Systems and methods for manufacturing products including fibrous materials - Patents.com

Abstract

Systems, devices and methods are provided for manufacturing products that include fibrous materials, such as filters. The system for manufacturing products that include fibrous materials includes a first device for isolating individual nanoparticles in a gaseous medium, and a second device for mixing the individual nanoparticles with fibers to form a product that includes fibers and nanoparticles. This distributes the nanoparticles more uniformly throughout the product and in depth to the internal structure of the product. The nanoparticles increase the overall surface area within the filter media, which increases its filtration efficiency and allows for the capture of sub-micron contaminants without significantly compromising other factors, such as pressure drop through the filter. In addition, the filters produced by the systems and methods described herein can withstand rigorous testing, which allows the filter to achieve the same level of filtration performance throughout the life of the filter.

Description

[Technical field]

[0001] This application claims priority to U.S. Provisional Application No. 63 / 329,161, filed April 8, 2022, which is incorporated herein by reference in its entirety. This application is also related to commonly assigned, co-pending U.S. Provisional Application Nos. 63 / 329,009, 63 / 328,983, 63 / 328,998, 63 / 328,970, 63 / 328,959, 63 / 329,018, 63 / 329,137, 63 / 329,158, 63 / 329,146, 63 / 329,155, 63 / 329,161, and 63 / 329,162, all of which are incorporated herein by reference in their entirety. No. 6,399,623, filed on Dec. 13, 2003, the entire disclosures of which are incorporated herein by reference in their entireties in this application. FIELD OF THE DISCLOSURE This description relates generally to systems and methods for manufacturing products that include fibrous materials, such as filter media, that incorporate nanoparticles within the material. [Background technology]

[0002] Fibrous materials are particularly useful for trapping contaminants in filtration devices due to their fine fiber size. The fibers of the filter media are measured on the micrometer scale and can be spunbonded, meltblown, electrospun, or formed by other techniques. The fine fibers trap and remove contaminants in the filter media while fluid flows through the filter media.

[0003] Two main types of filtration devices incorporating fibrous materials include surface filters and depth filters. Surface filters, such as membranes or films, act as a barrier where contaminants are captured before entering the filter media structure. These surface filters usually have submicron pore sizes and narrow pore size distributions. Surface filters tend to have relatively high particle capture efficiencies. However, they also have relatively high pressure drops and low dust collection capacities. High pressure drops result in reduced airflow through the filter. Low dust collection capacity significantly shortens the life of the filter. Thus, surface filters are used in only a limited number of applications in the air filtration industry. Depth filters are commonly used air filtration devices that have medium to high efficiency, low pressure drop, and relatively high particle collection capacity. Conventional residential and commercial air filters, e.g., HEPA filters, are usually rated by their ability to capture particles between about 0.3 and 10 microns. This rating is called the Minimum Efficiency Reporting Value, or MERV, and was developed by the American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE). MERV values ​​range from 1 to 16, with higher values ​​indicating greater efficiency in removing a particular type of particle.

[0004] Contaminants come in a wide range of sizes. However, contaminants smaller than 1 micron are the most harmful particles to humans and are relatively difficult to filter. For example, conventional mechanical air filters typically report a MERV rating of about 8-10 for fibrous filtration materials. Thus, these filter media typically do not capture sub-micron particles such as viruses and other harmful pathogens.

[0005] The filtration industry has focused on two different methods to capture these submicron particles: electrostatic forces and the use of nanoparticles in filter media. Electrostatic filters are formed by electrostatically charging fibers in fibrous materials using triboelectric methods, corona discharge, hydrocharging, electrostatic spinning, or other known methods. Electrostatic filters are most efficient at capturing submicron particles, fairly efficient at capturing particles between 1-3 microns in size, and only marginally efficient at capturing larger particles between 3-10 microns. Electrostatic fibers are commonly used in many filtration applications such as face masks and high efficiency filters that filter submicron contaminants such as viruses. One drawback of electrostatic filters is that the electrostatic charge decays over time and with use of the filter. Thus, the efficiency of the filter decreases relatively quickly, shortening its lifespan. For example, an electrostatic filter with an initial MERV rating of 13 may lose at least 2-3 MERV points after decay of the electrostatic force. This can impair the filter's lifespan and partially or completely inhibit its ability to capture submicron particles.

[0006] Another method to capture sub-micron contaminants is the use of nanoparticles in conjunction with fibers. A filtration system may employ a filter medium that includes fibers with diameters measured on a relatively large micrometer scale and nanoparticles that are smaller in comparison. The nanoparticles increase the surface area within the filter medium for particle capture by reducing the overall fiber size within the filter medium. The nanoparticles also tend to collapse together, increasing the packing density within the filter medium. Even a small amount of nanometer-sized fibers formed in a layer on a microfiber material can improve the filtration properties of the material.

[0007] The most common method for incorporating nanoparticles into filter media is to apply a continuous thin layer of nanofibers by electrospinning onto a fiber substrate.Nanoparticles usually spread parallel or perpendicular to the plane of the bulk filter media layer, providing high efficiency filtration of small particles in addition to the filtration of larger particles provided by coarse filter media.For example, US Patent No. 6,743,273 discloses a filter media in which a continuous nanofiber layer is deposited on the substrate surface.US Patent No. 10,799,820 also discloses an air filtration medium that includes a continuous nanofiber layer on the filter media surface.

[0008] Existing filter media incorporating nanoparticles have improved the relative efficiency of these filters, but the commercial viability of these filters has been limited in certain applications because the nanoparticles are typically dispersed on the surface of a fibrous material, and this relatively thin layer of nanoparticles on the surface of the filter provides only limited filtration of particles and has a relatively low particle retention capacity. Many attempts have been made to incorporate nanomaterials into filter media to increase overall filtration efficiency, but these attempts have been limited to so-called "wet" methods. These wet methods involve incorporating short cut nanofibers into a liquid slurry and separating the entangled nanofibers using a surfactant. For example, U.S. Pat. No. 10,252,201 discloses filter media made from a mixture of short cut nanofibers and short cut coarse fibers formed by a wet process. Similarly, U.S. Patent Application No. 2021 / 0023813 discloses a method for producing a composite structure consisting of a continuous nonwoven substrate containing discontinuous fibers such as carbon nanofibers. The method involves stretching a continuous fiber nonwoven substrate through a slurry of discontinuous fibers in which nanomaterials are embedded in the nonwoven substrate.

[0009] Although these constructions have demonstrated enhanced efficiency, they experience other problems such as reduced life span and / or decreased efficiency as the filter media is subjected to normal use conditions. Furthermore, these wet-laid processes are not successful in incorporating the nanoparticles uniformly throughout the nonwoven material, resulting in agglomeration of the nanoparticles within the material, thereby reducing its efficiency and overall particle retention capacity. Therefore, what is needed are improved systems and methods for manufacturing products that include fibrous materials, such as filters. It would be particularly preferable to incorporate nanoparticles throughout the fibrous material, thereby improving the performance characteristics of the filter. Summary of the Invention

[0010] The following presents a summary of the claimed subject matter in order to provide a basic understanding of some aspects of the claimed subject matter. This summary is not an exhaustive overview of the claimed subject matter. This summary is not intended to identify key or critical elements of the claimed subject matter, nor is it intended to delineate the scope of the claimed subject matter. Its sole purpose is to present some concepts of the claimed subject matter in a simplified form as a prelude to the more detailed description that is presented later. Systems, devices, and methods are provided for producing products that include fibrous materials. The fibrous materials may include substrates such as sheets, layers, films, perforated films, meshes, screens, or other filter media. The substrates include fibers and include nanoparticles incorporated into at least a portion of the substrate.

[0011] In one aspect, a system for producing a product comprising fibrous material includes a first apparatus for separating and / or isolating nanoparticles in a gaseous medium and a second apparatus for mixing the nanoparticles with fibers to form a product comprising fibers and nanoparticles. The nanoparticles can be separated or isolated in any suitable gaseous medium, such as air, helium, nitrogen, oxygen, carbon dioxide, etc., and dispersed into a product, substrate, or fiber stream via a gas stream, aerosol, vaporizer, sprayer, or other suitable delivery mechanism. Separating and / or isolating individual nanoparticles in a gaseous medium and then dispersing them in a substrate or gas stream allows the nanoparticles to be distributed more uniformly throughout the product. In addition, the nanoparticles are dispersed or distributed "depth-wise" in the product. As used herein, the term "depth-wise" means that the nanoparticles are dispersed beyond the first surface of the substrate, product or other filter media, so that at least some of the nanoparticles are disposed between the first and second opposing surfaces in the internal structure of the substrate. In certain embodiments, the products are filter media and filters, such as air filters, face masks, gas turbine and compressor air intake filters, panel filters, etc. The nanoparticles increase the overall surface area within the filter media, which increases its filtration efficiency and allows for the capture of submicron contaminants without significantly compromising other factors, such as the drop in pressure (i.e., the drop in airflow) through the filter. In addition, the filters produced by the systems and methods described herein can withstand rigorous testing, which allows the filters to achieve the same level of filtration performance throughout the life of the filter. In one particular embodiment, the first apparatus includes a feeder for introducing macroclusters, agglomerates, or other nanofibers into the system and a separator coupled to the feeder and configured to mechanically separate the macroclusters of nanofibers into smaller nanofibers, which may be of any suitable size and may or may not be intertwined with one another.

[0012] The first apparatus further comprises a fiberizer disposed between the separator and a suitable dispersion device. As used herein, the term "fiberizer" means converting (e.g., liberating, separating, isolating, and / or individualizing) clusters, agglomerates, or other groups of nanoparticles into individual nanoparticles having at least one dimension less than 1 micron. In one embodiment, the second apparatus includes a nozzle or similar device for dispersing the individual nanoparticles into the first stream. The second apparatus further includes a system for producing one or more fiber streams that are mixed with the stream of individual nanoparticles. The fiber streams can be produced by any suitable mechanism known in the art, such as meltblown, spunbonded or spunlaced, thermally bonded, carded, airlaid, wet-laid, co-formed, needle punched, stitched, hydroentangled, etc. In another embodiment, the second device includes a nozzle for dispersing the individual nanoparticles on a first surface of the substrate including fibers, whereby the nanoparticles penetrate at least through the first surface of the substrate. The nozzle is preferably configured to disperse the nanoparticles in a depth direction within the substrate. In a particular embodiment, the nozzle disperses the nanoparticles substantially throughout the entire filter medium from the first surface to the opposite second surface. In another embodiment, the nozzle disperses the nanoparticles through a portion of the filter medium from the first surface to a position between the first and second surfaces. In another embodiment, the nozzle disperses the nanoparticles in a density gradient from the first surface to the opposite second surface of the substrate. The density of the nanoparticles can be higher on either the first or second surface.

[0013] The second apparatus may further include a reduced pressure or vacuum source disposed underneath the substrate opposite the nozzle to enhance penetration depth and uniformity of the nanoparticles. The reduced pressure source may be any suitable suction device, such as a suction pump, that draws the nanoparticles through the substrate. The second apparatus may further include a feeder for advancing the substrate from the upstream end to the downstream end. A nozzle is preferably disposed between these two ends to disperse the nanoparticles onto the substrate. In certain embodiments, the feeder may further include a support surface extending between the two winders to support the substrate as the winders move downstream through the system. In other embodiments, the substrate is unwound directly from the unwinder to the winder without a separate support surface. The second apparatus may further include a coating apparatus for dispersing a binder on the fibers in the substrate. The binder may include a variety of conventional materials including naturally occurring materials such as starch, dextrin, guar gum, or synthetic resins such as EVA, PVA, PVOH, SBR, polyglycolide, and the like. In some embodiments, the substrate includes its own binder composition. In these embodiments, a binder or material may or may not be added to the substrate. In one such embodiment, the substrate includes biocomponent fibers, one of the components including an outer coating at least partially surrounding an inner core. The coating apparatus may include any suitable apparatus for dispersing the binder across the substrate. In one embodiment, the coating apparatus includes a spraying apparatus having an outlet and a nozzle adjacent the upstream end of the feeder. The spray coater may be positioned downstream of the fiberizer so that the binder can be sprayed after nanoparticle deposition. In another embodiment, the system may include two spray coaters, one positioned upstream of the fiberizer and a second spray coater positioned downstream of the fiberizer system, to coat the substrate with a second binder after nanoparticle deposition. The second device may further include a reduced pressure or vacuum source located underneath the substrate opposite the sprayer to increase nanoparticle penetration depth and binder uniformity. The reduced pressure source may be any suitable suction device, such as a suction pump, that draws the binder through the substrate. The second apparatus may further include a dryer, such as an IR oven, positioned near the downstream end of the feeder to heat the nanoparticles and fibers and bond the nanoparticles to the fibers within the substrate.

