "line of sight" between the nozzle outlet and the substrate surface). In specific instances, the opposing substrate is directly opposing the nozzle (e.g., configured orthogonal to nozzle conduit configuration, such as illustrated in <FIG>). In other specific instances, the opposing substrate is angled or offset from directly opposing the nozzle. In some instances, the substrate is affixed to or is a part of a conveyor system (e.g., to facilitate continuous manufacturing of coatings, or films). In specific instances, the substrate is attached to a conveyor belt or is a part of a conveyor belt.

The process described herein is a gas assisted or gas controlled process. A fluid stock as disclosed herein is sprayed with a gas stream. A fluid stock as described herein is injected into a gas stream during electrospraying. The process of producing of an electrostatically charged plume from a fluid stock further comprises providing a pressurized gas to a second inlet of a second conduit of a nozzle described herein. In specific instances, the second conduit has a second inlet and a second outlet, and at least a portion of the first conduit being positioned inside the second conduit (i.e., at least a portion of the second conduit being positioned in surrounding relation to the first conduit). The gap between the outer wall of the inner conduit and the inner wall of the outer conduit is small enough to facilitate a high velocity gas at the nozzle, such as to facilitate sufficient disruption of the charged fluid (jet) ejected from the nozzle (e.g., such as to provide plume or aerosol dispersions described herein). In some instances, the conduit gap is about <NUM> to about <NUM>, such as about <NUM> to about <NUM>, about <NUM> to about <NUM>, or the like. The gas stream (e.g., at the second outlet) has a high velocity of at least <NUM>/s, and preferably at least <NUM>/s, at least <NUM>/s, at least <NUM>/s, or more.

In some disclosed instances, a process disclosed herein comprises compressing of a film described herein. In certain instances, the film is compressed such as to provide a compressed composition having a density of about <NUM> per cubic centimeter (g/cc) or greater, such as about <NUM>/cc or greater, about <NUM> or greater, or the like. Films (e.g., collected, and/or compressed compositions) disclosed herein have any suitable thickness, such as an average thickness of about <NUM> or less, or about <NUM> micron or less (e.g., on the substrate). In some disclosed instances, very thin films are disclosed herein, such as having an average thickness of about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, or about <NUM> micron or less (e.g., down to about <NUM> micron, down to about <NUM> micron, down to about <NUM> micron, or the like). However, in processes of the invention, the manufactured film has a thickness of about <NUM> to about <NUM>. It will be appreciated that the films themselves are not according to the claimed invention.

In certain instances, the inclusion particles have an average aspect ratio of <NUM> to about <NUM>, such as <NUM> to about <NUM>. In further or alternative instances, inclusion particles have an average dimension (or an average smallest dimension) of about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, e.g., about <NUM> to about <NUM> micron, or about <NUM> micron to about <NUM> micron.

The processes disclosed herein are highly versatile and are optionally utilized to manufacture a number of different types of coatings (e.g., coherent film coatings). In specific instances, the processes disclosed herein are utilized to manufacture a thin layer deposition comprising a matrix material, such as a polymer (e.g., as a coherent film), a ceramic, or the like. An inclusion (e.g., nano-inclusion) is dispersed within the matrix (e.g., polymer film). In still more specific instances, the dispersion of the inclusion (e.g., nano-inclusion) in the matrix material is highly uniform. In yet more specific instances, the uniformity of dispersion is such that the most probable distance between inclusions (e.g., nano-inclusions) ranges from about <NUM> or more, or about <NUM> or more, or about <NUM> or more, or about <NUM> to about <NUM>.

In further or alternative instances, depositions disclosed herein have uniform thickness (e.g., the processes disclosed herein provide even distribution of droplets over the target surface area, and/or deliver small droplets to the surface, minimizing "high spots" caused by large droplets/particle deposition). In specific instances, the thin layer deposition has a thickness variation (e.g., in a selected area, such as when an entire surface is not coated, such as an area that is not near the edge of the coating, e.g., an area that is more than <NUM>% or <NUM>% of the length, width, or diameter away from the edge of the coating) of less than about <NUM>% of the average deposition thickness, e.g., about <NUM>% or less of the average deposition thickness, about <NUM>% or less of the average thickness, about <NUM> % or less of the average thickness, about <NUM>% or less of the average thickness, or the like. In some instances, the standard deviation of the film thickness is less than <NUM>% the average thickness, less than <NUM>% the average thickness, less than <NUM>% the average thickness, less than <NUM>% the average thickness, or the like.

In some instances, disclosed herein is a thin film comprising at least <NUM>% by weight of a solid particulate additive described herein (e.g., particles, nanoparticles, carbon inclusions (e.g., graphene oxide), and/or the like). In specific instances, such thin films have uniform thicknesses, such as described herein. In some instances, such thin films comprise at least <NUM>% solid particulate by weight (e.g., at least <NUM>%, at least <NUM>%, at least <NUM>%, at least <NUM>%, at least <NUM>%, at least <NUM>%, at least <NUM>%, or the like). In various instances, such thin films have an average thickness as described herein, such as about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, or the like. However, in processes of the invention, the manufactured film has a thickness of about <NUM> to about <NUM>. It will be appreciated that the films themselves are not according to the invention.

As discussed herein, a fluid stock disclosed herein comprises a liquid medium and an additive. The additive is present in the fluid stock in any suitable concentration, such as up to about <NUM> wt. %, e.g., up to about <NUM> wt. % (e.g., about <NUM> wt. % or more, about <NUM> wt. % or more, about <NUM> wt. % or more, about <NUM> wt. % or more, or the like). In specific instances, the additive is present in the fluid stock in a concentration of about <NUM> wt. % to about <NUM> wt. In certain instances, overall concentration of additive is capable of being very high due to the ability of the process herein to process high concentration and highly viscous stocks that are not possible using typical techniques.

In specific disclosed instances, the additive comprises a polymer (e.g., in a concentration low enough such that a nanofiber is not formed upon manufacturing using a process described herein). In specific instances, the concentration of the polymer in the fluid stock is about <NUM> wt. % or less (e.g., about <NUM> wt. % to about <NUM> wt. While any suitable polymer is optionally utilized, specific polymers include, by way of non-limiting example, polycarbonate (PC), poly(methyl methacrylate) (PMMA), polyethylene terephthalate (PET), polystyrene (PS), acrylonitrile butadiene styrene (ABS), polyacrylonitrile (PAN), polyvinyl acetate (PVAc), polyvinylalcohol (PVA), polyvinylidene fluoride (PVDA), and/or combinations thereof.

The fluid stock (and/or depositions disclosed herein) comprises an additive that is or comprises a plurality of solid inclusions. In disclosed instances, the inclusions (e.g., solid nano-structures) comprise a plurality of metal particles (e.g., nanoparticles), ceramic particles (e.g., nanoparticles), metal oxide particles (e.g., nanoparticles), carbon inclusions (e.g., nanostructures), or any combination thereof. In more specific instances, the inclusions (e.g., nano-structures) comprise particles (e.g., nanoparticles) comprising metal oxide or ceramic, e.g., silicon oxide, aluminum oxide or a titanium oxide. In further or additional instances, the solid inclusions comprise carbon inclusions (e.g., nanostructured carbon inclusions, or carbon nanostructures). In specific instances, carbon inclusions include, by way of non-limiting example, carbon nanotubes, graphene nanoribbons, carbon nanofibers, mesoporous carbon nanostructures, graphene oxide (e.g., sheets or nanoribbons), and/or any combination thereof. In processes of the invention, the inclusion comprises graphene, graphene oxide, or reduced graphene oxide.

In other disclosed instances, the fluid stock comprises (e.g., as a liquid medium and/or additive) polysilazane, silsesquioxane (e.g., polyhedral oligomeric silsesquioxane (POSS), or polysilsesquioxane (PSSQ)), and/or combinations thereof.

The fluid stock comprises a liquid medium, e.g., the liquid medium serving to dissolve and/or suspend the additives. Any suitable liquid medium is optionally used, but in specific instances, the liquid medium is or comprises, by way of non-limiting example, water, an alcohol, dimethylformamide (DMF), tetrahydrofuran (THF), Dimethylacetamide (DMAc), dicloromethane (DCM), chloroform, or N-methyl-pyrrolidone (NMP). As discussed herein, in some instances, the liquid medium is utilized to dissolve and/or suspend additives described herein. In some instances, e.g., to facilitate uniformity of the fluid stock (e.g., solutes and/or suspended agents therein), the fluid stock is agitated (e.g., by stirring, sonicating, and/or any other suitable mechanism) prior to being provided to the first inlet.

In certain instances, any suitable nozzle system configuration is acceptable. In specific instances, the first diameter is about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, or about <NUM> to about <NUM>). In further or alternative instances, the second diameter is any suitable diameter that is larger than the first diameter. In specific instances, the second diameter is about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>). In certain instances, the conduit gap (the average distance between the exterior surface of the inner conduit wall and the interior surface of the outer conduit wall) is any suitable distance, such as a distance configured to allow suitable airflow quantity and/or velocity to the nozzle tip and beyond to break up and/or otherwise facilitate reducing the size of the droplets produced by the spraying process and/or system. In specific instances, the conduit gap is about <NUM> or more (e.g., about <NUM> or more). The spraying process disclosed herein comprises applying a voltage to the nozzle, the voltage being about <NUM> kV to about <NUM> kV (e.g., about <NUM> kV to about <NUM> kV). In certain instances, a power supply is configured to provide a voltage to the nozzle. In some instances, higher voltage are optionally utilized when a voltage is applied to nozzle system comprising a number of nozzles.

In certain instances, processes disclosed herein allow high flow rates (e.g., relative to other spray systems). In specific instances, the flow rate of the fluid stock (e.g., provided to the first inlet of the nozzle) is about <NUM> or more (e.g., about <NUM> to about <NUM>/min, about <NUM> or more, about <NUM> or more, about <NUM> or more, or the like). In certain instances, processes disclosed herein allow the processing of highly viscous fluids (e.g., relative to other spray systems). For example, in some instances, the viscosity of a fluid stock provided herein is about <NUM> cP or more, about <NUM> cP or more, about <NUM> cP or more, about <NUM> cP or more, and/or up to <NUM> Poise or more.

In certain disclosed instances, the disclosed process is for producing a deposition (e.g., a thin layer deposition), the process comprising coaxially electrospraying a fluid stock with a gas, thereby forming a jet, and a plume, the gas at least partially surrounding the jet, the plume comprising a plurality of droplets (e.g., nanodroplets), the fluid stock, the jet, and the plume comprising a fluid and an additive, the additive comprising polymer, an inclusion (e.g., a nanoinclusion, also referred to herein as a nanostructure), or a combination thereof. However, in processes of the invention, the process comprises generating a plume or aerosol by providing a fluid stock to a first inlet of a first conduit of an electrospray nozzle, the fluid stock comprising a liquid and an inclusion comprising graphene, graphene oxide, or reduced graphene oxide; the plume or aerosol being generated by providing a voltage to the nozzle and electrospraying the fluid stock in the presence of a high velocity gas (<NUM>), wherein the high velocity gas is provided by providing a pressurized gas to a second inlet of a second conduit of the electrospray nozzle thereby providing the high velocity gas with a velocity of <NUM>/s or more at a second outlet of the second conduit; the high velocity gas (<NUM>) and the plume or aerosol having a directional mean within <NUM> degrees of one another; and the film or coating (<NUM>) having a thickness of about <NUM> to about <NUM>.

In specific instances, a process disclosed herein is suitable for manufacturing a superhydrophobic surface (e.g., on a substrate such as glass or polycarbonate). The fluid stock comprises a liquid medium and an additive, the additive comprising transparent polymer (e.g., polycarbonate) and/or ceramic particle (e.g., silicon oxide, such as silica, nanoparticles (e.g., having a diameter of about <NUM> micron or less, <NUM> or less, about <NUM> or less, about <NUM> or less, or about <NUM> to about <NUM>)). In specific instances, the superhydrophobic surface has a water contact angle of about <NUM> degrees or more, or about <NUM> degrees or more. In more specific instances, the fluid stock comprises a transparent polymer and ceramic particles (e.g., silicon oxide, such as silica, nanoparticles). In further or alternative instances, the fluid stock (or additive thereof) further comprises a polysilazane (or a sol, sol gel, or ceramic thereof), and/or a silsesquioxane (e.g., polyhedral oligomeric silsesquioxane (POSS), or polysilsesquioxane (PSSQ)). In still further or alternative instances, the fluid stock (or additive thereof) comprises fluroalkyl silane or perflouropolyether alkoxy silane. In specific instances, fluid stock comprises (or a process disclosed herein comprises combining into a fluid stock) polycarbonate, ceramic particles (e.g., silica nanoparticles), organic polysilazane, and fluoroalkyl silane. In specific instances, the ratio of polycarbonate to ceramic particles (e.g., silica nanoparticles) to organic polysilazane to fluoroalkyl silane being about <NUM> to about <NUM> weight parts polycarbonate to about <NUM> to about <NUM> weight parts ceramic particles (e.g., silicon, such as silica, nanoparticles) to about <NUM> to about <NUM> weight parts organic polysilazane to about <NUM> to about <NUM> weight parts fluoroalkyl silane. However, in processes of the invention, the process comprises generating a plume or aerosol by providing a fluid stock to a first inlet of a first conduit of an electrospray nozzle, the fluid stock comprising a liquid and an inclusion comprising graphene, graphene oxide, or reduced graphene oxide; the plume or aerosol being generated by providing a voltage to the nozzle and electrospraying the fluid stock in the presence of a high velocity gas (<NUM>), wherein the high velocity gas is provided by providing a pressurized gas to a second inlet of a second conduit of the electrospray nozzle thereby providing the high velocity gas with a velocity of <NUM>/s or more at a second outlet of the second conduit; the high velocity gas (<NUM>) and the plume or aerosol having a directional mean within <NUM> degrees of one another; and the film or coating (<NUM>) having a thickness of about <NUM> to about <NUM>.

Disclosed herein are articles of manufacture, such as those having one or more glass or polycarbonate surface, at least one surface being coated with a surface coat, the coated surface having a water contact angle of at least <NUM> degrees, and the surface coat comprising polycarbonate and ceramic particles (e.g., silica nanoparticles) (and, optionally a polysilizane or silsesquioxane, or ceramic resulting from the curing thereof, and/or a fluoro-compound (e.g., associated with the ceramic particles (e.g., silica nanoparticles)), such as described herein). The articles themselves are not according to the claimed invention.

In addition, disclosed herein are scalable manufacturing processes for the fabrication of new materials (e.g., depositions) with tailored nanostructures, e.g., meeting an unmet need. In some instances, processes and systems disclosed herein (e.g., gas controlled electrospray processes and systems) employ high speed, circumferentially uniform air flow that can provide enhanced deformation of electrospray droplets (and/or particles), offering a high production rate (tens to hundreds of folds higher than other electrospray techniques), better control of dispersion of inclusions (e.g., nanoinclusions) in the droplets, and/or better control of directing droplets toward a collector with more uniform and thin depositions (e.g., films and coatings).

In addition, disclosed herein are the various compositions prepared by, preparable by, or otherwise described in the processes herein, although the compositions themselves are not according to the claimed invention. In some instances, disclosed herein are films, plumes or aerosols, fluid stocks, systems comprising any one or more of the same, and the like described herein, although said films, plumes or aerosols, fluid stocks, and systems are not according to the claimed invention.

These and other objects, features, and characteristics of the system and/or process disclosed herein, as well as the processes of operation and functions of the related elements of structure and the combination of parts and economies of manufacture, will become more apparent upon consideration of the following description and the appended claims with reference to the accompanying drawings, all of which form a part of this specification, wherein like reference numerals designate corresponding parts in the various figures. As used in the specification and in the claims, the singular form of "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. In addition, unless otherwise stated, values and characteristics described for individual components herein also include disclosure of such values and characteristics as an average of a plurality (i.e., more than one) of such components. Similarly, disclosure of average values and characteristics herein also includes a disclosure of an individual value and characteristic as applied to a single component herein.

Disclosed in certain instances herein are systems and processes for manufacturing depositions, and the like. In some instances, depositions provided herein are thin layer depositions, which are suitable for any number of applications. In various instances, the depositions are coatings (e.g., films) comprising a matrix material (e.g., polymer or ceramic) and further comprising inclusions (e.g., nanostructured inclusions). In some instances, the inclusions are dispersed in and/or on the matrix. In other instances, depositions disclosed herein are coatings comprising a plurality of structures, such as nanostructures (e.g., the nanostructures forming the coating and being dispersed on a substrate). Also disclosed in some instances herein are articles of manufacture comprising a deposition (e.g., film) or coat, e.g., a thin-layered coat manufactured or capable of being manufactured according to the processes described herein. In certain instances, disclosed herein is a substrate comprising a coating or deposition described herein on the surface thereof. It will be appreciated that the depositions, substrates, systems and articles of manufacture are not themselves according to the claimed invention.

In some instances, disclosed herein is a process for producing a thin layer deposition, the process comprising electrospraying a fluid stock with a gas (e.g., a controlled gas flow). The fluid and the gas are ejected from an electrospray nozzle in a similar direction. The direction of ejection of the fluid stock and the gas from the electrospray nozzle is within <NUM> degrees of one another (e.g., within about <NUM> degrees or within about <NUM> degrees of one another). In certain instances, the fluid stock and the gas are configured to be ejected from the nozzle in a coaxial configuration. In some instances, configurations and processes described herein allow for an enhanced driving force of electrospray, combining the driving forces of electric field gradient with high speed gas. In certain instances, configurations and processes described herein provided for several improvements in electrospray processing, including in the manufacture of depositions, such as described herein. In addition, in some instances, such configurations allow for process throughput up to tens or hundreds of times greater than simple electrospray manufacturing and allow for the electrospray of high viscosity and/or highly loaded fluids. Moreover, in some instances, such electrospray techniques and systems allow for the manufacture of highly uniform depositions and coatings. By contrast, other or conventional electrospray is not generally of commercial use in coatings applications because of, e.g., non-uniform deposition of drops and dispersion of fillers in droplets, especially for high loaded systems.