[0014] The fiberizer may further include a gas source, such as compressed air or another suitable gas, and a pump to draw the smaller nanofiber clusters from the separator through the passageway and into the device. The compressed air source provides a moving fluid that circulates the nanofibers throughout the fiberizer and ultimately out into a nozzle. The pump may include any suitable pump, such as positive displacement, centrifugal, axial, etc. In one embodiment, the pump includes an evacuation device configured to generate sufficient reduced pressure to draw the small clusters of nanofibers from the separator through the passageway and into the pump. The system may further include an energy source, such as a second pump, a second ejector, coupled to the first ejector and configured to advance the small nanofiber clusters from the first ejector against the surface at a velocity sufficient to break down the nanofibers and convert at least some of the small nanofiber clusters into individual nanoparticles. Applicants have discovered that advancing the nanofibers against a suitable surface at a velocity of about 500 feet per minute (fpm) to about 10,000 fpm, preferably about 2,000 fpm to about 6,000 fpm, is sufficient to break down at least some of the nanofibers into individual nanoparticles.

[0015] The surface may be any surface that impedes the flow of nanofibers through the passageway, such as an interior wall of the passageway at a junction, or a change in direction of another interior wall, e.g., a curved surface, a vertical surface, etc. Alternatively, the passageway may include a wall or other surface disposed within the passageway, or a protrusion into the passageway of a fluid path. In one embodiment, the passageway extends to a substantially T-shaped junction that includes two separate passageways extending from the junction. The second ejector is configured to advance the nanofibers against the wall of the T-shaped junction at a rate sufficient to break down at least some of the nanofibers.

[0016] In certain embodiments, the fiberizer further comprises one or more reactors for separating the previously isolated individual nanoparticles from the nanofiber agglomerates that have not yet been completely broken down. The reactor comprises a housing connected to the passageway and having an internal chamber and a reduced pressure source configured to draw smaller clusters of nanofibers away from the individual nanoparticles. In some embodiments, the reactors each include a rod or tube extending through the internal chamber, and one or more inlets located at one end of the internal chamber and substantially surrounding the tube, which in some embodiments may extend substantially through the center of the internal chamber. The inlets are connected to a passageway whereby the nanofiber clusters and individual nanoparticles are drawn into the chamber through the inlets. The central tube includes an opening at one end opposite the inlets. The opening is connected to an inner channel within the tube, with an outlet connected to a nozzle or other dispersion device. This allows the nanoparticles to pass through the inlets into the reactor before passing into the tube and into the dispersion device. The inlets may be oriented at an angle relative to the central tube, such that the nanofibers and nanoparticles enter the inner chamber at a transverse angle relative to the outer surface of the reactor. In a preferred embodiment, at least one or more inlets are oriented such that as the nanofibers and nanoparticles enter the reactor, they move in a direction approximately tangential to the central tube. As the nanofibers and nanoparticles enter the annular chamber around the tube, the velocity vectors (speed and direction) of the nanofibers and nanoparticles create a vortex within the reactor, causing them to spin from one end to the other around the central tube. Because the individual nanoparticles are significantly lighter than the tangled nanofibers that are still clustered, these individual nanoparticles are drawn into the inlet of the central tube. The vortex within the chamber may also further break up (e.g., loosen, separate, and / or individualize) the clusters of nanofibers as they pass through the reactor. The reactor may further include one or more outlets located opposite the inlet. The larger, heavier clusters of nanofibers that have not yet been broken down are drawn through these outlets. Thus, the isolated and individualized nanoparticles are drawn into the nozzle, and the clusters of nanofibers are drawn through the outlets. These outlets may be connected to a first or second pump, or to additional pumps within the fiberizer designed to further break down the clusters of nanofibers and recirculate them.

[0017] In another aspect, a method of making a product comprising fibrous material includes separating and / or isolating nanoparticles in a gaseous medium and mixing the nanoparticles with fibers to form a product, which can include, for example, filtration media or filters, such as air filters, face masks, gas turbine and compressor air intake filters, panel filters, and the like. In one embodiment, a first stream of nanoparticles is mixed with one or more fiber streams to form a fibrous material. The fiber streams can be produced by any system known in the art, such as meltblown, spunbonded or spunlaced, thermally bonded, carded, airlaid, wet-laid, co-formed, needle punched, stitched, hydroentangled, etc. In another embodiment, the individual nanoparticles are dispersed on a first surface of a substrate comprising fibers, such that the nanoparticles penetrate at least through the first surface of the substrate. In certain embodiments, the nanoparticles are dispersed substantially throughout the entire filter medium to a second surface opposite the first surface. In other embodiments, the nanoparticles are dispersed through a portion of the filter medium from the first surface to a location between the first and second surfaces. In other embodiments, the nanoparticles are dispersed in a density gradient from the first surface of the substrate to the opposite second surface. The density of the nanoparticles can be higher on either the first or second surface. In certain embodiments, the substrate is advanced from the upstream end to the downstream end, and a nozzle is preferably disposed between these two ends to disperse the nanoparticles onto the substrate.

[0018] In certain embodiments, the binder is dispersed on the fibers in the substrate. The binder may include a variety of conventional materials, including naturally occurring materials such as starch, dextrin, guar gum, or synthetic resins such as EVA, PVA, PVOH, SBR, polyglycolide, and the like. In some embodiments, the substrate includes its own binder composition. In these embodiments, the binder or material may or may not be added to the substrate. In one such embodiment, the substrate includes biocomponent fibers, one of the components including an outer coating at least partially surrounding an inner core. In certain embodiments, nanoparticles are separated from macroclusters, agglomerates, or other nanofibers in a gaseous medium, such as compressed air. The macroclusters may be of any suitable size and may or may not be intertwined with one another. These nanofiber macroclusters are first mechanically separated from one another to form smaller nanofibers having a size suitable for advancing through a fiberizer. The fiberizer breaks down the nanofibers into individual nanoparticles.

[0019] The method may further include applying a reduced pressure to the nanofibers to suck the nanofibers into a compressed air stream and advancing the nanofibers against a surface to break up at least some of the nanofibers into individual nanoparticles. The surface may be, for example, an inner wall of a passageway at a junction, or a surface having a change in direction of other inner walls, e.g., a curved surface, a vertical surface, etc. In one embodiment, the nanofibers are advanced into a substantially T-shaped junction that includes two separate passageways extending from the junction. The velocity of the nanofibers may be from about 500 fpm to about 10,000 fpm, preferably from about 2,000 fpm to about 6,000 fpm.

[0020] In certain embodiments, the method further comprises separating the individual nanoparticles already isolated from the nanofiber agglomerates that have not yet been completely broken down. In these embodiments, the particles (both nanofiber agglomerates and individual nanoparticles) are fed into the interior chamber of one or more reactors. The particles are separated in the reactor, whereby the nanoparticles enter the nozzle and the remaining nanofiber agglomerates exit the reactor for recirculation through the system. In a preferred embodiment, the particles are advanced into the reactor at various angles relative to the central rod, whereby the velocity vectors (speed and direction) of the nanofibers and nanoparticles create vortexes within the reactor, causing them to swirl from one end to the other around the central rod. Because the individual nanoparticles are significantly lighter than the still clustered entangled nanofibers, these individual nanoparticles are drawn into the inlet of the central rod. The vortexes within the chambers further break down (e.g., free, separate and / or individualize) the nanofiber clusters as they pass through the reactor. The recitation of desirable objects herein as being met by various embodiments of the present description is not intended to mean or imply that any or all of those objects are present as essential features, either individually or collectively, in the most general embodiment of the present description, or in any of its more specific embodiments. [Brief description of the drawings]

[0021] [Figure 1] FIG. 2 is a side view of a fibrous material having nanoparticles dispersed throughout a portion of the material. [Diagram 2] FIG. 1 is a side view of a fibrous material having nanoparticles dispersed throughout the material. [Diagram 3] FIG. 1 is a side view of a fibrous material having nanoparticles dispersed in a gradient throughout the material. [Figure 4] 1 shows a dual layer filter medium. [Diagram 5] 5A-5C show biocomponent fibers incorporated into a fibrous material. [Figure 6] 1 shows a pleated fiber filter medium. [Figure 7]A representative air filter is shown. [Figure 8] 1 shows a gas filter having first and second support membranes and a filter medium. [Figure 9] 9A and 9B show an apertured film for use as a support membrane. [Figure 10A] 1 illustrates different embodiments of apertured films that incorporate nanoparticles into the film. [Figure 10B] 1 illustrates different embodiments of apertured films that incorporate nanoparticles into the film. [Figure 10C] 1 illustrates different embodiments of apertured films that incorporate nanoparticles into the film. [Figure 10D] 1 illustrates different embodiments of apertured films that incorporate nanoparticles into the film. [Figure 10E] 1 illustrates different embodiments of apertured films that incorporate nanoparticles into the film. [Figure 11] A gas filter is shown. [Figure 12] 1 illustrates a schematic of a system for producing fibrous material within a substrate. [Figure 13] 1 illustrates a schematic of a system for converting nanofiber clusters into individual nanoparticles. [Figure 14] 14A-14C are photographs of macroclusters of nanofibers, smaller clusters of nanofibers, and individualized nanoparticles, respectively. [Figure 15] 14 shows an exhaust device for the system of FIG. 13. [Figure 16] 14 shows a reactor for the system of FIG. 13. [Figure 17] 1 illustrates another embodiment of a system for converting nanofiber clusters into individual nanoparticles. [Figure 18] 1 illustrates a system for producing a dual layer fibrous material. [Figure 19] 1 shows a fibrous material with nanoparticles dispersed throughout the depth of the material. [Figure 20] 1 shows a fibrous material with nanoparticles dispersed throughout the depth of the material, with a scrim layer overlying the nanoparticles. [Figure 21] 1 shows a bi-layer fibrous material with nanoparticles dispersed on the inner surface of the two layers. [Figure 22] 1 illustrates an alternative embodiment of a system for producing a fibrous material in a fluid stream. [Figure 23A] 1 is a photograph of a fibrous material without a binder. [Figure 23B] 1 is a photograph of a fibrous material with a binder. [Figure 24A] Photograph of a fibrous material with nanoparticles dispersed in agglomerates or clusters throughout the material. [Figure 24B] 1 is a photograph of a fibrous material with nanoparticles substantially uniformly dispersed throughout the material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] This description and the accompanying drawings show exemplary embodiments and should not be considered limiting, with the claims defining the scope of this description including equivalents. Various mechanical, compositional, structural, and operational changes may be made without departing from the scope of this description and the claims. In some instances, well-known structures and techniques have not been shown or described in detail so as not to obscure this description. Similar numbers in two or more figures represent the same or similar elements. Furthermore, elements and their associated aspects, whenever possible, may be included in other embodiments where they are not specifically shown and described. For example, if an element is described in detail with respect to one embodiment and not described with respect to a second embodiment, the element may nevertheless be claimed to be included in the second embodiment. Furthermore, the descriptions herein are for illustrative purposes only and may not necessarily reflect the actual shape, size, or dimensions of the system or of the illustrated components.

[0023] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the," and any singular use of any word, include plural referents unless expressly and unambiguously limited to one referent. As used herein, the term "include" and its grammatical variations are intended to be open-ended, and thus, the recitation of listed items does not exclude other similar items that may be substituted for or added to the listed items. Unless otherwise noted, any quantitative values ​​are approximate, whether or not indicated by the phrase "about" or "approximately." The materials, methods, and examples described herein are illustrative only and are not intended to be limiting.

[0024] Systems, devices, and methods are provided for manufacturing products that include fibrous materials. The fibrous materials can include substrates such as sheets, layers, films, perforated films, meshes, nets, or other filter media. The substrates include fibers, and include fibers and nanoparticles that are incorporated into at least a portion of the substrate. As used herein, the term "nanoparticle" refers to any particle that has a dimension of less than 1 micron in at least one axis or dimension. For example, fibers that have a diameter or width of less than 1 micrometer and fibers that have a length of greater than 1 micrometer are nanoparticles as used herein.

[0025] In certain embodiments, each individual nanoparticle may be a small particle ranging in size between about 1 and about 1000 nanometers, preferably between about 1 and about 650 nanometers. At least half of the particles in the number size distribution may measure 100 nanometers or less. Most nanoparticles are typically composed of only a few hundred atoms. As the size of nanoparticles approaches the atomic scale, the material properties change. This is due to the increased ratio of surface area to volume, where the surface atoms dominate the material performance. Due to their very small size, nanoparticles have an extremely large volume to surface area ratio when compared to bulk materials such as powders, plates, sheets, or larger fibers. This property allows nanoparticles to have unexpected optical, physical, and chemical properties, since they are small enough to confine their electrons and create quantum effects. In some embodiments, the nanoparticles include nanofibers having at least one dimension less than 1 micron (i.e., diameter, width, height, etc., depending on the cross-sectional shape of the fiber). The nanofibers can have a continuous length, or the nanofibers can have a discrete length, such as between 1 and 100,000 microns, preferably between about 100 and 10,000 microns.

[0026] The nonwoven substrates discussed herein may include structures of individual fibers or strands interleaved, intertwined, or bonded together. Nonwovens include sheet or web structures that are bonded together by mechanical, thermal, or chemical entanglement of fibers or filaments (and by perforated films). They may be substantially flat, porous sheets made directly from separate fibers, molten plastic, or plastic films. Examples of suitable nonwoven materials include, but are not limited to, meltblown, spunbonded, spunlaced, bonded-carded, airlaid, wet-laid, co-formed, needle-punched, seamed, hydroentangled, and the like fibers, layers, or webs.

[0027] In certain embodiments, the substrate may comprise a knitted fabric and / or a woven material. The knitted fabric may comprise any knit pattern suitable for the intended application. Suitable knitted fabrics for filter applications include weft knit, warp knit, knitted mesh panels, compressed knit mesh, and the like. Suitable woven materials for filter applications include woven filter media such as monofilament fabric, multi-fiber fabric, nylon mesh, polyester mesh, polypropylene mesh, and the like. Woven fabrics may be used, for example, in mesh filter press fabrics, woven filter pads and other die-cut pieces, centrifugal filter bags, liquid filter bags, dust collection bags, bed dryer bags, rotary drum filters, filter belts, leaf filters, roll filter media, and the like. In some embodiments, the fibrous material may include structures that include interwoven or entangled short-cut fibers and / or filaments. As used herein, short-cut fibers refer to fibers of finite length. As used herein, filaments refer to fibers having a substantially continuous length. In some embodiments, the substrate may include short-cut coarse microfibers and / or fine fibers. As used herein, "fine fibers" refer to fibers having a diameter less than 1 micron, "coarse fibers" refer to fibers having a diameter greater than 10 microns, and microfibers are synthetic fibers having a diameter less than 10 microns.

[0028] In certain embodiments, the nanoparticles are "depth-dispersed" within the substrate. As used herein, the term "depth-dispersed" means that the nanoparticles are dispersed beyond a first surface of the substrate, such that at least some of the nanoparticles are disposed within the internal structure of the substrate or filter medium between the first and second opposing surfaces. In certain embodiments, the nanoparticles are dispersed substantially throughout the filter medium to a second surface opposite the first surface. In other embodiments, the nanoparticles are dispersed through a portion of the filter medium from the first surface to a location between the first and second surfaces. In some embodiments, the nanoparticles are distributed three-dimensionally in space relative to the supporting fibers, which can increase the fiber surface area and microvolume within the fibrous material. The three-dimensional distribution also provides resistance to complete blockage of certain portions of the fibrous material, which is particularly useful in filter media, as it allows fluids (e.g., air and other gases) to pass through the filter, thereby reducing the total pressure drop across the filter. In other embodiments, the nanoparticles are arranged in a density gradient across the thickness of the substrate, such that a higher density of nanoparticles is arranged near one surface than on the opposite surface, or a higher density of nanoparticles is arranged on the surface compared to the center of the substrate. The density gradient presented therein may be substantially linear, which may be reduced to a series of discrete steps, or the gradient may be random (i.e., a generally non-linear or step-like reduction in density scheme). This density gradient provides several advantageous features (as discussed below) for certain applications, such as filters. The nanoparticles may comprise any suitable material, such as glass, biosoluble glass, ceramic materials, acrylics, carbon, metals such as alumina, polymers (nylon, polyethylene terephthalate, etc.), polyvinyl chloride (PVC), polyolefins, polyacetals, polyesters, cellulose ethers, polyalkylene sulfides, poly(arylene oxides), polysulfones, modified polysulfone polymers and polyvinyl alcohols, polyamides, polystyrene, polyacrylonitrile, polyvinylidene chloride, polymethyl methacrylate, polyvinylidene fluoride, and any combination thereof. In some embodiments, nanoparticles can be produced as bipartite pie and islands-in-the-sea. The filaments are then stretched to a degree that results in submicron filaments. The continuous filament nanofibers are cut to the desired length, preferably about 100 to about 10,000 microns. In some embodiments, the nanoparticles are absorbents and adsorbents. In some embodiments, the nanoparticles are activated carbon fibers or activated carbon powder. In some embodiments, the nanoparticles are catalytic particles or catalytic fibers. In some embodiments, the nanoparticles can be obtained by feeding sub-micron fibers into a shredder or grinder or edge trimmer device that inputs bonded fibers and results in short cut fibers. For example, lightweight biocomponent meltblown or nano meltblown fabrics can be fed into a shredder to obtain sub-micron nanoparticles.

[0029] In some embodiments, different nanoparticles may be mixed. For example, nanofibers and nanobeads can be mixed. Two different nanofibers with different melting points can also be mixed so that the lower melting point nanoparticles can act as binders for the higher melting point nanofibers. Nanoparticles with different diameters and different lengths can be mixed as well. In some embodiments, the nanoparticles are selected from environmentally sustainable raw materials. The nanoparticles may be adult soluble glass nanofibers, biodegradable nanoparticles, compostable nanoparticles, or recyclable compositions. Different types of nanoparticles can be mixed. Some nanoparticles can be functional nanoparticles. For example, functional nanoparticles can include activated carbon and / or antibacterial substances deposited and / or bonded to the fibers in the fibrous material. This can improve the gas absorption efficiency and bacteria killing efficiency of the fibers. In addition, fibrous microfibers with glass and carbon deposited nanoparticles provide filtering and deodorizing functions as a filter medium.

[0030] In some embodiments, the nanoparticles are bonded to the fibers through mechanical entanglement. This mechanical bond can be supplemented with adhesives or binders, as discussed in more detail below. In certain embodiments, the nanoparticles are not crimped (i.e., they do not contain the large wavy, bent, twisted, spiral-serrated, or similar shapes associated with nanoparticles in a relaxed state). In other embodiments, the nanoparticles can have a crimped body structure with discrete lengths. For example, when these crimped nanofibers with discrete lengths are bonded to a fiber, they entangle with tight bonds among themselves and with, on, and around the fiber to form a modified fiber. In other embodiments, the bond of the nanofibers to the micron fibers is achieved by electrostatic and / or van der Waals attractions between the fiber and the nanoparticles. Filter media and filters, such as air filters, face masks, gas turbine and compressor air intake filters, panel filters, and the like, are also provided, which include nanoparticles distributed in depth within the filter media. In some embodiments, the filters include one or more support layers bonded to the filter media. The support layers and / or filter media may include nanoparticles distributed in depth within the layer. In some embodiments, polymer layers, membranes, or films are provided in which the nanoparticles are arranged in depth within the polymer layer, with one or more openings for the flow of gas or liquid therethrough. In other embodiments, the fibrous material comprises a flexible surface layer for finger bandage pads, face masks, and the like.

[0031] Provided herein are systems, apparatus, and methods for producing fibrous materials and products that include fibrous materials (e.g., gas filters). Systems and methods may also be provided for isolating individual nanoparticles in a gaseous (rather than liquid) medium, such as air, helium, nitrogen, oxygen, carbon dioxide, etc., and that can be dispersed into another product, film, layer, or substrate via a gas stream, aerosol, vaporizer, spray, or other suitable delivery mechanism. Although the following description is presented primarily with respect to fibrous materials and filter media, it should be understood that the devices and methods disclosed herein can be easily adapted for use in a variety of other applications. For example, the fibrous materials disclosed herein can be useful for use in household cleaning products, roofing and flooring products, automotive interior decoration and headline photoengraving machines, reusable bags, wallpaper, filtration devices, insulation, and the like. In addition, the individual nanoparticles isolated and produced by the methods described herein can be utilized in various coatings, composites and / or environmental applications, such as additives for polymers, food packaging, flame retardants, fuel cells, batteries, capacitors, nanoceramics, light sources, materials manufacturing, manufacturing methods, composites, reinforcement of cement and other materials, medical diagnostic applications, medical therapeutic devices or treatments, tissue engineering such as scaffolds for bone or tissue repair, drinking water, industrial processes, food and beverage products, pharmaceutical and biological products, tissue imaging, medical therapy delivery, biodegradable compounds, and the like.

[0032] FIG. 1 illustrates a fibrous material or substrate 10 including a plurality of fibers 12 and nanoparticles 14. The substrate 10 has a first surface 16 and a second surface 18 opposite the first surface 16, defining a width or thickness between the first and second surfaces 16, 18. Nanoparticles 14 are deposited in the substrate through the first surface 16. As shown, the nanoparticles 14 penetrate through the first surface 16 into the "depth" of the substrate 10 between the first and second surfaces 16, 18. In some embodiments, the nanoparticles 14 penetrate at least 25% of the width or thickness between the first and second surfaces 16, 18, or more preferably at least 50% of the thickness from the first surface. In other embodiments, the nanoparticles 14 penetrate substantially throughout the substrate 10 from the first surface 16 to the second surface 18. The nanoparticles 14 preferably comprise individual nanoparticles that have been broken down, separated and isolated from one another prior to dispersion in the substrate 10 (as shown in FIG. 24B). Thus, the nanoparticles 14 are not present in the fibrous product in the layer and do not have large aggregates or clumps of nanofibers (as shown in FIG. 24A). This provides a greater dispersion of the nanoparticles throughout the substrate, which in some applications, such as gas filters, results in a more efficient filtration capacity for filtering out contaminants. In addition, this provides a fibrous material with a greater areal density of nanoparticles in grams per square meter (gsm) or "add-on amount" in the material. The term "add-on amount" as used herein means the areal density (gsm) of material, fiber or particles in a thin layer, sheet or film material. In certain embodiments, the nanoparticles have a density of about 0.1 g / m 2 ~about 20g / m 2 , preferably at least about 2.0 g / m 2 The specific add-on amount or areal density may depend on the application. For example, applicants have determined that a higher areal density or add-on amount increases the efficiency of the fibrous material in filtering out contaminants. Thus, the specific add-on amount of nanoparticles may depend on the intended efficiency of the filter media.

[0033] FIG. 2 illustrates a fibrous material or substrate 20 including a plurality of fibers 12 and nanoparticles 14. As shown, the nanoparticles 14 penetrate the entire width of the substrate 20 from the first surface 16 to the second surface 18. In certain embodiments, the nanoparticles 14 are dispersed throughout substantially the entirety of the substrate fibers 12 as illustrated in FIG. 2. In certain embodiments, the density of nanoparticles located at the first surface 16 differs by less than 50% of the density of nanoparticles dispersed within the central portion of the substrate 20 between the surfaces 16, 18. In some embodiments, this difference is less than 25%, and preferably less than 10%. In certain embodiments, the amount or number of individual nanoparticles dispersed within the central portion of the substrate 20 is at least about 50%, preferably at least about 75%, and more preferably about 90% of the amount of individual nanoparticles dispersed at or near the first surface 16. In other embodiments, the nanoparticles 14 are arranged in a density gradient from the first surface 16 to the second surface 18. For example, FIG. 3 shows a substrate 30 in which the nanoparticles 14 form a density gradient, with a higher density of nanoparticles 14 dispersed near the first surface 16 than at the second surface 18. In certain embodiments, the density of the nanoparticles located at the first surface 16 differs from the density of the nanoparticles dispersed at the second surface 18 by more than about 75%. In some embodiments, the difference is more than 50%. In some embodiments, the difference is more than 25%. In certain embodiments, the amount or number of individual nanoparticles dispersed at or near the second surface 18 is at least about 50% less, preferably at least about 25% less, and more preferably less than about 10% of the amount of individual nanoparticles dispersed at or near the first surface 16.