In some instances, electrospray (e.g., using a process and/or system disclosed herein) of the fluid stock results in the formation of a jet, which subsequently deforms into a plume comprising a plurality of droplets (collectively referred to herein so as to encompass, e.g., droplet solutions, droplet suspensions, and/or solid particles in an plume or aerosol). Electrospray (e.g., using a process and/or system provided herein) of a fluid stock, such as disclosed herein results in the formation of a plume comprising a plurality of droplets (collectively referred to herein so as to encompass, e.g., droplet solutions, droplet suspensions, and/or solid particles in an electrospray plume). In some instances, the processes described herein results in the formation of small droplets (e.g., micro- or nano-scale droplets) having highly uniform size distributions (e.g., especially relative to standard electrospray techniques. <FIG> illustrates high speed imaging of electrospray of a fluid stock using conventional electrospray techniques <NUM> and an exemplary gas controlled electrospray technique provided herein <NUM>. As illustrated in <FIG>, the "plume" of the conventional electrospray process near the nozzle <NUM> comprises much larger droplets <NUM> having a less uniform size distribution than the droplets <NUM> of the plume resulting near the nozzle <NUM> of the gas controlled electrospray processes described herein. In some instances, smaller and more uniform droplet size provides improved uniformity of depositions, such as illustrated in <FIG> illustrates depositions manufactured by an exemplary conventional electrospray techniques (left panels) and an exemplary gas controlled electrospray process provided herein (right panels). As illustrated in <FIG>, depositions formed by conventional electrospray techniques provide depositions that are not uniform and comprise large particles, relative to the depositions formed by exemplary gas controlled electrospray systems and processes described herein. <FIG> shows an exemplary illustration of a gas controlled electrospray system disclosed herein <NUM> and an exemplary illustration of a non-gas controlled electrospray system <NUM>. In some instances, a non gas-controlled system results, upon spraying from a nozzle <NUM>, in the formation of large droplets <NUM>, which droplets are large and not well dispersed in the "plume" and irregular depositions <NUM> on the collector <NUM>. This illustration is further demonstrated in <FIG> and <FIG> by the high speed imaging of spraying <NUM> (<FIG>), and as collected (<FIG>, left panels). By contrast, in some instances, gas-controlled systems (and processes) disclosed herein provide electrospray of a fluid stock with a gas (illustrated by the downward arrows) <NUM> (e.g., having a controlled flow, such as circumferentially configured with the dispensing of the fluid stock) from a nozzle <NUM> (e.g., coaxially arranged, as illustrated in <FIG>). In some instances, with the flow of air, the droplets <NUM> proximal to the nozzle are smaller relative to non-gas controlled techniques (e.g., in some instances due to the controlled air flow at the nozzle end <NUM>), and even smaller still as the droplets <NUM> move away from the nozzle toward the collector (droplets distal to the nozzle <NUM> and/or proximal to a collector <NUM>). In some instances, such uniformity (e.g., uniformity of size, horizontal distribution, etc.) of dispersion of small droplets provides for a deposition <NUM> having a greatly improved uniformity of thickness, dispersion of inclusions, etc. This illustration is further demonstrated in <FIG> and <FIG> by the high speed imaging of spraying <NUM> (<FIG>), and as collected (<FIG>, right panels).

In certain instances, uniformity in the plume/aerosol allows for much greater control of deposition formation, such as thickness, thickness uniformity, compositional uniformity (e.g., in composites), and the like. In certain disclosed instances, films disclosed herein have an average thickness (df) that is about <NUM> or less, such as about <NUM> or less, about <NUM> or less, or about <NUM> or less. However, in processes of the invention, the film or coating has a thickness of <NUM> to <NUM>. In certain instances, such as wherein the film is utilized as coating, such as a transparent coating, the thickness of the film is about <NUM> micron (micrometer, µm) or less, such as about <NUM> micron or less, about <NUM> micron or less, about <NUM> micron or less, about or the like (e.g., down to <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM> micron, about <NUM> micron, about <NUM> micron, <NUM> micron, <NUM> micron, <NUM> micron, or the like, depending on the desired thickness). In some instances, the thickness of the film is controlled by limiting or lengthening the residence time of a collector surface opposite an active nozzle system (e.g., using batch or continuous (e.g., using a conveyor) system). In certain instances, the films disclosed herein have good thickness uniformity, such as wherein the thinnest portion of the film is > df/<NUM>, > df/<NUM>, > df/<NUM>, > df/<NUM>, > df/<NUM>, or the like. In further or alternative instances, the thickest portion of the film is < <NUM> x dε, <<NUM> x dε, <<NUM> x dε, <<NUM> x dε, <<NUM> x dε, <<NUM> x dε, or the like. In preferred instances, the minimum thickness of the film is greater than <NUM> dε, (more preferably greater than <NUM> dε) and the maximum thickness of the flim is less than <NUM> dε, (more preferably, less than <NUM> df).

The disclosed process comprises producing an electrostatically charged plume comprising a plurality of particles and/or droplets (e.g., an area or section of air comprising a plurality of particles and/or droplets dispersed therein). In specific instances, the plurality of particles and/or droplets are (e.g., nanoscaled) particles and/or droplets. In more specific instances, the plurality of particles and/or droplets have an average diameter of about <NUM> microns or less, about <NUM> microns or less, less than <NUM> micron, about <NUM> microns or less, less than <NUM> micron, or about <NUM> microns or less. In still more specific instances, the plurality of particles and/or droplets have an average diameter of about <NUM> microns or less, e.g., about <NUM> micron or less. In certain instances, the size of the particles and/or droplets is highly uniform, with the standard deviation of the particle and/or droplet size being about <NUM>% of the average size of the particles and/or droplets, or less (e.g., about <NUM>% or less, about <NUM>% or less, about <NUM>% or less, about <NUM>% or less, or the like) (e.g., at any given distance from the nozzle, e.g., about <NUM> or more, about <NUM> or more, about <NUM> or more, about <NUM> or more, from the nozzle).

The fluid stock, the jet, and/or the plume comprises a fluid (e.g., water) and an inclusion. Compositions disclosed herein comprise a plurality of droplets, a jet, or a fluid stock comprising a fluid (e.g., water) and an inclusion. Although the compositions themselves are not according to the claimed invention. Individual droplets comprise one or more inclusion type and optionally other additive (e.g., polymer). Further, some or all of the fluid of the droplets (of the plume) may be evaporated during the electrospray process (e.g., prior to deposition). In various instances, concentrations of inclusion materials in droplets described herein, or a composition comprising the same, are generally higher than the concentrations of such materials in the fluid stock, or even in the jet (where evaporation of the fluid begins). In certain instances, droplets or compositions comprising the droplets having inclusions concentrations of at least <NUM>. 5x, at least 2x, at least 3x, at least 5x, at least 10x, or the like (e.g., wherein the inclusions make up to <NUM> wt. % or more, <NUM> wt. % or more, <NUM> wt. % or more, or even <NUM> wt. % of the droplets or composition/plume comprising the same) of the concentrations of the droplets or composition/plume comprising the same.

In specific instances, the plume (e.g., particles and/or droplets thereof) comprises a plurality of additive particles (e.g., nanoparticles) and optionally a polymer. The plume (e.g., particles and/or droplets thereof) further comprises a liquid medium (e.g., wherein the liquid medium of a fluid stock is not completely evaporated). In some instances, a process or system disclosed herein allows for high throughput electrospraying (e.g., relative to other non-gas controlled electrospray techniques). In some instances, the controlled air flow allows for a increase rate and uniformity in dispersion and breaking up of the jet and the plume, allowing for increased fluid stock flow rates, while also increasing deposition uniformity. In various instances, the fluid stock is provided to the nozzle at any suitable flow rate, such as about <NUM>/min or more, about <NUM>/min or more, about <NUM>/min or more, about <NUM>/min or more, or about <NUM>/min to about <NUM>/min. In certain instances, the fluid stock is provided to the first inlet at a rate of about <NUM> to about <NUM>/min, e.g., about <NUM>/min to about <NUM>/min, or about <NUM>/min to about <NUM>/min.

In specific instances, an electrospray process described herein comprises providing a fluid stock to a first inlet of a first conduit of an electrospray nozzle, the first conduit being enclosed along the length of the conduit by a wall having an interior surface and an exterior surface, the first conduit having a first outlet. In specific instances, the walls of the first conduit form a capillary tube, or other structure. In some instances, the first conduit is cylindrical, but instances herein are not limited to such configurations.

<FIG> illustrates exemplary electrospray nozzle apparatuses <NUM> and <NUM> provided herein. Illustrated by both nozzle components <NUM> and <NUM> some instances, the nozzle apparatus comprises a nozzle component comprising a first (inner) conduit, the first conduit being enclosed along the length of the conduit by a first wall <NUM> and <NUM> having an interior and an exterior surface, and the first conduit having a first inlet (or supply) end <NUM> and <NUM> (e.g., fluidly connected to a first supply chamber and configured to receive a fluid stock) and a first outlet end <NUM> and <NUM>. Generally, the first conduit has a first diameter <NUM> and <NUM> (e.g., the average diameter as measured to the inner surface of the wall enclosing the conduit). In further instances, the nozzle component comprising a second (outer) conduit, the second conduit being enclosed along the length of the conduit by a second wall <NUM> and <NUM> having an interior and an exterior surface, and the second conduit having a second inlet (or supply) end <NUM> and <NUM> (e.g., fluidly connected to a second supply chamber and configured to receive a gas - such as a high velocity or pressurized gas (e.g., air)) and a second outlet end <NUM> and <NUM>. In some instances, the second inlet (supply) end <NUM> and <NUM> is connected to a supply chamber. In certain instances, the second inlet (supply) end <NUM> and <NUM> are connected to the second supply chamber via a supply component. <FIG> illustrates an exemplary supply component comprising a connection supply component (e.g., tube) <NUM> and <NUM> that fluidly connects <NUM> and <NUM> the supply chamber (not shown) to an inlet supply component <NUM> and <NUM>, which is fluidly connected to the inlet end of the conduit. The figure illustrates such a configuration for the outer conduit, but such a configuration is also contemplated for the inner and any intermediate conduits as well. Generally, the first conduit has a first diameter <NUM> and <NUM> (e.g., the average diameter as measured to the inner surface of the wall enclosing the conduit). The first and second conduits have any suitable shape. In some instances, the conduits are cylindrical (e.g., circular or elliptical), prismatic (e.g., a octagonal prism), conical (e.g., a truncated cone - e.g., as illustrated by the outer conduit <NUM>) (e.g., circular or elliptical), pyramidal (e.g., a truncated pyramid, such as a truncated octagonal pyramid), or the like. In specific instances, the conduits are cylindrical (e.g., wherein the conduits and walls enclosing said conduits form needles). In some instances, the walls of a conduit are parallel, or within about <NUM> or <NUM> degrees of parallel (e.g., wherein the conduit forms a cylinder or prism). For example, the nozzle apparatus <NUM> comprise a first and second conduit having parallel walls <NUM> and <NUM> (e.g., parallel to the wall on the opposite side of the conduit, e.g., as illustrated by 801a / 801b and 805a / 805b, or to a central longitudinal axis <NUM>). In other instances, the walls of a conduit are not parallel (e.g., wherein the diameter is wider at the inlet end than the outlet end, such as when the conduit forms a cone (e.g., truncated cone) or pyramid (e.g., truncated pyramid)). For example, the nozzle apparatus <NUM> comprise a first conduit having parallel walls <NUM> (e.g., parallel to the wall on the opposite side of the conduit, e.g., as illustrated by 831a / 831b, or to a central longitudinal axis <NUM>) and a second conduit having non-parallel walls <NUM> (e.g., not parallel or angled to the wall on the opposite side of the conduit, e.g., as illustrated by 835a / 835b, or to a central longitudinal axis <NUM>). In certain instances, the walls of a conduit are within about <NUM> degrees of parallel (e.g., as measured against the central longitudinal axis, or half of the angle between opposite sides of the wall), or within about <NUM> degrees of parallel. In specific instances, the walls of a conduit are within about <NUM> degrees of parallel (e.g., within about <NUM> degrees or <NUM> degrees of parallel). In some instances, conical or pyramidal conduits are utilized. In such instances, the diameters for conduits not having parallel walls refer to the average width or diameter of said conduit. In certain instances, the angle of the cone or pyramid is about <NUM> degrees or less (e.g., the average angle of the conduit sides/walls as measured against a central longitudinal axis or against the conduit side/wall opposite), or about <NUM> degrees or less. In specific instances, the angle of the cone or pyramid is about <NUM> degrees or less (e.g., about <NUM> degrees or less). Generally, the first conduit <NUM> and <NUM> and second conduit <NUM> and <NUM> having a conduit overlap length <NUM> and <NUM>, wherein the first conduit is positioned inside the second conduit (for at least a portion of the length of the first and/or second conduit). In some instances, the exterior surface of the first wall and the interior surface of the second wall are separated by a conduit gap <NUM> and <NUM>. In certain instances, the first outlet end protrudes beyond the second outlet end by a protrusion length <NUM> and <NUM>. In certain instances, the ratio of the conduit overlap length-to-second diameter is any suitable amount, such as an amount described herein. In further or alternative instances, the ratio of the protrusion length-to-second diameter is any suitable amount, such as an amount described herein, e.g., about <NUM> or less.

<FIG> also illustrates cross-sections of various nozzle components provided herein <NUM>, <NUM> and <NUM>. Each comprises a first conduit <NUM>, <NUM> and <NUM> and second conduit <NUM>, <NUM>, and <NUM>. As discussed herein, in some instances, the first conduit is enclosed along the length of the conduit by a first wall <NUM>, <NUM> and <NUM> having an interior and an exterior surface and the second conduit is enclosed along the length of the conduit by a second wall <NUM>, <NUM> and <NUM> having an interior and an exterior surface. Generally, the first conduit has any suitable first diameter <NUM>, <NUM> and <NUM> and any suitable second diameter <NUM>, <NUM>, and <NUM>. The cross-dimensional shape of the conduit is any suitable shape, and is optionally different at different points along the conduit. In some instances, the cross-sectional shape of the conduit is circular <NUM> / <NUM> and <NUM> / <NUM>, elliptical, polygonal <NUM> / <NUM>, or the like.

In some instances, coaxially configured nozzles provided herein and coaxial gas controlled electrospraying disclosed herein comprises providing a first conduit or fluid stock along a first longitudinal axis, and providing a second conduit or gas (e.g., pressurized or high velocity gas) around a second longitudinal axis (e.g., and electrospraying the fluid stock in a process thereof). In specific instances, the first and second longitudinal axes are the same. In other instances, the first and second longitudinal axes are different. In certain instances, the first and second longitudinal axes are within <NUM> microns, within <NUM> microns, within <NUM> microns, or the like of each other. In some intances, the first and second longitudinal axes are aligned within <NUM> degrees, within <NUM> degrees, within <NUM> degrees, within <NUM> degrees, within <NUM> degree, or the like of each other. For example, <FIG> illustrates a cross section of a nozzle component <NUM> having an inner conduit <NUM> that is off-center (or does not share a central longitudinal axis) with an outer conduit <NUM>. In some instances, the conduit gap (e.g., measurement between the outer surface of the inner wall and inner surface of the outer wall) is optionally averaged - e.g., determined by halving the difference between the diameter of the inner surface of the outer wall <NUM> and the diameter of the outer surface of the inner wall <NUM>. In some instances, the smallest distance between the inner surface of the outer wall <NUM> and the diameter of the outer surface of the inner wall <NUM> is at least <NUM>% (e.g., at least <NUM>%, at least <NUM>%, or any suitable percentage) of the largest distance between the inner surface of the outer wall <NUM> and the diameter of the outer surface of the inner wall <NUM>.

A fluid stock disclosed herein comprises any suitable components. In The fluid stock comprises a liquid medium and an additive In more specific instances, the additive is a a solid particulate inclusion (e.g., nanoscaled - such as less than about <NUM> micron in at least one dimension - particulate; e.g., nanoparticles being less than about <NUM> micron in all dimensions, and nanorods and nanofibers being less than about <NUM> micron in diameter and greater or less than about <NUM> micron in a second dimension) and optionally a polymer. In specific nstances, nano-inclusions (e.g., nanoparticles) have nanoscale moprhologies that are about <NUM> or less. In more specific instances, at least one dimension (e.g., all dimensions for a nanoparticle) is about <NUM> or less, or about <NUM> or less or about <NUM> or less, or about <NUM> to about <NUM>, or any other suitable size. In other instances, processes described herein are optionally utilized with larger particles, such as micro-sized particles having a (e.g., average) dimension of about <NUM> micron to about <NUM> micron, about <NUM> micron to about <NUM> micron, or the like. In various instances, the additives are dissolved and/or otherwise dispersed into the liquid medium. In additional instances, further additives are optionally included, as desired. For example, in some instances, an additive optionally includes a fluorinated organosilane (e.g., fluoroalkyl silane (e.g., F<NUM>C(CF<NUM>)a(CH<NUM>)bSi(OR)<NUM>, wherein a is <NUM> to <NUM>, e.g., <NUM>-<NUM>, b is <NUM>-<NUM>, e.g., <NUM>-<NUM>, each R is independently a hydrocarbon described herein, such as a C1-<NUM> alkyl), and/or flouropolyether alkoxy silane, such as a perfluoropolyetheralkoxy silane (e.g., F<NUM>C((CF<NUM>)aO)c(CH<NUM>)bSi(OR)<NUM>, wherein each a is independently <NUM> to <NUM>, e.g., <NUM>-<NUM>, b is <NUM>-<NUM>, e.g., <NUM>-<NUM>, c is <NUM>-<NUM>, e.g., <NUM>-<NUM>, each R is independently a hydrocarbon described herein, such as a C1-<NUM> alkyl or fluoroalkyl), a metal, metal oxide, or ceramic precursor, surfactants, and/or other suitable additives. In processes of the invention, the additive comprises graphene, graphene oxide, or reduced graphene oxide.