[0034] 3 may be substantially linear from the first surface 16 to the second surface 18. Alternatively, the density of nanoparticles 14 may be reduced in a series of discrete steps from the first surface 16 to the second surface 18, or the gradient may be random (i.e., a generally non-linear or step-like scheme of density reduction). In other embodiments, nanoparticles may be added into the substrate from both the first and second surfaces 16, 18. In these embodiments, the areal density or "add-on amount" of the first and second surfaces 16, 18 may be substantially the same as one another, or may differ depending on the application. In these embodiments, the areal density or "add-on amount" present in the center of the substrate is lower than the surfaces 16, 18. For example, the areal density of the center of the substrate may be 75% of the areal density of the surfaces 16, 18, or it may be about 50%, 40%, or 25%. The distribution of nanoparticles throughout the thickness of the fibrous material can be measured, for example, using imaging techniques. A close-up of the textile product taken at a horizontal cross-section of the product in the middle of the thickness of the product using electron microscopy or other techniques can be compared with images taken at the top or bottom surface of the product, or all three images can be compared to measure the varying degrees of deposited nanoparticle amounts. Computerized image analysis processes can be employed. For example, in FIG. 3, a cross-section can be taken at line AA, and a cross-section can be taken at BB. Planar images of each cross-section can be taken by electron microscopes, scanning electron microscopes, and other microscopes. The planar image of the cross-section taken at cross-section AA can be compared, for example, with the planar image taken at cross-section BB. The number of microfibers, the number of nanoparticles, or both in samples of the same two-dimensional size can be evaluated and compared. In addition, imaging techniques can be used for three-dimensional samples. These techniques can be used to evaluate fiber orientation and other properties. These techniques can be used to determine whether nanoparticles have been deposited into the depth of the substrate, substantially throughout a significant portion of the substrate, substantially throughout the entire depth, or throughout some portion of the substrate depth.

[0035] The contemplated fibers of the substrate can be made by any method including, but not limited to, airlaid processes, spinneret, gel spinning, melt spinning, wet spinning, dry spinning, islands-in-the-sea staple fiber, or spunbond. Such methods are described in U.S. Patent Nos. 4,406,950, 6,338,814, 6,616,435, 6,861,142, 7,252,493, 7,300,272, 7,309,430, 7,422,071, 7,431,869, 7,504,348, 7,774,077, 9,522,357, 9,993,761 and U.S. Patent Application Publication No. 2009 / 266,759, the complete disclosures of which are incorporated herein by reference. Contemplated fibers may have many cross-sectional shapes, including, but not limited to, ring, kidney, dogbone, trilobal, barbell, bow tie, star, Y-shape, etc. These and / or other conventional shapes may be used in some embodiments to achieve desired performance characteristics. The fibers in the substrate remain interconnected through a binder such as an adhesive, by being intertwined with each other, by thermal bonding, chemical bonding. The fibers may be man-made or natural fibers. Suitable materials for the fibers include, but are not limited to, polypropylene, polyester (PET), PEN polyester, PCT polyester, polypropylene, PBT polyester, copolyamide, polyethylene, high density polyethylene ("HDPE"), LLDPE, cross-linked polyethylene, polycarbonate, polyacrylate, polyacrylonitrile, polyfumaronenitrile, polystyrene, styrene maleic anhydride, polymethylpentene, cycloolefin copolymers or fluorinated polymers, polytetrafluoroethylene, perfluorinated ethylene and copolymers with PVDF such as hexafluoropropylene or P(VDF-TrFE) or P(VDF-TrFE). Examples of suitable fibrous materials include terpolymers such as ethylene-propylene copolymers (FE-CFE), propylene, polyimides, polyetherketones, cellulose esters, nylons and polyamides, polymethacrylic acid, poly(methyl methacrylate), polyoxymethylene, polysulfonates, acrylics, styrenated acrylics, pre-oxidized acrylics, fluorinated acrylics, vinyl acetate, vinyl acrylate, ethylene vinyl acetate, styrene-butadiene-styrene-butadiene, ethylene / vinyl chloride, vinyl acetate copolymers, latex, polyester copolymers, carboxylated styrene acrylics or vinyl acetate, epoxies, acrylic multipolymers, phenolics, polyurethanes, cellulose, styrene, or any combination thereof. Other conventional fibrous materials are also contemplated. The fibers may include fibers of different sizes, with the fibers typically having diameters ranging from about 1 to about 1,000 microns and lengths ranging from about 0.5 to 3 inches. The fibers may be configured as a gradient density filter medium, where the pore size decreases from the top (upstream) to the bottom (downstream) surface of the filter to increase capture efficiency and dust holding capacity. This configuration also allows for different amounts of nanoparticles to be dispersed at different depths into the filter medium. For example, the upstream side of the filter medium has the largest fiber size and a greater nanoparticle density to allow for more voids, while the downstream side of the filter medium has smaller sized fibers to obtain a lower nanoparticle density. Alternatively, this structure may be reversed to obtain a greater nanoparticle density in the downstream portion of the filter medium. The fibers in the filter media may remain connected to other fibers by thermal bonding, chemical bonding, or intertwining. In particular, mechanical filtration may use bicomponent fibers, which are formed by extruding two polymers from the same spinneret, both polymers contained within the same filament. Suitable materials for bicomponent fibers include, but are not limited to, polypropylene (PP) / polyethylene (PE), polyethylene terephthalate (PET) / polypropylene (PP), and the like.

[0036] In some embodiments, the substrate may include "high loft" fibrous materials, including spunbond or air-through bonded carded fibers. As used herein, the term "high loft" means that the volume of voids is greater than the volume of total solids. For air-through bonded carded nonwoven fibers, the loft of the substrate may be controlled by various means known to those skilled in the art. For example, the loft may be increased by applying less compressive force to the filter media during bonding. In another example, the high loft nonwoven material may be produced using fibers having a greater thickness, such as 3.3 decitex (3 denier) or more, 5.6 decitex (5 denier) or more, 6.7 decitex (6 denier) or more (discussed in more detail below). In other embodiments, the loft may be increased using eccentric biocomponent fibers, as shown in FIG. 5C and discussed in more detail below.

[0037] In certain embodiments, the fibers may include a silicone-based coating to improve the efficiency of the filter media in capturing contaminants, particularly contaminants in the range of E2 and E3 particle groups. The silicone-based coating may include a reactive silicone macroemulsion. The silicone emulsion may include, for example, a dimethyl silicone emulsion, an amino-type silicone emulsion, an organofunctional silicone emulsion, a resin-type silicone emulsion, a film-forming silicone emulsion, and the like. In one embodiment, the reactive silicone macroemulsion includes an amino-functional polydimethylsiloxane and / or a polyethylene glycol monotridecyl ether. Suitable silicone coatings are described in commonly assigned U.S. Provisional Patent Application No. 63 / 406,686, filed September 14, 2022, the entire disclosure of which is incorporated herein by reference. The filter medium may contain a charging additive to adjust the triboelectric charging of the fibers in the filter and increase the stability and / or duration of the triboelectric charging. This increases the overall filtration efficiency of the filter without compromising other important filter properties such as lifespan, dust holding capacity, and pressure drop of the airflow through the filter. Suitable charging additives for triboelectric charging are described in commonly assigned U.S. Provisional Patent Application No. 63 / 410,731, filed September 28, 2022, the entire disclosure of which is incorporated herein by reference.

[0038] The fibers may have a thickness suitable for the application. In some embodiments, the fibers have at least one dimension in the range of about 1 to about 10,000 micrometers, or about 1 to about 1,000 micrometers, or about 10 to 100 micrometers. The thickness of the fibers may also be measured in decitex (denier), which is a unit of measure of the linear mass density of the fiber. In some embodiments, the fibers may have a linear density of about 1.1 decitex (about 1 denier) to about 11 decitex (about 10 denier). The nanoparticles are fibers having at least one dimension in the range of about 1 to about 1,000 nanometers, or about 1 to about 100 nanometers. The fiber and nanoparticle dimensions may be diameter or width, depending on the shape of the fiber or nanoparticle.

[0039] For gas filters, such as pleated or non-pleated air filters, the fibers may have a linear density of about 1.1 dtex (about 1 denier) to about 11 dtex (about 10 denier). The filter media may include fibers having the same or different linear densities. Fibers in air filters typically have a linear density of about 3.3 dtex (about 3 denier) or less to ensure that the fibers are fine enough to capture contaminants passing through the filter. Applicant has unexpectedly found that with nanoparticles dispersed throughout the filter media, the fibers can have a greater linear density, for example, greater than 3.3 dtex (3 denier). This is because the nanoparticles provide greater filtering capacity. In some cases, the fibers can have a linear density of 3.3 dtex (3 denier), 5.6 dtex (5 denier) or more, or 6.7 dtex (6 denier) or more, or even as much as 7.8-11 dtex (7-10 denier). Applicants have also found that in some applications, fibers having a greater linear density than those used in conventional filters (e.g., about 3.3 decitex (about 3 denier)) provide more open space or pores within the filter media, which allows for a greater density of nanoparticles to be dispersed therein. Although this may be counterintuitive to one of ordinary skill in the art, Applicants have found that fibers having a greater linear density that incorporate nanoparticles actually improve the overall efficiency of the filter.

[0040] In certain embodiments, the filter medium may include at least two different fiber thicknesses or linear densities, resulting in at least two different filter layers within the same filter medium. For example, in some cases, a portion of the filter medium includes fibers with a linear density of more than 3.3 dtex (3 denier), such as 5.6 dtex (5 denier) or more or 6.7 dtex (6 denier) or more. Another portion of the filter medium includes fibers with a more standard linear density of 3.3 dtex (3 denier) or less. This dual layer filter medium creates a first filter portion that primarily filters contaminants with nanoparticles having a high density within the fibers of a larger thickness, and a second filter portion that primarily filters contaminants with fibers having a lower linear density, but both portions may include nanoparticles dispersed throughout the fibers. In certain embodiments, the filter medium may include three or more separate portions or layers with different denier fiber ranges within each portion.

[0041] FIG. 4 shows a dual layer filter medium including a first substrate 40 having a first surface 42 and a second surface 44 opposite the first surface; and a second substrate 50 having a first surface 52 and a second surface 54 opposite the first surface. The second substrate 40 second surface 44 is bonded to the second substrate 54 by any method known to those skilled in the art. The first substrate 40 includes fibers 46 of a relatively smaller linear density, for example, on the order of 3.3 dtex (3 denier) or less. The second substrate 50 includes fibers 56 of a relatively larger linear density, for example, on the order of 3.3 dtex (3 denier) or more, for example, 5.6 dtex (5 denier), 6.7 dtex (6 denier) or more. The second substrate 50 also includes individual nanoparticles 58 dispersed throughout and bonded to the fibers 56 and / or retained on the second substrate 50. The first substrate 40 may or may not include nanoparticles as well. The first substrate 40 is configured to filter contaminants primarily with the fibers 46, although as previously mentioned, the first substrate 40 may also include nanoparticles. The second substrate 50 is configured to filter contaminants with both the fibers 56 and the nanoparticles 58. In some embodiments, the substrate may be detrimental to additives such as antimicrobial and / or antiviral compositions, such as organic compounds containing silver, zinc, copper, organosilicon, tributyltin, chlorine, bromine, or fluorine compounds. The fibers may include biocomponent fibers, which include fibers bonded together, that are two or more different fibers. The fibers may be comprised of the same material or different materials.