Depending on the coating and/or deposition application, any number of polymers are optionally utilized. In some instances, polymers include, by way of non-limiting example, polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polyethylene oxide (PEO), polyvinyl ether, polyvinyl pyrrolidone, polyglycolic acid, hydroxyethylcellulose (HEC), ethylcellulose, cellulose ethers, polyacrylic acid, polyisocyanate, and the like. In some embodiments, the polymer is polystyrene (PS), polymethacrylate (PMA), polyvinylpyridine (PVP), polyvinylalkane, polyvinylcycloalkane (e.g., polyvinylcyclohexane), a polyimide, a polyamide, a polyalkene (e.g., polypropylene (PP)), a polyether (e.g., polyethyelene oxide (PEO), polypropylene oxide (PPO)), a polyamine, or the like. In specific instances, the polymer is polycarbonate (PC), poly(methyl methacrylate) (PMMA), polyethylene terephthalate (PET), polystyrene (PS), acrylonitrile butadiene styrene (ABS), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), or polyvinylidene fluoride (PVDF). In certain instances, such as wherein a transparent coat is desired, a transparent polymer is utilized (e.g., a polymer that is transparent at a thickness of a deposition or coat applied (e.g., about <NUM> or less). <FIG> illustrates a glass substrate without coating and a glass substrate with an exemplary transparent coating disclosed herein. As can be seen in <FIG>, use of a transparent polymer results in a transparent coat through which underlying objects are visible. In certain instances, a deposition or coat disclosed herein has a transmittance (<NUM> ~ <NUM>) of about <NUM>% or greater, or about <NUM>% or greater. Moreover, use of electrospinning techniques to deposit a similar coat of nanofibers onto the surface resulted in an unacceptably opaque coat, rendering the underlying objects "blurry" or not visible. In some instances, the polymer has any suitable molecular weight. For example, in certain embodiments, the polymer has a molecular weight of at least <NUM>,<NUM> atomic mass units ("amu"), at least <NUM>,<NUM> amu, at least <NUM>,<NUM> amu, at least <NUM>,<NUM> amu, and the like. A polymer in used in a process or found in a composition herein has any suitable PDI (weight average molecular weight divided by the number average molecular weight). In some instances, the polymer has a polydispersity index of about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, or the like.

In certain instances, any suitable amount of polymer is optionally utilized in a fluid stock provided herein. In some instances, the amount of polymer utilized is less than the amount that would inhibit the formation of a plume (dispersion and/or breaking-up of the jet) when being electrosprayed. In some instances, with the use of the gas controlled electrospray processes, greater amounts of polymer are optionally utilized when compared to conventional electrospray techniques because of the effect of the gas to further break-up the jet and/or plume, providing greater formation, dispersion and control of droplets. In certain instances, the amount of polymer present in the fluid stock is less than <NUM> wt. In more specific embodiments, the amount of polymer present in the fluid stock is <NUM> wt. % to about <NUM> wt. % (e.g., about <NUM> wt. % to about <NUM> wt. %, or about <NUM> wt. % to about <NUM> wt.

The fluid stock comprises an additive, such as a non-polymer additive, a solid particle additive (e.g., dispersed in the fluid stock), or the like. In some instances, processes for preparing and systems configured to prepare depositions, such as those described herein, do not require the use of a polymer. For example, depositions comprising dispersed particles (e.g., nanostructured particles) are prepared using a fluid stock with or without a polymer. In some instances, when a polymer is included in a fluid stock (e.g., along with a plurality of particles), a deposition comprising a polymer matrix with particles dispersed in and/or on the polymer matrix is formed (e.g., a polymer matrix deposition being formed on a substrate surface). In some other instances, when a fluid stock (comprising a plurality of particles) without a polymer is used, a deposition comprising particles dispersed directly on a substrate is formed. In processes of the invention, the additive comprises graphene, graphene oxide, or reduced graphene oxide.

The fluid stock and deposition comprise an additive, such as a plurality of solid inclusion particulates. In specific instances, the additive comprises a plurality of nano-structured particles. In various instances, nanostructured particles include, by way of non-limiting example, nanoparticles, nanoscale sheets, nanoribbons, nanorods, nanofibers (including, e.g., high aspect ratio nanorods), and the like. In certain instances, the additive comprises metal, ceramic, metal oxide, carbon (e.g., a carbon allotrope), and/or the like. In specific instances, the additive comprises metal particles (e.g., nanoparticles), ceramic particles (e.g., nanoparticles), metal oxide particles (e.g., nanoparticles), or a combination thereof. In further or alternative instances, the additive comprises a carbonaceous inclusion (e.g., carbon allotrope), such as, by way of non-limiting example, carbon nanotubes (e.g., multi-walled carbon nanotubes (MWCNT), and/or single-walled carbon nanotubes (SWCNT)), graphene (e.g., pristine or defective graphene, such as produced from by reducing, e.g., thermal or irradiation reduction of graphene oxide), graphene oxide, reduced graphene oxide, graphite, amorphous carbon, graphene nanoribbons (GNRs), or the like. In processes of the invention, the additive comprises graphene, graphene oxide, or reduced graphene oxide.

In specific instances, an additive disclosed herein comprises a plurality of nanofibers, the nanofibers comprising a metal, metal oxide, ceramic, carbon (e.g., amorphous carbon) or a combination thereof. Such nanofibers are optionally manufactured by any suitable method, such as those described in <CIT>, published on <NUM> March <NUM>, and entitled "Metal and Ceramic Nanofibers,". In more specific instances, the nanofibers comprise a composite comprising a matrix material and an inclusion material, the inclusion material embedded in the matrix material. Such nanofibers are optionally manufactured by any suitable method, such as those described in <CIT>, and entitled "Carbonaceous Metal/Ceramic Nanofibers,". The nanofibers have any suitable length. In some instances, a given collection of nanofibers comprise nanofibers that have a distribution of fibers of various lengths. In some instances, the nanofiber has an average length of about <NUM> micron or more, or about <NUM> micron or more, or about <NUM> micron or more, or about <NUM> micron or more, or about <NUM> micron or more, or ever larger sizes, up to and including any size capable of being dispersed in a fluid stock and electrosprayed using a process described herein. In some instances, nanofibers described herein have an aspect ratio of about <NUM> or more. In more specific instances, the aspect ratio is about <NUM> or more, about <NUM> or more, about <NUM> or more, about or even larger. "Aspect ratio" is the length of a nanofiber divided by its diameter. In processes of the invention, the additive comprises graphene, graphene oxide, or reduced graphene oxide.

In some disclosed instances, metal, metal oxide, or ceramic materials (e.g., solid inclusions, precursors, or the like) provided in a metal, metal oxide, or ceramic herein optionally comprise any suitable elemental components, such as a transition metal, alkali metal, alkaline earth metal, post-transition metal, lanthanide, or actinide. Transition metals include: scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), rutherfordium (Rf), dubnium (Db), seaborgium (Sg), bohrium (Bh), and hasium (Hs). Alkali metals include: lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr). Alkaline earth metals include: beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). Post-transition metals include: aluminum (Al), gallium (Ga), indium (In), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi). Lanthanides include the elements with atomic number <NUM> to <NUM> on the periodic table. Actinides include the elements with atomic number <NUM> to <NUM> on the periodic table. In addition, silicon (Si), germanium (Ge), antimony (Sb) and polonium (Po) are considered metals for the purposes of the present disclosure. In some instances, silicon is used in the process described herein to produce silicon nanofibers. In some instances, metal oxides include, by way of non-limiting example, Al<NUM>O<NUM>, ZrO<NUM>, Fe<NUM>O<NUM>, CuO, NiO, ZnO, CdO, SiO<NUM>, TiO<NUM>, V<NUM>O<NUM>, VO<NUM>, Fe<NUM>O<NUM>, SnO, SnO<NUM>, CoO, CoO<NUM>, Co<NUM>O<NUM>, HfO<NUM>, BaTiO<NUM>, SrTiO<NUM>, and BaSrTiO<NUM>. Other additives, such as metal precursors, are also optionally utilized. In such cases, upon calcination (e.g., thermal treatment of about <NUM> or more, e.g., about <NUM> or more, about <NUM> or more), the metal precursors may be converted to a metal or metal oxide material described herein. Metal precursors include metal iodides, bromides, sulfides, thiocyanates, chlorides, nitrates, azides, fluorides, hydroxides, oxalates, nitrites, isothiocyanates, cyanides, alko-oxides (e.g., methoxide, ethoxide, propoxide, butlyoxide, or the like), or the like. In some examples, the precursor is a metal complex such as metal acetate, metal chloride, metal nitrate, or metal alko-oxide. In processes of the invention, the additive comprises graphene, graphene oxide, or reduced graphene oxide.

In specific instances, the additive and/or particles (e.g., nano-structured particles) comprise silicon, a silicon oxide (e.g., SiOx, wherein <NUM> < x ≤ <NUM>), an aluminum oxide, or a titanium oxide (e.g., TiOx, wherein <NUM> < x ≤ <NUM>). In processes of the invention, the additive comprises graphene, graphene oxide, or reduced graphene oxide.

In specific instances, the additive comprises carbon nonstructures, such as carbon nanotubes, graphene nanoribbons, carbon nanofibers, mesoporous carbon nanostructures, or any combination thereof. In specific instances, an additive provided herein comprises a graphene component (e.g., graphene or a fully reduced graphene oxide), such as an oxidized graphene component (e.g., graphene oxide, reduced graphene oxide (that is still partially oxidized), or the like). In processes of the invention, the additive comprises graphene, graphene oxide, or reduced graphene oxide.