[0042] 5A-5C show various examples of biocomponent fibers that may be used with the fibrous materials disclosed herein. FIG. 5A shows a fiber 60 having a core fiber 62 and surrounding sheath fibers 64. In this embodiment, the core 62 is substantially concentric with the sheath. FIG. 5B shows a biocomponent fiber 70 having first and second fibers 72, 74 arranged alongside one another. FIG. 5C shows a biocomponent fiber 80 having a core fiber 82 and a sheath fiber 84. In this embodiment, the core 82 is off-center with respect to the longitudinal axis of the sheath 84, which increases the overall loft of the biocomponent fiber. Of course, other configurations are possible. For example, the core can include shapes other than circular, such as dog bone shapes, squares, triangles, diamonds, etc. Alternatively, the fiber can include multiple cores, or it can be divided into three, four or more quadrants. In certain embodiments, the fibrous material (i.e., fibers and / or nanoparticles) is electrostatically charged, so that, for example, contaminants are captured by both mechanical and electrostatic filtration. The bond between the fibers and the nanoparticles can be enhanced by electrostatically charging the nanoparticles, the fibers, or both. For example, in certain embodiments, the fibers are electrostatically charged, so that mechanical filtration can be achieved by the nanoparticles and, at the same time, electrostatic filtration can be achieved through the electret substrate. The electrostatic or electret substrate can be a bulky triboelectric filter medium made by carding and needling. In one embodiment, the nanoparticles are preferably deposited in the substrate before needling, and then both the electrostatic fibers and the nanoparticles are needling processed together.

[0043] The substrate, the nanoparticles, or both may be electrostatically charged using triboelectric methods, corona discharge, electrospinning, hydrocharging, charging bars, or other known methods. Corona charging may be suitable for charging monopolymer fibers or fiber blends, or fabrics. Tribocharging may be suitable for charging fibers with different electronegativities. Electrospinning combines the charging of the polymer and the spinning of the fibers in a one-step process. Suitable charging additives for tribocharging are described in commonly assigned U.S. Provisional Patent Application No. 63 / 410,731, filed Sep. 28, 2022, the entire disclosure of which is incorporated herein by reference. Nanoparticles can be selected with different triboelectric properties relative to the fibers to enhance particle removal using the triboelectric effect. Using this method, the nanoparticles produced are formed in an electric field and are less exposed to chemical contamination that may suppress the triboelectric effect. Nanoparticles with different adsorption or surface charge properties than the coarse fibers can be used similarly, for example, in oil or water filtration. This difference can be used to enhance or create a localized electric field gradient within the filter media to enhance particle removal. Nanoparticles and coarse fibers can have different wetting properties.

[0044] The fibrous material may include a binder or material, such as an adhesive or binder, that facilitates bonding between the fibers and / or retention of the nanoparticles in the substrate, whereby the nanoparticles can adhere to the fibers or be held by the fibers within the substrate to form a stable matrix. The binder or material is preferably present in a relatively small amount to bind the individual nanoparticles to the fibers throughout the substrate. Binders may include a variety of conventional materials including naturally occurring materials such as starch, dextrin, guar gum, or synthetic resins such as EVA, PVA, PVOH, SBR, polyglycolide, etc. In certain embodiments, solvent-based adhesives are used where bonding occurs upon solvent evaporation.

[0045] In one preferred embodiment, the binder or binding material comprises dextrin. In yet another embodiment, the binder comprises a composition of various substances such as water, 2-hexoxyethanol, isopropanolamine, sodium dodecylbenzenesulfonate, lauramine oxide, and ammonium hydroxide. In yet another embodiment, the binder comprises at least PVOH. The binder can be a solution, emulsion, suspension, hot melt, hardenable, undiluted, and / or combinations. In some embodiments, adhesive resins are used that may undergo crosslinking after coating of the adhesive onto the substrate. Adhesion (water / solvent resistance) may be promoted by self-crosslinking with evaporation of solvents in the adhesive formulation or by thermal activation during the drying process. In the case of certain adhesives, crosslinking may be achieved by high energy wavelengths of electromagnetic radiation, including but not limited to RF, UV, or electron beam. The amount of adhesive may be controlled by adjusting the nozzle size of the spray coater 140 or by adjusting the flow rate of the adhesive composition. The bonding agent may be applied using a spray nozzle, dip coating, or other methods. In some embodiments, the binder or bonding material may include a surfactant to lower the surface or interfacial tension of the binder, thereby enhancing its dispersion and wetting properties and allowing the binder to more easily penetrate the depth of the substrate.Suitable surfactants for use with the adhesives disclosed herein include nonionic, anionic, cationic and amphoteric surfactants, such as sodium stearate, 4-(5-dodecyl)benzenesulfonic acid, sodium dodecylbenzenesulfonate wetting agent, docusate (sodium dioctyl sulfosuccinate), alkyl ether phosphates, benzalkonium chloride (BAC), perfluorooctane sulfonic acid (PFOS), and the like.

[0046] In some embodiments, the substrate comprises its own binding composition. In these embodiments, a binder or material may or may not be added to the substrate. In one such embodiment, the substrate comprises biocomponent fibers, one of the components comprising an outer covering at least partially surrounding an inner core (see Figures 5A and 5C). The sheath may include a material that bonds to the nanoparticles. For example, the sheath may include a material that becomes sticky and / or fluid upon heating and / or drying. During the heating / drying step (discussed below), the sheath portion of the fiber is heated to its melting point until it becomes sticky and / or fluid and bonds the nanoparticles to the substrate. In a preferred embodiment, bonding and drying are performed simultaneously.

[0047] Figure 23A is a magnified image of a textile with nanoparticles deposited without the use of a binder material. Figure 23B is a magnified image of a textile where the nanoparticles were adhered to the fibers using a binder material of dextrin and water. As can be seen, the use of a binder causes the nanoparticles to adhere more uniformly to the fibers. The examples of Figures 23A and 23B used a substrate having a bicomponent microfiber with an inner portion of polyester and an outer portion of high density polyethylene ("HDPE"). Figure 23A shows a microfiber textile product having a bicomponent microfiber substrate that deposits biosoluble glass nanofibers only on the surface of the substrate and relies on electrostatic forces to hold the nanofibers. Nanofiber clumping and poor nanofiber retention can be seen in Figure 23A. The substrate can be made using meltblown, spunbonded, or other methods described herein. In the example of FIG. 23B, a binder material was used. The substrate was sprayed with a mixture of dextrin and water, and the nanoparticles were applied to the substrate with greater uniformity and greater retention of nanofibers. In further examples, any of the binder materials disclosed herein can be used. Additionally, nanoparticles of biosoluble glass were deposited into the depth of the substrate. In this example, the bicomponent microfiber substrate itself has a MERV value of 4-10, which can be achieved using any of the methods described herein. With nanoparticles deposited into the depth of the substrate and carrying a static charge, in one example, a microfiber substrate originally having a MERV value of 8 was used to produce a textile product with a MERV value of 13. In another example, a microfiber substrate originally having a MERV value of 6 was used to produce a textile product with a MERV value of 15. The substrate can be applied to a roll in a roll-to-roll continuous process, such as any of the processes and methods described herein, and textile products can be produced on a commercial scale. In one example, the roll-to-roll process is run at 30 feet per minute.

[0048] In certain embodiments, the fibrous materials discussed herein may be included as part of a filter device that removes or absorbs contaminants, such as liquid filters, gas filters for home and commercial air filtration, surgical masks or other face coverings, etc. The filter device may be a mechanical filter, an absorption filter, a sequestration filter, an ion exchange filter, a reverse osmosis filter, a surface filter, a depth filter, etc., and may be designed to remove many different types of contaminants from air, water, etc. In one such embodiment, the fibrous material is incorporated into air filters that remove particles and contaminants from the air, such as HEPA filters (i.e., pleated mechanical air filters), UV light filters, electrostatic filters, washable filters, filter media, spun glass filters, pleated or non-pleated air filters, activated carbon filters, pocket filters, V-bank compact filters, filter sheets, flat cell filters, filter cartridges, and the like. The fibrous material comprises a filter media for air filters, and may be supported by a support layer, a scrim layer, or may be included in other layers or materials. Applicants have discovered that incorporating nanoparticles in the depth direction of the fibrous material, as discussed herein, substantially increases the efficiency of the air filter without compromising the pressure drop (i.e., airflow drop) through the filter. In addition, these materials increase the overall dust holding capacity and therefore the life of the filter, especially compared to filters that rely solely or primarily on electrostatic effects to increase efficiency.

[0049] Conventional home and commercial air filters, e.g., HEPA filters, are typically rated by their ability to capture particles between about 0.3 and 10 microns. This rating is called the Minimum Efficiency Reporting Value, or MERV, and was developed by the American Society of Heating, Refrigeration, and Air-Conditioning Engineers (ASHRAE). MERV values ​​range from 1 to 16, with higher values ​​indicating greater efficiency in removing a particular type of particle. Conventional mechanical air filters typically report a MERV value of about 8 for fibrous filtration materials. Air filters are typically rated based on their initial efficiency (i.e., the efficiency of the air filter before use), and their efficiency over time and use. This latter efficiency is usually tested by a conditioning process, called ASHRAE Standard 52.2 Supplement J.

[0050] The air filters provided herein have an initial MERV value of greater than about 10 and a pressure drop of less than about 0.5 inches of water. In some cases, the initial MERV value is about 11 and the pressure drop is less than about 0.17 inches of water, or about 13 and less than about 0.36 inches of water, or about 14 and less than about 0.5 inches of water. The gas filters provided herein have a MERV rating of 10 or greater after the gas filters are conditioned to ASHRAE Standard 52.2 Supplement J. In some embodiments, the gas filters have a MERV rating of 13 or greater after they are conditioned to ASHRAE Standard 52.2, ISO Standard 16890, or any other industry acceptable standard. The MERV values ​​of the fibrous filter media discussed herein vary with many factors, including the type and size of fibers used in the filter media, the density of individual nanoparticles within the filter media, the width of the filter media, the number and size of pleats (if any), etc. MERV values ​​can be measured for sheets of the textile as well as for textiles formed into pleated filter media, and the pressure drop for each can vary. Similarly, the pressure drop across the filter media also depends on many factors, including those mentioned above.

[0051] One factor that influences the MERV value and pressure drop is the density or add-on amount of nanoparticles in the substrate relative to the density of fibers in the substrate. Applicants have discovered that the smaller the ratio between substrate density and nanoparticle density, the higher the MERV value and pressure drop of the filter. In certain embodiments, the filter media described herein have a nanoparticle density of about 0.1 g / m 2 ~about 20g / m 2 , preferably at least about 2 g / m 2 has a nanoparticle areal density of In some cases, the density of the nanoparticles also depends on the density of the actual filter media (the density of the coarse fibers). As discussed in more detail with reference to Table 2 below, a density ratio (base material gsm divided by add-on nanoparticle gsm) of about 67 resulted in a pressure drop of about 0.14 inches of water and an initial MERV value of 10. A density ratio of about 33.4 increased the MERV value to 10 while at the same time increasing the pressure drop to only about 0.17 inches. A density ratio of about 22.3 increased the initial MERV value to 12 and the pressure drop to about 0.24 inches of water. Thus, the efficiency or MERV value of the filter may be increased with a higher add-on amount of nanoparticles. In particular, Applicant has determined that the nanoparticles may be present in a concentration of at least 2 g / m 2 It has been found that a filter with a MERV value of about 10 can be achieved with an add-on amount of 4 or 6 g / m 2 add-on amounts of 10 g / m2 result in filters with MERV values ​​of approximately 12 and 13, respectively. 2 The above add-on amounts will result in a filter with a MERV rating of 15 or higher.

[0052] Applicants have also discovered that the inclusion of fibers having a greater thickness or linear density results in a larger pore size and therefore a larger pore volume, thereby allowing for a higher density of nanoparticles within the substrate. This results in a higher MERV value and pressure drop (as discussed below with reference to Table 2). For example, Applicants have been able to produce air filters containing 5.6 dtex (5 denier) biocomponent fibers with a MERV value of 14 and a pressure drop of 1.3 centimeters (0.5 inches) of water. Similarly, Applicants have been able to produce filters containing 5.6 dtex (5 denier) biocomponent fibers with a MERV value of 13 and a pressure drop of only about 0.74 centimeters (0.29 inches) of water. One embodiment of a pleated filter media 90 is shown in FIG. 6. The filter 90 may include approximately 0-10 pleats per inch depending on the application. The filter media may be mounted on a cardboard or metal frame for use as an easily replaceable filter product. (FIG. 7). As shown, a gas filter 94 is fabricated from the fibrous materials described herein. As shown, the filter 94 includes a pleated fibrous filter media 96 and a support layer 98 that provides rigidity and structure to the filter media 96.