In some instances, a film or coating disclosed herein comprises a carbon (e.g., graphene) matrix or web (e.g., wherein the graphene matrix or web comprises a graphene structure or analog as described herein). In certain instances, the carbon matrix or web comprises any suitable amount of a graphene component (e.g., graphene, graphene oxide, or reduced graphene oxide). In specific instances, the carbon matrix or web comprises about <NUM> wt. % or more (e.g., about <NUM> wt % or more, about <NUM> wt % or more, about <NUM> wt % or more, about <NUM> wt % or more, about <NUM> wt % or more, or about <NUM> wt % or more) graphene component. In certain instances, the film further comprises a plurality of structures (e.g., micro- or nano-structures, such as comprising metal, metal oxide, and/or ceramic material), such as provided from preformed inclusions provided in a fluid stock herein, or metal or ceramic precursor materials provided in the fluid stock. In certain instances, the inclusion materials are embedded within the carbon matrix or web (e.g., graphenic matrix or web), and/or on the surface thereof. In some instances, the inclusions comprise nanoscale and/or microscale inclusions (e.g., such nanostructures comprising a nanoscale (e.g., having an average dimension of less than <NUM> micron, or less than <NUM> micron) structure in any one or more dimension, such as nanostructured fibers, particles, sheets, rods, and/or the like). In specific instances, the carbon inclusion is a nanostructured carbon having a nanoscale (e.g., less than <NUM> micron, less than <NUM> micron, or less than <NUM>) structure in any one or more dimension, such as nanostructured fibers, particles, sheets (e.g., grapheme sheets), rods, and/or the like). In some instances, the inclusion comprises microstructures (e.g., having an average dimension of less than <NUM> micron, less than <NUM> micron, or less than <NUM> micron, less than <NUM> micron, less than <NUM> micron, less than <NUM> micron, less than <NUM> micron, or the like, such as down to about <NUM>, about <NUM>, about <NUM> micron, or the like). Other details of the suitable materials, inclusions, or structures are as described herein. Further, in some instances, such as wherein larger structures are utilized, larger droplets or particles are necessarily formed upon electrospray according to the processes described herein. In processes of the invention, the inclusion comprises graphene, graphene oxide, or reduced graphene oxide. It will be appreciated that the films and coatings themselves are not according to the claimed invention.

In specific instances disclosed herein is a composition or material comprising a graphene component, such as an oxidized graphene component (e.g., graphene oxide). In certain instances, oxidized graphene components are converted to reduced materials via reductive reaction conditions, such as through thermal, irradiation, chemical, and/or other processes described herein. In specific instances, thermal conditions using reductive (e.g., hydrogen gas, hydrogen gas mixed with an inert gas, or the like) or inert atmosphere (e.g., nitrogen gas, argon gas, or the like) is utilized. In specific instances, the oxidized graphene component is a graphene component functionalized with oxygen, such as with carbonyl groups, carboxyl groups (e.g., carboxylic acid groups, carboxylate groups, COOR groups, such as wherein R is a C1-C6 alkyl, or the like), -OH groups, epoxide groups, ether, and/or the like. In certain instances, the oxidized graphene component (or graphene oxide) comprises about <NUM>% or more carbon (e.g., <NUM>% to <NUM>%). In more specific instances, the oxidized graphene component comprises about <NUM> wt. % to about <NUM> wt. % carbon, or about <NUM> wt. % to about <NUM> wt. In further or alternative specific instances, the oxidized graphene component comprises about <NUM> wt. % oxygen or less, such as about <NUM> wt. % oxygen to about <NUM> wt. % oxygen, about <NUM> wt. % oxygen or less, about <NUM> wt. % to <NUM> wt. % oxygen, or the like. In various instances, oxidized graphene included graphene oxide, such as illustrated by the non-limiting exemplary structures in <FIG>, and/or reduced graphene oxide, such as illustrated by the non-limiting exemplary structures in <FIG>. It will be appreciated that the compositions and materials themselves are not according to the claimed invention.

In certain instances, the graphene component (e.g., reduced graphene oxide) comprises about <NUM>% or more carbon (e.g., <NUM>% to <NUM>%), such as about <NUM> wt. % or greater, about <NUM> wt. % or more, about <NUM> wt. % or greater, about <NUM> wt. % or greater, about <NUM> wt. % or greater, or about <NUM> wt. % or greater (e.g., up to about <NUM> wt. % or more). In certain instances, the graphene component (e.g., rGO) comprises about <NUM> wt. % or less (e.g., <NUM> wt. % to <NUM> wt. %) oxygen, e.g., about <NUM> wt. % or less (e.g., <NUM> wt. % to <NUM> wt. %) oxygen, or about, about <NUM> wt. % or less, about <NUM> wt. % or less, about <NUM> wt. % or less (e.g., down to about <NUM> wt. %, down to about <NUM> wt. %, down to about <NUM> wt. % or the like) oxygen. In specific instances, the graphene component (e.g., rGO) comprises about <NUM> wt. % to about <NUM> wt. % oxygen, e.g., about <NUM> wt. % to about <NUM> wt. %, about <NUM> wt, % to about <NUM> wt, %, or the like. In certain instances, e.g., wherein an oxidized carbon inclusion material (e.g., graphene component) is reduced, higher ratios of carbon to oxygen are contemplated for the graphene component.

In some instances, processes described herein are useful for high throughput processing of graphenic components (e.g., oxidized graphene components) to form highly uniform films and coatings. In certain instances, higher concentrations of graphenic inclusion components are able to be processed than are possible using conventional techniques. In certain instances, a fluid stock disclosed herein comprises at least <NUM> wt. %, or at least <NUM> wt. % graphenic inclusion component, e.g., at least <NUM> wt. % graphenic inclusion component, at least <NUM> wt. % graphenic inclusion component, at least <NUM> wt. % inclusion component, at least <NUM> wt. % graphenic inclusion component, or the like (e.g., up to <NUM> wt. %, up to <NUM> wt. %, or the like). In certain instances, the fluid stock comprises about <NUM> wt. % to about <NUM> wt. % (e.g., about <NUM> wt. % to about <NUM> wt. %) graphenic inclusion component.

The additive is present in a fluid stock disclosed herein in any concentration desired and up to which electrospraying according to a process or using a system described herein is possible. In some instance, electrospraying a fluid stock with a controlled gas steam, such as described in certain instances herein, allows for the electrospraying of fluid stocks comprising very high concentrations of polymer and/or additive. In some instances, the concentration of the additive in the fluid stock is up to about <NUM> wt. In specific instances, the concentration of the additive in the fluid stock is about <NUM> wt. % to about <NUM> wt.

In certain instances, the liquid medium comprises any suitable solvent or suspending agent. In some instances, the liquid medium is merely utilized as a vehicle and is ultimately removed, e.g., by evaporation during the electrospraying process and/or upon drying of the deposition. In certain instances, the liquid medium comprises water, an alcohol (e.g., methanol, ethanol, isopropanol, propanol, butyl alcohol, or the like), dimethylformamide (DMF), tetrahydrofuran (THF), Dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), or a combination thereof. In certain instances, the liquid medium comprises a liquid precursor material that is converted upon deposition to a desired material, such as a ceramic. In some specific instances, the liquid medium comprises polysilazane, a silsesquioxone (e.g., polyhedral oligomeric silsesquioxane (POSS), or polysilsesquioxane (PSSQ)), or a combination thereof - e.g., wherein a deposition comprising ceramic matrix is desired.

In some instances, a polysilazane has a structure of general formula (I):.

In some instances, the polysilazane has a chain, cyclic, crosslinked structure, or a mixture thereof. <FIG> illustrates an exemplary silazane structure having a plurality of units of Formula I with cyclic and chain structures. In various instances, the polysilzane comprises any suitable number of units, such as <NUM> to <NUM>,<NUM> units and/or n is any suitable value, such as an integer between <NUM> and <NUM>,<NUM>. In certain instances, the polysilazane of formula I has an n value such that the <NUM> to <NUM>,<NUM>, and preferably from <NUM> to <NUM>,<NUM>. Additional units are optionally present where each R<NUM> or R<NUM> is optionally cross-linked to another unit at the N group - e.g., forming, together with the R<NUM> of another unit a bond - such cross-links optionally form links between separate linear chains, or form cyclic structures, or a mixture thereof. In an exemplary instance, a compound of formula I comprises a plurality of units having a first structure, e.g., -[SiHCH<NUM>-NCH<NUM>]-, and a plurality of units having a second structure, e.g., - [SiH<NUM>NH]-. In specific instances, the ratio of the first structure to the second structure is <NUM>:<NUM> to <NUM>:<NUM>. Further, in certain instances, the compound of Formula I optionally comprises a plurality of units having a third structure, such as wherein the ratio of the first structure to the third structure is <NUM>:<NUM> to <NUM>:<NUM>. The various first, second, and optional third structures may be ordered in blocks, in some other ordered sequence, or randomly. In specific instances, each R<NUM>, R<NUM>, and R<NUM> is independently selected from H and substituted or unsubstituted alkyl (straight chain, branched, cyclic or a combination thereof; saturated or unsaturated). Exemplary, polysilazanes disclosed herein comprise one or more unit of <FIG>, wherein x, y, and z are individually any suitable integer, such as <NUM> to about <NUM> or <NUM> to about <NUM>,<NUM> or more, and R is as described above for R<NUM> or R<NUM>.

In some instances, the silsesquioxane compound used in a liquid medium herein comprises a structure of general formula (II):.