[0053] 11 shows a gas filter 109 made with the fibrous materials described herein. The gas filter 109 includes a fibrous substrate having nanoparticles dispersed throughout the fibers and the depth of the substrate. The substrate can then be rolled into a cylinder, cone, or other suitable shape and used in applications such as gas turbine and compressor air intakes, panel filters, and the like. Other types of filters that can be developed with the fibrous materials disclosed herein include conical filter cartridges, square end cap filter cartridges, pocket filters, V-bank compact filters, panel filters, flat cell filters, pleated or non-pleated bag cartridge filters, and the like.

[0054] The textile products disclosed herein may be used in medical masks or other medical applications, such as respirator cartridges. Medical masks are designed to protect health care workers and / or patients from microorganisms and other substances. For example, medical masks can block bacteria, which may have dimensions of, for example, about 3 microns, and can also block viruses, which may have dimensions of, for example, about 0.1 microns. The masks are made with multiple layers of fibrous material and have ear loops, drawstrings, or other structures that attach the mask to a person's face. Wires may be incorporated into at least the top of the mask to conform at least a portion of it to the person's face. The masks may include a rigid polymer structure designed to hold the multi-layered fibrous material to the front of the person's face. In one embodiment, the mask has three layers. The outer and inner layers include a fibrous material, such as spunbond polypropylene, which provides breathability, although any of the materials mentioned herein may be used. The middle layer is disposed between the inner and outer layers and includes a microfiber substrate having nanoparticles deposited into the depth of the substrate to provide an initial MERV of greater than 8, preferably greater than 10, and more preferably a MERV of 13. For breathability, the pressure drop through the mask is 3-6 mm of water, more preferably 4 mm of water. Desirably, the mask has an efficiency of about 95%. Other embodiments of the mask have four or more layers. Multiple layers of textile products can be combined in a single mask.

[0055] In certain embodiments, the fibrous material may be included in a thin film or layer that includes openings, pores, or perforations. The openings are embossed with a pattern (e.g., circular, diamond-shaped, hexagonal, elliptical, triangular, rectangular, etc.) and then stretched until openings are formed in the thinned areas created by the embossing. Such perforated substrates can be formed from many polymers, such as polypropylene, polyethylene, high density polyethylene ("HDPE"). Polymer layers include, for example, extruded films. Perforated films are commercially available and are marketed under the trademark Delnet®. The substrate is supplied in a roll and the nanofibers are deposited into the substrate in a roll-to-roll process. Figures 10A-10E show examples of perforated films that may be formed by the methods described herein. In another embodiment, a gas filter includes a filter media and a substantially rigid support layer coupled to the filter media, the support layer including fibers and discrete nanoparticles dispersed depthwise within the layer, the nanoparticles configured to filter contaminants passing through the support layer.

[0056] 8, a composite filter element 814 includes an inner filter substrate 812 and one or more filter support elements or membranes 810. The support elements 810 may be formed from extruded sheets of polymers such as polypropylene film, high density polyethylene film, polylactic acid film, or extrudable fluoroplastic materials, in some embodiments, thermoplastic polymer materials such as perfluoroalkoxyalkane (PFA) made from comonomers of polytetrafluoroethylene and perfluoroalkylvinylether. However, other polymer materials such as fluoroplastics may be used, for example, ethylene chlorotrifluorethyle (ECTFE); ethylene tetrafluroethylene (ETFE) of polyvinylidene fluoride (PVDF). In certain embodiments, as discussed above, support membrane 810 includes individual nanoparticles dispersed depthwise within membrane 810. The nanoparticles enable the support membrane to filter at least a portion of the contaminants passing through filter membrane 814 (i.e., in addition to the filtration provided by inner filter substrate 812). In other embodiments, filter substrate 812 and / or support membrane 810 include such nanoparticles. Fluoroplastic materials such as PFA are highly desirable for use in filters intended to purify semiconductor components and other environments where extreme cleanliness is required and the potential for contamination is minimized. Such support membranes are designed to direct the fluid to be filtered along their surfaces and, in addition, to direct the fluid through the structure into the underlying filter substrate to remove undesirable particles from the filtrate.

[0057] As shown in Figures 9A and 9B, the support film 810 may include a plurality of apertures 828. The apertures are preferably round in shape, although it will be understood that other shapes are possible, such as square, rectangular, triangular, etc. The substrate may be wound into a roll and then unwound and guided through a punch press to form the desired predetermined pattern of apertures 828 running through it in the Z direction (Figure 9A). Alternatively, after setting, the sheet may be guided in a continuous run through a punch press where the predetermined pattern of apertures 828 is formed.

[0058] Referring to FIG. 9B, after the apertures are formed, the filter support member can be stretched lengthwise to elongate the apertures 828, as indicated by double-ended arrow 940, to provide a larger open area through which fluid to be filtered by the filter media or substrate 812 can pass. In an alternative embodiment, the support membrane 810 may be porous (i.e., instead of or in addition to being porous with openings 828). In this embodiment, additional fluid flow can be achieved with a substantially porous support membrane. In an exemplary embodiment, the support membrane has a porosity value of at least 0.5, i.e., 50%, preferably 0.8, i.e., 80%, and more preferably about 0.86, i.e., 86%. The porosity value is defined as the non-solid or pore volume fraction of the total volume of the material. A more complete description of such composite filter media can be found in U.S. Patent International Application No. US2020 / 040941, the full disclosure of which is incorporated herein by reference in its entirety.

[0059] The support membrane of the present invention for filters can be prepared by any method known to those skilled in the art. In one embodiment shown in Figures 9A and 9B, the support membrane includes ribs. For example, the support membrane can be made by extruding a polymeric material into a sheet form and then passing the sheet through a nip area provided by opposing rollers; at least one of the rollers has an outer surface with a counterbore groove. The counterbore groove of one roller is aligned with the outer surface or counterbore groove of the nip area of ​​the other roller to form a ribbed sheet with ribs upstanding from at least one surface of the sheet. Alternatively, the ribs can be formed during the extrusion process or known embossing methods. Once the ribs are formed, the support membrane can be wound into a roll and then unwound and guided by a press to form openings running through it in the Z direction in the desired predetermined pattern. Alternatively, after setting, the support membrane can be guided in a continuous operation through a punch press where a predetermined pattern of openings can be formed, as best seen in Figure 9A. If necessary, the support membrane can be stretched lengthwise (as indicated by the double arrow in FIG. 9B) to elongate the openings, e.g., to provide a larger open area through which fluid to be filtered by the filter layer or substrate can pass.

[0060] 12 shows a schematic diagram of an overall system 110 for producing fibrous materials and other products as described above. As shown, the system 110 includes a feeder 120 for advancing a substrate 130 of fibers or other material through a manufacturing process. The system 100 includes a coater 140, a fiberizing system 150, and a heating and / or drying device 160. In certain embodiments, the system 100 further includes a vacuum or other reduced pressure source 170 below the substrate 130 and opposite the fiberizing system 150. In one embodiment, the feeder 120 includes a winder 122 at a downstream end of the process and an unwinder 124 at an upstream end to continuously wind up the substrate 130 through the system 100. In certain embodiments, the feeder 120 further includes a support surface (not shown) that extends between the unwinder / winder for the support substrate 130 as it moves downstream through the system 100. In other embodiments, the substrate is unwound directly from the unwinder 124 to the winder 122 without a separate support surface.

[0061] The applicator 140 is configured to spray droplets of a binder or bonding material, such as an adhesive or binder, onto the substrate 130 so that the nanoparticles can adhere to the fibers in the substrate 130 and form a stable matrix. The binder is preferably present in a relatively small amount to bond the individual nanoparticles to the fibers throughout the substrate 130. In a preferred embodiment, the applicator 140 includes a spray nozzle sized to produce adhesive droplets having a diameter of about 20-30 microns, increasing the penetration depth of the adhesive through the substrate 130. Of course, droplet size can be affected by numerous other parameters including air pressure, air volume, air temperature, humidity, spray horn design, rheological properties / viscosity of the adhesive, carrier, etc. Of course, it will be understood that coating the substrate with the binder or binding material may be accomplished by other coating methods including ultrasonic spraying, dip coating, spin coating, gravure coating, kiss roll coating, screen coating, powder coating, electrostatic sputter coating, or similar coating techniques. As discussed above, binders may include a variety of conventional materials including naturally occurring materials such as starch, dextrin, guar gum, or synthetic resins such as EVA, PVA, PVOH, SBR, etc. In certain embodiments, solvent-based adhesives are used where bonding occurs upon solvent evaporation.

[0062] In one preferred embodiment, the binder comprises dextrin. In another embodiment, the binder comprises a composition of various substances such as water, 2-hexoxyethanol, isopropanolamine, sodium dodecylbenzenesulfonate, lauramine oxide, and ammonium hydroxide. In yet another embodiment, the binder comprises PVOH. The binder may be a solution, emulsion, suspension, hot melt, hardenable, undiluted, and / or combinations. In some embodiments, adhesive resins are used that may undergo crosslinking after coating of the adhesive onto the substrate 130. Adhesion (water / solvent resistance) may be promoted by self-crosslinking with evaporation of solvents in the adhesive formulation or by thermal activation during the drying process. In the case of certain adhesives, crosslinking may be achieved by high energy wavelengths of electromagnetic radiation, including but not limited to RF, UV, or electron beam. The amount of adhesive may be controlled by adjusting the nozzle size of the spray coater 140 or by adjusting the flow rate of the adhesive composition.

[0063] In some embodiments, the binder may include a surfactant to reduce the surface or interfacial tension of the binder, thereby enhancing its dispersion and wetting properties and allowing the binder to more easily penetrate the depth of the substrate. Suitable surfactants for use with the binders disclosed herein include nonionic, anionic, cationic and amphoteric surfactants, such as sodium stearate, 4-(5-dodecyl)benzenesulfonic acid, sodium dodecylbenzenesulfonate wetting agent, docusate (sodium dioctyl sulfosuccinate), alkyl ether phosphates, benzalkonium chloride (BAC), perfluorooctane sulfonic acid (PFOS), and the like. In some embodiments, the spray coater 140 is positioned upstream of the fiberization system 150 so that the binder is sprayed before the nanoparticles are deposited. In other embodiments, the spray coater 140 is positioned downstream of the fiberization system 150 so that the binder can be sprayed after the nanoparticles are deposited. In other embodiments, the system 100 includes two spray coaters; one positioned upstream of the fiberization system 150 and a second spray coater (not shown) positioned downstream of the fiberization system 150 to coat the substrate 130 with a second binder after the nanoparticles are deposited. In some embodiments, there are two or more nozzle heads, each with a spray coater 140. The nozzle heads may be arranged in series, for example, for better uniformity or to increase the fiber spray width. Alternatively, the nozzle heads may be arranged in parallel, i.e., across the entire width of the substrate, to ensure that the binder is coated across the entire width of the substrate.

[0064] In a preferred embodiment, a reduced pressure or vacuum source (not shown) is positioned underneath the substrate 130 opposite the spray coater 140 to increase the penetration depth and uniformity of the binder. The reduced pressure source may be any suitable suction device, such as a suction pump, that draws the binder through the substrate.

[0065] In some embodiments, the substrate includes its own binding composition. In these embodiments, a binder may or may not be added to the substrate. In one such embodiment, the substrate includes a biocomponent fiber 600, one of the components including an outer covering 64 at least partially surrounding an inner core 62. In certain embodiments, the sheath 64 and the core 62 may be substantially concentric with one another (FIG. 5A). In other embodiments, the core 84 may be eccentric with the sheath 82 (FIG. 5C). In other embodiments, the core 72 and the sheath 74 may be located alongside one another (FIG. 5B). Of course, other configurations are possible. For example, the core 184 may include shapes other than circular, such as a dogbone shape, a square, a triangle, a diamond, etc. Alternatively, the fiber 180 may include multiple cores, or it may be divided into three, four or more quadrants. The sheath 64 may include a material that bonds to the nanoparticles. For example, the sheath 64 may include a material that becomes sticky and / or fluid upon heating and / or drying. During the heating / drying step, the sheath 64 portion of the fiber is heated to its melting point until it becomes sticky and / or fluid and bonds the nanoparticles to the substrate. In a preferred embodiment, bonding and drying occur simultaneously in the drying apparatus 160.

[0066] FIG. 13 shows a schematic diagram of a fiberization system 150 for converting nanofibers into individual nanoparticles. As used herein, the term "fiberization" means converting (e.g., liberating, separating, isolating, and / or individualizing) clusters, agglomerates, or other nanoparticles, which may or may not be intertwined, into individual nanoparticles having at least one dimension less than 1 micron. FIGS. 14A-14C show examples of macroclusters of entangled nanofibers (FIG. 14A), smaller clusters of entangled nanofibers (FIG. 14B), and individual nanoparticles (FIG. 14C). As shown, fiberization system 150 includes a feeder 200, such as a hopper, for introducing larger or macro-clusters / agglomerates of nanoparticles (see FIG. 14A) into system 150. Feeder 200 may include any suitable hopper device known by those skilled in the art and preferably configured to introduce macro-particle clusters into the process at a specified rate that is dependent on the downstream fiberization rate. Nanoparticles may be introduced continuously at a specified rate or may be introduced at intervals at a specified rate. Macro-clusters of nanoparticles in the bundles are broken down prior to introduction into feeder 200. It should be understood that the nanoparticles can be introduced to the fiberizer 150 in many different forms. For example, raw nanofibers can be produced as long, separated fibers. In this form, the nanofibers can be cut to obtain a desired length-to-diameter ratio.

[0067] The system 150 further includes a separator 210, such as a mixer, to separate or break down macroclusters / agglomerates of nanoparticles into smaller clusters / agglomerates of nanoparticles (see FIG. 14B). The feeder 200 transfers the nanofibers into the separator 210 in a steady, continuous manner by any mechanical means. The rate of transfer depends on various factors, such as the speed of the substrate 130 along the feeder 120, the rate of fiberization of the nanoparticles, etc. The amount of nanoparticles dropped into the separator 210 can be adjusted to control the amount of nanoparticles dispersed in the substrate, creating a continuous manufacturing process.

[0068] In one embodiment, the separator 210 includes a housing 212 having a first opening 214 connected to the feeder 200 and a second opening 216 connected to a downstream process. The second opening 216 is preferably sized to allow only clusters of nanofibers having a particular size to pass through it. The separator 210 may include multiple rotatable blades (not shown) designed to rotate about a vertical axis within the housing 212 to separate and release coarse clusters of nanofibers. The blades may have the same or different pitch and camber to allow for the continuous breaking down or "opening" of entangled fibers as they pass from the first opening 214 to the second opening 216.

[0069] Fiberization system 150 further includes a gas stream that extends through the system from separator 210 to nozzle 220 (discussed in more detail below). The gas stream (in addition to a series of pumps, as discussed below) provides the transport force that moves the nanofibers through system 150. In one embodiment, the gas stream is formed by an air compressor 230 configured to provide compressed air to the system, although it will be understood that other forms of gas may be used to transport the nanofibers through system 150. The system 150 includes one or more pumps that move the nanofiber clusters and ultimately the individual nanoparticles throughout the system. The pumps may include any suitable pumps, such as positive displacement, centrifugal, axial, etc. In one embodiment, a first pump 240 includes a first inlet fluidly connected to an air compressor 230 by a first passageway 242 and a second inlet fluidly connected to the separator 210 by a second passageway 244. Compressed air is drawn into the first pump 240, creating a reduced pressure (e.g., vacuum) that draws the nanofiber clusters from the separator 210 into the pump (discussed in more detail below). The system 150 may further include second and third pumps 250, 260, each fluidly connected to an outlet of the first pump 240. In a similar manner, the second and third pumps 250, 260 create a reduced pressure that draws the nanofiber clusters through the third passageway 252. In a particular embodiment, the pump 240 includes an eductor 300. As shown in FIG. 15, the eductor 300 includes a movable fluid inlet 302 and a nanofiber inlet 304, each connected to an outlet 306 via a fluid passage 308. The fluid passage 308 includes a convergent inlet nozzle 310, a diffuser throat 312, and a divergent outlet diffuser 314. The high pressure, low velocity air is converted to low pressure, high velocity air, thus creating the pressure difference required for suction. Based on the Venturi effect and Bernoulli's principle, a primary fluid medium (e.g., compressed air) is used to create a vacuum, drawing the nanofibers into the eductor 300 and expelling them through the outlet 306. The diameter of the eductor 300 depends on the volumetric flow rate of the compressed air, the suction requirements, the pressure drop, and the fluid pressure of the compressed air.

[0070] Referring back to FIG. 13, the third passageway 252 includes a junction 254 that divides the third passageway 252 into two separate passageways that lead to the second and third pumps 250, 260, respectively. The junction 254 preferably includes a surface or wall disposed substantially perpendicular to the third passageway 252 to form a T-shaped intersection. The surface may be any surface that impedes the flow of nanofibers through the passageway, such as an interior wall of the passageway at the junction, or a change in direction of another interior wall, e.g., a curved surface, a vertical surface, etc. Alternatively, the passageway may include a wall or other surface disposed within the passageway, or a protrusion into the passageway of the fluid path. In one embodiment, the passageway extends to a substantially T-shaped junction that includes two separate passageways extending from the junction. The second ejector is configured to draw the nanofibers into the T-shaped junction at a rate sufficient to break down at least some of the nanofibers.

[0071] As the nanofiber clusters move through the third passageway 252, they are propelled against this surface or wall by the reduced pressure applied by the second and third pumps 250, 260. This velocity relative to the nanofiber junctions 254 creates collisions with sufficient kinetic energy to break down at least some of the nanofiber clusters into smaller nanofiber clusters and / or individual nanoparticles having at least one dimension less than 1 micron. To generate the kinetic energy necessary to break down the nanoparticle clusters, air is advanced through the system 150 at a velocity of about 500 fpm to about 10,000 fpm, preferably about 2,000 fpm to about 6,000 fpm. The system 150 includes a sufficient amount of inlet pressure, at least about 20 psi, to generate a total pressure throughout the system of at least about 100 psi.

[0072] In certain embodiments, the system 150 further includes fourth and fifth fluid passages 262, 264 connecting the outlets of the second and third pumps 250, 260 with the reactor 270. As shown in FIG. 16, the reactor 270 includes an upper surface 272, a lower surface 274, and an interior annular chamber 276 extending from the upper surface 272 to the lower surface 274. The reactor 270 further includes a central tube 275 having an open top inlet 278 and an outlet 280. The reactor 270 may further include one or more outlets 282. The reactor 270 may be coupled to an energy source (not shown) configured to create a swirling gas vortex within the annular chamber 276. The energy source may include any suitable energy source, such as a pump, a compressor, a generator, etc. The swirling gas preferably flows from the bottom to the top of the reactor 270 around the central tube 275 , moving the nanofiber clusters and individual nanoparticles from the lower surface 275 upward toward the upper surface 272 .

[0073] In another embodiment, the vortex is created without a separate energy source. In this embodiment, nanofiber clusters 290 and individual nanoparticles 292 enter the reactor 270 through bottom inlets 284, 285, 286, 287. The inlets 284, 285, 286, 287 are tilted upward to facilitate the movement of the nanofibers and nanoparticles around the central tube 275. In a preferred embodiment, at least one or more of the inlets 284, 285, 286, 287 are tilted such that as the nanofibers and nanoparticles enter the reactor 270, they are tangential to the central tube 275. As they enter the annular chamber 276, the velocity vectors (speed and direction) of the nanofibers and nanoparticles create a vortex within the reactor 270, causing them to swirl upward around the central tube 275 to the top of the chamber 276. The swirling gas preferably flows from the bottom to the top of the reactor 270 around the central tube 275, moving the nanofiber clusters and individual nanoparticles from the lower surface 275 upward toward the upper surface 272. Without any interruption, the nanofibers 290 and nanoparticles 292 are blown from the bottom to the top of the reactor. The vortex within the chamber 276 may further break down (e.g., loosen, separate, and / or individualize) the nanofiber clusters 290 as they pass through the reactor 270. In some embodiments, reactor 270 may also be coupled to an energy source (not shown) configured to create a swirling gas vortex within annular chamber 276. The energy source may include any suitable energy source, such as a pump, a compressor, a generator, or the like.

[0074] The system 100 may further include another pump or reduced pressure source (see, e.g., FIG. 17 ) connected to the top outlet 282. This reduced pressure draws the fibers 290 through the outlet 282 as they exit the reactor 270. Because the individual nanoparticles 292 are significantly lighter than the entangled nanofibers 290 that are still clustered together, these individual nanoparticles 292 are drawn into the top inlet 278 of the central tube 275. Meanwhile, the larger, heavier clusters of nanofibers 290 that have not yet been broken down are drawn through the top outlet 284. The top outlet 284 may be connected to another pump (not shown) or may be connected to the first pump 240. In this manner, the nanofiber clusters 290 are sent back through the process for further break down, creating a re-feed system to further break down the remaining nanofiber clusters.

[0075] An outlet 280 of the central tube 275 is connected to a nozzle 220 (see FIG. 13). Individual nanoparticles 292 are drawn into the nozzle 220 where they are dispersed onto the surface of the substrate or into a fiber stream (discussed below). The nozzle 220 may include any suitable nozzle known by those of skill in the art. In one embodiment, the nozzle 220 has multiple outlets with external dimensions adapted to the size (i.e., area) of the substrate passing under it. The nozzle 220 disperses the nanoparticles onto the substrate at a rate driven by the pressure of the entire system.

[0076] In certain embodiments, the system 100 includes two or more nozzles coupled to the outlet 280 of the reactor 270. The nozzles may be arranged in any suitable configuration on the substrate, such as in parallel, in series, in parallel, etc. It will be appreciated that pump 240, or pumps 250, 260, may supply the nanofiber / air mixture stream directly to nozzle 220 (i.e., bypassing reactor 270). In this embodiment, the pressure within the system is designed to create enough kinetic energy to break down or release nearly all of the nanofibers into individual nanoparticles, such that reactor 270 is not required to separate the nanoparticles from the larger fiber clusters.

[0077] 17, another embodiment of a fiberization system 320 will now be described. As shown, the fiberization system 320 includes a separator 325 for separating larger or macro-clusters of nanofibers into smaller clusters of nanofibers that pass through the system 320. A first ejector 326 is coupled to the outlet of the separator 325 and serves to draw the nanofibers from the separator 325 into the system 320. An air compressor (not shown) is also coupled to the ejector 326 to provide the motive fluid discussed above. As in the previous embodiment, the second and third ejectors 330, 340 are connected to the outlet of the first ejector 326. The nanofibers are drawn through the first ejector 320 and advanced against a surface of a T-shaped intersection 350 to break down at least some of the nanofibers into smaller nanoparticle clusters or individual nanoparticles. Each of the second and third ejectors 330, 340 is connected to an additional T-junction 360, 370. As before, the nanofibers are advanced against the surface of the T-junction 360, 370 where they are further broken down. Each of the T-junctions 360, 370 is connected to two fluid passages that enter the bottom part 380 of the reactor. The bottom part 380 of the reactor thus has four separate inlets 382, ​​384, 386, 388 for the passage of the nanofibers. Each of these inlets is preferably inclined upwards and located at opposite corners of the reactor. This allows the nanofibers to enter the vortex of the reactor and then swirl upwards to the top 390 of the reactor.