In some instances, the compound is a silsesquioxane having a cage (e.g., polyhedral oligomeric) or opened cage (e.g., wherein an SiR<NUM> is removed from the cage) structure. <FIG> illustrates an exemplary cage wherein n is <NUM> (wherein the R group of <FIG> is defined by R<NUM> herein). <FIG> illustrates an exemplary opened cage wherein n is <NUM> (wherein the R group of <FIG> is defined by R<NUM> herein). In some instances, an R<NUM> or R<NUM> group of one unit is taken together with an R<NUM> or R<NUM> group of another unit to form an -O-. In certain instances, a cage structure is optionally formed when several an R<NUM> or R<NUM> groups are taken together with the R<NUM> or R<NUM> groups of other units (e.g., as illustrated in <FIG>). In various instances, the polysilazane comprises any suitable number of units, such as <NUM> to <NUM> units and/or n is any suitable value, such as an integer between <NUM> and <NUM>, e.g., <NUM>-<NUM>. In certain instances, the cage comprises <NUM> units, but larger cages are optional. In additional, opened cages, wherein one of the units is absent are also optional.

In some instances, the fluid stock has any suitable viscosity. In addition, the process and systems described herein allow for the electrospray manufacture of depositions and coatings using highly viscous (and, e.g., highly loaded) fluid stocks, if desired. For example, in some instances, fluid stocks utilized in systems and processes herein have a viscosity of about <NUM> centipoise (cP) or more, e.g., about <NUM> cP or more, or about <NUM> cP to about <NUM> Poise. In more specific instances, the viscosity is about <NUM> cP to about <NUM> Poise. In some instances, gas-driven systems and processes described herein allow for the production of an aerosol or plume that has enough inclusion component to facilitate good, high through-put formation of films that would not be possible using conventional techniques. In certain instances, the viscosity of the fluid stock is at least <NUM> centipoise (cP), such as at least <NUM> cP, at least <NUM> cP, at least <NUM> cP, at least <NUM>,<NUM> cP, at least <NUM>,<NUM> cP, at least <NUM>,<NUM> cP, or the like (e.g., up to <NUM>,<NUM> cP, up to about <NUM>,<NUM> cP, or the like). In certain instances, the viscosity of the fluid stock is about <NUM>,<NUM> cP to about <NUM>,<NUM> cP.

A process described herein comprises providing a voltage to an electrospray nozzle, such as one disclosed herein. In specific instances, the voltage is provided to the inner conduit (e.g., the walls thereof). In certain instances, application of the voltage to the nozzle provides an electric field at the nozzle (e.g., at the outlet of the inner conduit thereof). In some instances, the electric field results in the formation of a "cone" (e.g., Taylor cone) (e.g., as illustrated by <NUM> and <NUM> of <FIG>) at the nozzle (e.g., at the outlet of the inner conduit thereof), and ultimately a jet. In certain instances, after the formation of a cone, the jet is broken up into small and highly charged liquid droplets, which are dispersed, e.g., due to Coulomb repulsion.

In some instances, any suitable voltage (e.g., direct current voltage) is applied (e.g., to the nozzle). In specific instances, the voltage applied about <NUM> kV to about <NUM> kV. In more specific instances, the voltage applied is about <NUM> kV to about <NUM> kV. In certain instances, a power supply is configured to provide the voltage to the nozzle.

In certain instances, a process disclosed herein comprises providing a pressurized gas to an outer inlet of an outer conduit of an electrospray nozzle. In some instances, the outer conduit is enclosed along the length of the conduit by an outer wall having an interior surface, the outer conduit having an outer conduit inlet and an outer conduit outlet. In some instances, the pressurized gas is provided from a pressurized canister, by a pump, or by any other suitable mechanism. Providing pressurized gas to the inlet of the outer channel results in a high velocity gas being discharged from the outlet of the outer channel of the electrospray nozzle. Any suitable gas pressure is optionally utilized in processes and/or systems herein. In specific instances, the gas pressure applied (e.g., to the inlet of the outer channel) is about <NUM> psi or more. In more specific instances, the gas pressure is about <NUM> psi or more, about <NUM> psi or more, or about <NUM> psi or more. The velocity of the gas at the nozzle (e.g., the outlet of the outer channel thereof) is <NUM>/s or more, such as about <NUM>/s or more, about <NUM>/s or more, or the like. In more specific instances, the velocity is about <NUM>/s or more. In still more specific instances, the velocity is about <NUM>/s or more, e.g., about <NUM>/s or more, or about <NUM>/s. In certain instances, the gas is any suitable gas, such as comprising air, oxygen, nitrogen, argon, hydrogen, or a combination thereof.

In certain instances, the inner and outer conduits have any suitable diameter. In some instances, the diameter of the outer conduit is about <NUM> to about <NUM>, e.g., about <NUM> to about <NUM>. In more specific instances, the diameter of the outer conduit is about <NUM> to about <NUM>, e.g., about <NUM> to about <NUM>. In certain instances, the diameter of the inner conduit is about <NUM> (e.g., about <NUM>) to about <NUM>, e.g., about <NUM> to about <NUM>, e.g., about <NUM> to about <NUM>. Generally, as discussed herein, the inner conduit is configured inside the outer conduit, preferably along an identical axis, but slight offset configurations are also considered to be within the scope of the instant disclosure. In some instances, an outer wall surrounds the outer conduit, the outer wall having an interior surface (e.g., defining the outer conduit). In some instances, the average distance between the exterior surface of the inner wall and the interior surface of the outer wall (referred to herein as the conduit gap) is any suitable distance. In specific instances, the conduit gap is about <NUM> or more, e.g., about <NUM> or more. In more specific instances, the conduit gap is about <NUM> to about <NUM>. The gap is small enough to facilitate a high velocity gas at the nozzle and to facilitate sufficient disruption of the charged fluid (jet) ejected from the nozzle (e.g., such as to provide sufficiently small droplet sizes and sufficiently uniform inclusion dispersion in the plume and on the collection substrate). In some instances, the inner channel and the outer channel run along an identical or similar longitudinal axis, the length of which both the inner and outer channels running along that axis being the conduit overlap length. In some instances, the inner conduit length, the outer conduit length, and the conduit overlap length is about <NUM> to about <NUM>, or more. In specific instances, the inner conduit length, the outer conduit length, and the conduit overlap length is about <NUM> to about <NUM>, e.g., about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, or the like. In certain instances, the ratio of the conduit overlap length to the first diameter being about <NUM> to about <NUM>, e.g., about <NUM> to about <NUM>. In some instances, the inner conduit is longer than the outer conduit, the inner conduit protruding beyond the outer conduit, e.g., as illustrated in <FIG> (<NUM> and <NUM>) and <FIG>. In some instances, the protrusion length is about -<NUM> to about <NUM>, e.g., about <NUM> to about <NUM>.

In certain instances, processes disclosed herein comprise collecting and/or systems herein are configured to collect nanoscale particles and/or droplets of the plume onto a substrate. In specific instances, collection of these small particles/droplets allows for the formation of a uniform deposition on the substrate. Further, given the small size of the particles and/or droplets formed by systems and processes described herein, it is possible to form depositions having thin and/or uniform layers, and to have good control of the thickness thereof. In some instances, the substrate is positioned opposite the outlet of the nozzle. <FIG> illustrates an exemplary system <NUM> provided herein comprising a bank <NUM> of electrospray nozzles <NUM> positioned opposite a substrate <NUM>. <FIG> also illustrates an exploded view <NUM> of a nozzle <NUM> and a substrate <NUM>. As is exemplarily illustrated in <FIG>, electrospraying a fluid stock onto a substrate forms a deposition <NUM> (e.g., nanoscale coating) thereon. In some instances, the substrate and/or the electrospray bank is configured to be mobile, allowing facile deposition onto a substrate. As illustrated in <FIG>, the substrate <NUM> is optionally configured to be affixed to a roll <NUM>, and/or the bank is configured to move along the surface of a substrate, depositing a coating on the substrate as the bank moves. In specific instances, the substrate is itself grounded or positioned between a grounded component (the "collector") and the nozzle. Alternatively, a voltage, such as described herein, is applied to the "collector" and the nozzle is grounded.

In some instances, depositions disclosed herein are thin layer depositions, which are suitable for any number of applications. In various instances, the depositions are coatings comprising a matrix material (e.g., polymer or ceramic) and further comprising inclusions (e.g., nanostructured inclusions). In some instances, the inclusions are dispersed in and/or on the matrix. In other instances, depositions disclosed herein are coatings comprising a plurality of structures, such as nanostructures (e.g., the nanostructures forming the coating and being dispersed on a substrate). Also disclosed in some instances herein are articles of manufacture comprising a deposition or coat, e.g., a thin-layered coat manufactured or capable of being manufactured according to the processes described herein. In certain instances, provided herein is a substrate comprising a coating or deposition described herein on the surface thereof. It will be appreciated that the coatings, depositions, articles of manufacture and substrates are not themselves according to the claimed invention.

As discussed herein, processes and systems described herein allow for good control of the thickness of depositions described herein. In some instances, a deposition disclosed herein is a thin layer deposition, e.g., having an average thickness of <NUM> or less, e.g., about <NUM> micron to about <NUM>. In specific embodiments, the deposition has a thickness of about <NUM> micron or less, e.g., about <NUM> micron to about <NUM> micron, about <NUM> micron to about <NUM> micron, or about <NUM> micron to about <NUM> micron. However, in processes of the invention, the manufactured film has a thickness of about <NUM> to about <NUM>. Further, the processes and systems described herein not only allow for the manufacture of thin layer depositions, but of highly uniform thin layer depositions. In some instances, the depositions disclosed herein have an average thickness, wherein the thickness variation is less than <NUM>% of the average thickness, e.g., less than <NUM>% of the average thickness, or less than <NUM>% of the average thickness. In addition, in some instances wherein nano-inclusions (additives) are included in the fluid stock and/or deposition (e.g., wherein the deposition comprises a matrix material, such as a polymer matrix material), the dispersion of the nano-inclusions (additives) is such that the most probable distance between the nano-inclusions is from about <NUM> to about <NUM>.

Further, in some instances, it is desirable that any additives in the fluid stock are dissolved and/or well dispersed prior to electrospray, e.g., in order to minimize clogging of the electrospray nozzle, ensure good uniformity of dispersion of any inclusions in the resulting deposition, and/or the like. In specific instances, the fluid stock is agitated prior to being provided to the nozzle (e.g., inner conduit inlet thereof), or the system is configured to agitate a fluid stock prior to being provided to the nozzle (e.g., by providing a mechanical stirrer or sonication system associated with a fluid stock reservoir, e.g., which is fluidly connected to the inlet of the inner conduit of an electrospray nozzle provided herein).

In a specific and exemplary instance, processes provided herein are useful for manufacturing a deposition on a substrate that is transparent and/or imposes hydrophobic and/or oleophobic (anti-fingerprinting) characteristics to the surface. In addition, in some instances, the surface is anti-reflective. In specific instances, a process and/or system provided herein is utilized to manufacture such a surface. In some instances, the fluid stock suitable therefore comprises, for example, a polysilazane and/or a silsesquioxane (e.g., polyhedral oligomeric silsesquioxane (POSS) and/or polysilsesquioxane (PSSQ)). In further or alternative instances, the fluid stock comprises a transparent polymer (e.g., a polymer that is transparent in the form of a coating, such as a film (e.g., a coherent film), at a thickness less than the thickness of the deposition coating, such about <NUM> or less). A non-limiting example of such a polymer is polycarbonate (poly(bisphenol a carbonate)), or any other suitable polymer described herein. In preferred instances, the polymer is not soluble or swellable in water. The fluid stock further or alternatively comprises nanostructured inclusions, such as any other suitable inclusion described herein. In processes of the invention, the inclusion comprises graphene, graphene oxide, or reduced graphene oxide. In some instances, the fluid stock further or alternatively comprises fluoroalkyl silane or perfluoropolyether alkoxy silane (e.g., wherein alkyl or alk is a saturated or unsaturated straight chain or branched hydrocarbon having <NUM>-<NUM> carbon atoms, e.g., <NUM>-<NUM> carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, or the like). In specific embodiments, the fluid stock comprises polycarbonate, silica nanoparticles, organic polysilazane, and fluroalkyl silane the ratio of polycarbonate to silica nanoparticles to organic polysilazane to fluoroalkyl silane being about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, or about <NUM> to about <NUM>) weight parts polymer (e.g., polycarbonate) to about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, or about <NUM> to about <NUM>, or about <NUM> to about <NUM>) weight parts inclusions (e.g., silica nanoparticles) to about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, or about <NUM>) weight parts ceramic precursor (e.g., organic polysilazane). In additional embodiments, the fluid stock further comprises a fluorinated organosilane, e.g., with about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, or about <NUM> to about <NUM>) weight parts thereof (e.g., fluoroalkyl silane).

In certain instances, superhydrophobic surfaces disclosed herein have a contact angle (e.g., of water) of about <NUM> degrees or more, e.g., about <NUM> degrees or more. <FIG> illustrates non-limiting, and exemplary super hydrophobic surfaces <NUM> prepared according to the processes and with the systems described herein. As is demonstrated in the exploded view <NUM> of a droplet <NUM> on a surface <NUM> of a non-limiting exemplary surface prepared in accordance with the processes and using the systems described herein is shown to be superhydrophobic, wherein a bead of water <NUM> on the surface <NUM> has a contact angle <NUM> of about <NUM> degrees.

In some instances, articles of manufacture are disclosed herein comprising, e.g., a coat described herein. In certain instances, an article of manufacture disclosed herein comprises a deposition (e.g., thin layer deposition) described herein. In specific instances, disclosed herein is an article of manufacture comprising a substrate with a surface, the surface being at least partially coated with a material that imparts to the surface superhydrophobic characteristics, such as described herein. In specific instances, an article of manufacture disclosed herein comprises a coating or deposition comprising a polymer matrix and a plurality of nano-inclusions embedded therein (and/or on the surface thereof). In yet more specific instances, the polymer matrix comprises polycarbonate and the nano-inclusions comprise silica nanoparticles. In some instances, the article of manufacture comprising a surface is any suitable article, such as, by way of non-limiting example, a window pane, such as in a building or automobile, eye glasses, laptop computers, computer monitors, televisions, tablets, mobile telephones (e. Smartphones), personal digital assistants (PDAs), watch, and other articles. The articles of manufacture are not themselves according to the claimed invention.

In certain instances, the substrate is any suitable substrate (e.g., a grounded substrate, or a substrate located between the electrospray nozzle and a grounded plate). In some instances, collected films are optionally removed from the substrate to provide self-supporting film (e.g., that is optionally deposited on a secondary surface).

In some instances, material or films/depositions provided herein are high density (e.g., about <NUM>/cm<NUM> or more, about <NUM>/cm<NUM> or more (such as about <NUM>/cm<NUM>, about <NUM>/cm<NUM> or more, greater than <NUM>/cm<NUM>, about <NUM>/cm<NUM> to about <NUM>/cm<NUM>, or the like), flexible, and/or thin layer films or depositions.

In some instances, relatively small amounts of inclusion are required to form a coating or film disclosed herein, such as wherein the coating or film has good performance uniformity over the surface of the coating or film. In some instances, processes provided herein are well designed to not only manufacture high performance materials, but to also manufacture thin materials having very good uniformity and very low defect characteristics (e.g., which defects may result in reduced performance over time).

In various instances herein, inclusions and materials are described as having specific characteristics. It is to be understood that such disclosures include disclosures of a plurality of such inclusions having an average equal to the specific characteristics identified, and vice-versa.

Example <NUM> is according to the invention. Examples <NUM> and <NUM> are reference examples.

A fluid stock comprising <NUM> wt. % polyvinylalcohol (PVA) in water is prepared. The solution is provided to a non-gas-controlled electrospray nozzle, to which a direct voltage of about <NUM> kV to about <NUM> kV is maintained. A grounded collector is positioned opposite the electrospray nozzle, at a distance of about <NUM> to about <NUM>. High speed imaging of the electrospray process is illustrated in <FIG> (left panel), and a PVA deposition is collected on the collector, as illustrated in <FIG> (left panels). As is illustrated in <FIG>, the deposition is irregular, with large PVA beads being evident.

A <NUM> wt. % PVA solution is also electrosprayed by injecting the solution into a gas (air) stream (Qair of about <NUM> SCFH) using a coaxially configured nozzle as described herein. A direct voltage of about <NUM> kV to about <NUM> kV is maintained at the nozzle. A grounded collector is positioned opposite the electrospray nozzle, at a distance of about <NUM> to about <NUM>. High speed imaging of the electrospray process is illustrated in <FIG> (right panel), and a PVA deposition is collected on the collector, as illustrated in <FIG> (right panels). As is illustrated in <FIG>, the deposition is highly uniform, with no large PVA beads being evident.

A fluid stock comprising polycarbonate, silica nanoparticles, organic polysilazane, and fluoroalkyl silane in a ratio of about <NUM>/<NUM>/<NUM>/<NUM> is prepared in DMF (additive:liquid medium = <NUM>:<NUM>). The fluid stock is electrosprayed on a glass substrate using a non-gas controlled process and a gas-controlled process similar to Example <NUM>. <FIG> illustrates the surface coated using a gas-controlled process. Surfaces prepared according to both processes are tested for hydrophobicity, the gas-controlled process yielding a surface having a contact angle (of water) of about <NUM> degrees (as illustrated by <FIG>), whereas the base glass has a contact angle of about <NUM> degrees and the non-gas-controlled process yields a surface having a contact angle (of water) of about <NUM> degrees. A surface is also manufactured using an air-only spray process, such process yielding a surface having a contact angle of about <NUM> degrees. Further, as illustrated in <FIG>, the coated glass substrate retains good transparency. By contrast, a solution with increased polymer concentration produces a coating comprising nanofibers (rather than a coherent film), which has poor transparency (being blurry to opaque).

Claim 1:
A process for manufacturing a film or coating (<NUM>), the process comprising generating a plume or aerosol by providing a fluid stock to a first inlet of a first conduit of an electrospray nozzle,
the fluid stock comprising a liquid and an inclusion comprising graphene, graphene oxide, or reduced graphene oxide;
the plume or aerosol being generated by providing a voltage to the nozzle and electrospraying the fluid stock in the presence of a high velocity gas (<NUM>), wherein the high velocity gas is provided by providing a pressurized gas to a second inlet of a second conduit of the electrospray nozzle thereby providing the high velocity gas with a velocity of <NUM>/s or more at a second outlet of the second conduit;
the high velocity gas (<NUM>) and the plume or aerosol having a directional mean within <NUM> degrees of one another; and
the film or coating (<NUM>) having a thickness of <NUM> to <NUM>.