[0078] As previously discussed with reference to FIG. 16, the reactor includes an annular chamber with a central tube having an open top end and a bottom end connected to a nozzle. Nanofibers that have been sufficiently broken down into individual nanoparticles flow through the open top end into the central tube for dispersion via the nozzle. Heavier nanoparticle clusters that have not yet been broken down exit the reactor through one of four separate outlets 392, 394, 396, 398. As discussed above, ejectors 410, 420 provide a transport force for drawing the nanofibers from the reactor 400. Each of the outlets 392, 394 is connected to the ejector 410 via a T-shaped intersection 412, and each of the outlets 396, 398 is connected to the ejector 420 via a T-shaped intersection 422. In this case, the nanofibers flow from two passages to one passage as they pass through the intersections 412, 422. The ejectors 410, 420 are connected to T-junctions 430, 440, respectively. As previously described, the nanofibers are advanced to the T-junctions 430, 440 to further break them down into individual nanoparticles. The T-junctions 430, 440 are then connected to the bottom portion 380 of the reactor 400 (via inlets 432, 434, 442, 444), respectively. This allows the nanofibers to be returned to the reactor 400 for further processing. This process continues for each cluster of nanofibers until it is completely broken down into nanoparticles and passes through the central tube to the nozzle. As a final step, the individualized nanofibers are air-blown from the nozzle onto any substrate or mixed with any fiber spinning stream. During this process, the suction force is up to 20 psi and the pressure is up to 100 psi.

[0079] In certain embodiments, the fiberization system 150 may include a separate control system that monitors the nanofibers to determine when they have broken down into individual nanoparticles suitable for passing through a nozzle. The control system may, for example, simply monitor the pressure throughout the system to ensure that sufficient pressure is being applied to the nanofibers to break them down into nanoparticles. Alternatively, the control system may include a variety of different sensors located throughout the system to detect properties of the nanoparticles, such as mass or size. Sensors may be located within the reactor 400, for example, so that the control system may control various parameters, such as reduced pressure applied to the outlets 392, 394, 396, 398 of the reactor 400, the speed of the vortex passing around the annular chamber, or the pressure applied to the central tube that then draws the nanoparticles into the nozzle.

[0080] 18 illustrates another embodiment of a system 500 for manufacturing a multi-layered fibrous material. As shown, the system 500 includes first and second unwinders 502, 504 and a single winder 506 for winding up first and second substrates 510, 512 downstream through the system 500. As in some previous embodiments, the system 500 may further include a support surface (not shown) for each substrate 510, 512. The first and second unwinders 502, 504 serve to advance the first and second substrates 510, 512 through the process where they are joined together and then wound onto the single winder 506, as discussed below. The system 500 includes first and second spray coaters 520, 522 disposed downstream of the first and second unwinders 502, 504, respectively, for applying a binder to the first and second substrates 510, 512. The system 500 further includes first and second fiberization systems / apparatuses 530, 532 disposed downstream of the respective spray coaters 520, 522. As previously discussed, the fiberization apparatuses 530, 532 generate individual nanoparticles and disperse the nanoparticles onto the substrates 510, 512. Once the nanoparticles are dispersed in the substrates 510, 512, the two substrates are joined together at a joining point 540 and they are advanced downstream together. The two substrates may be bonded to each other at this point or they may simply be placed one on top of the other.

[0081] The system 500 further includes a heater / drying device, such as an IR oven 550, downstream of the juncture 540 of the two substrates. The heater / drying device heats and dries the two substrates, bonding them to one another and bonding the nanoparticles to the fibers within the substrates. The substrates may be, for example, stacked on top of one another. In certain embodiments, the nanoparticles are dispersed in both substrates 510, 512. In one such embodiment, the system 500 is designed such that the nanoparticles are dispersed through a first surface of each substrate. The substrates can then be joined such that the first surfaces face each other. Alternatively, the first surfaces may face away from each other (i.e., joining the substrates at a second, opposite surface of each substrate). In yet another embodiment, the first surface of the first substrate is joined to the second surface of the second substrate.

[0082] 19 illustrates a filter product 700 including a fibrous material filter media 710 including fibers 722 and nanoparticles 720 dispersed throughout at least a portion of the filter media 710. As shown, the filter media 710 has a first upper surface 712 and a second lower surface 714. The nanoparticles are dispersed throughout the upper surface 712 such that they extend beyond the upper surface 712 and into the depth of the filter media 710. The filter product 700 further includes a support layer 730, which may be any suitable support layer known in the art, such as a substantially rigid polymer that provides support for the filter media 710, or an apertured film having a plurality of openings (discussed above) for the passage of gas or fluid therethrough.

[0083] 20 illustrates another filter product 740 that includes a fibrous material filter media 710 that includes fibers 722 and nanoparticles 720 dispersed throughout a portion of the filter media 710. In this embodiment, the product 740 includes a scrim layer 750 bonded to a support layer 730.

[0084] 21 illustrates a dual layer filter product 760 including first and second filter media 762, 764 bonded together. As shown, nanoparticles 720 are dispersed throughout the entire depth of each filter media 762, 764. In this embodiment, nanoparticles 720 are dispersed throughout the interior surfaces 766, 768 of filter media 762, 764. In another embodiment (not shown), nanoparticles are dispersed throughout the exterior surfaces 770, 772 of filter media 762, 764. In yet another embodiment, nanoparticles 720 may be deposited on the interior surface 766 of filter media 762 and the exterior surface 772 of filter media 764. In another aspect, a system for producing a fibrous material includes a first device for generating one or more fiber streams and a second device for isolating nanoparticles in a gaseous medium. The second device disperses the nanoparticles in a stream and feeds the stream into a fiber stream to form the fibrous material. The system may further include a dispersing device, such as a nozzle, coupled to the second device and configured to feed the nanoparticles substantially uniformly into the fiber stream. The fiber stream may be refined by any suitable mechanism known in the art, such as meltblown, spunbonded or spunlaced, thermally bonded, carded, airlaid, wet-laid, extruded, co-formed, needle punched, stitched, hydroentangled, etc. In one embodiment, the system may include a spunbond line where filaments are formed by spinning molten polymer and drawing the molten filaments. Fiber bundles of filaments are separated and opened and then layered on a screen to form a web. The fibers are bonded into a sheet by thermal bonding and embossing. The first stream 630 may be introduced, for example, before an attenuation region or before a bonding (solidification) step. In another embodiment, the system may include two carding devices arranged in series with each other. The first stream 630 is introduced at any position after the first carding line and before the second carding line, so that the nanoparticles are sandwiched between the two carded fiber webs. Then, all the fibers containing the nanoparticles are bonded together in an air-through bonding oven (the nanoparticles are thermally entangled).

[0085] Another embodiment for producing one or more streams is shown in Figure 22. In this embodiment, the nanoparticles are placed between two meltblowing dies, forcing the molten polymer through small holes to create fibers. When the nanoparticles meet the still-tacky fibers, they are mechanically entangled with the fibers and thermally bonded to the fibers. Thus, in some embodiments, no additional bonding step is necessary. 22, an apparatus 600 for forming a fiber structure includes a fiberization system 610 similar to one of the systems and devices described above. The fiberization system 610 includes a nozzle 620 or similar device for dispersing the individual nanoparticles into a first stream 630. The apparatus 600 further includes a system for producing one or more fiber streams that are mixed with the stream of individual nanoparticles 630. This system may include any system known in the art, such as spunbond, carding, extrusion, etc.

[0086] In another embodiment, the apparatus includes first and second feeders, such as hoppers 640, 642, coupled to first and second extruders 650, 652. Each extruder includes an extrusion screw (not shown), for example, driven by a conventional drive motor (not shown). Rotation of the extrusion screw by the drive motor continuously heats the polymer to a molten state as it advances through the extruders 650, 652. Heating of the thermoplastic polymer to a molten state may be accomplished in multiple separate steps, with its temperature gradually increased as it advances through separate heating zones in the extruders 650, 652 toward two meltblowing dies 660, 662, respectively. The meltblowing dies 660, 662 may be yet another heating zone where the temperature of the thermoplastic is maintained at an elevated level for extrusion.

[0087] Each meltblowing die 660, 662 is configured such that the attenuating gas streams from the two per die come together to form a single gas stream that mixes and attenuates the molten yarns 20 as they exit small holes or orifices 672 in the meltblowing die. The molten yarns 20 are either lengthened into fibers or attenuated depending on the degree of attenuation of small diameter microfibers that are typically less than the diameter of the orifices 672. Thus, each meltblowing die 660, 662 has a corresponding single primary air stream 680, 690 of gas that contains the mixed and attenuated polymeric fibers. The primary air streams 680, 690 containing polymer fibers are aligned to meet at the forming region 700. In addition, a first stream 630 of individual nanoparticles is added to the two primary air streams 680, 690 of thermoplastic polymer fibers or microfibers at the forming region 30. The introduction of the individual nanoparticles into the two fibers primary air streams 680, 690 is designed to result in a distribution of the second fibrous material 32 within the mixed primary air streams 680, 690. This can be achieved by mixing the first stream 630 of individual nanofibers between the two primary air streams 680, 690 to bring all three gas streams together in a controlled manner.

[0088] Examples of suitable meltblowing dies that may be utilized to produce nonwoven materials are discussed in more detail in U.S. Patent Nos. 6,972,104, 8,017,534, and 7,772,456 and U.S. Patent Application Publication No. 20200216979A1, the entire disclosures of which are hereby incorporated by reference in their entireties in this application.

[0089] Example 1 A bicomponent microfiber substrate having an inner annular portion of polyester and an outer concentric HDPE portion was provided in roll form. The substrate was sprayed with adhesive and biosoluble glass fibers or nanoparticles were deposited in a roll-to-roll process. The nonwoven product was then heated in an oven and the cooled nonwoven product was collected on another roll. The nanoparticles were deposited according to the method described in Figures 12-16. In the experiments, adult soluble glass nanofibers are used. The nanofiber diameter is about 700 nm and the length is about 500 microns. A carded air-through bonded nonwoven fabric made from bicomponent fibers is used as the substrate in the following examples. Flat sheet media samples were tested at a filtration rate of 110 fpm (0.559 m / s). Sample size was 12" x 12" (30.48 cm x 30.48 cm). NaCl salt particles ranging from 0.3 to 10 microns were used as the contaminant.

[0090] Example 2 A carded nonwoven fabric made from 3.3 dtex (3 denier) PET / PE bicomponent fibers was used as the substrate. The binder used was a composition containing water, 2-hexoxyethanol, isopropanolamine, sodium dodecylbenzenesulfonate, lauramine oxide, and ammonium hydroxide. The amount of nanofiber add-on was controlled by adjusting the line speed. [Table 1] This example shows that by controlling the amount of nanoparticle add-on, the MERV value can be increased from MERV 7 to MERV 13.

[0091] Example 3 A 5.6 dtex (5 denier) bicomponent high loft air-through carded nonwoven fabric was used as the substrate. A typical starch binder was diluted and sprayed prior to nanofiber deposition. The starch-bound nanofibers were evaporated as the solvent was evaporated appropriately and dried under an IR heater. [Table 2]

[0092] Example 4 Spunbond or meltblown filter media was used as the substrate, and nanoparticles were incorporated into the substrate as described herein after IPA discharge. Spunbond fibers were made from molten polymers that were spun and drawn to produce filaments. The average basis weight of the substrate was about 90 gsm, and the average thickness was about 0.57 mm. A base sample was used that did not incorporate any nanoparticles. Four separate samples were prepared that included nanoparticles incorporated into the substrate as described herein. In sample 2, nanoparticles were incorporated into the meltblown fibers after IPA discharge. In samples 1, 3, and 4, nanoparticles were incorporated into the spunbond fibers after IPA discharge. The results of this test are shown in Table 3 below. [Table 3] As shown, the efficiency of the nanoparticle-incorporated filter media samples increased over the base sample for all three particle sizes, with a significant increase for the E2 and E3 particle sizes. The overall MERV value of the samples increased from MERV 7 (base sample) to MERV 12 with nanoparticles, and then to MERV 16. The base sample without nanoparticles had a pressure drop of 0.18 cm (0.07 in) of water. Samples 1-4 had slight pressure drop increases ranging from 0.43-1.0 cm (0.17-0.41 in) of water. Sample 2, which had nanoparticles incorporated into the meltblown fibers, had a MERV value of 14 and a pressure drop of 0.61 cm (0.24 in) of water.

[0093] Example 5 A 5.6 decitex (5 denier) air-through carded fabric was used as the substrate. A base sample was used without nanoparticles incorporated. Two separate samples were prepared with nanoparticles incorporated into the substrate as described herein. The results of this testing are shown in Table 4 below. [Table 4] As shown, the efficiency of the nanoparticle incorporated filter media samples increased substantially compared to the base sample for all three particle groups. The overall MERV value of the samples increased from MERV 6 (base sample) to MERV 13 with nanoparticles. The base sample without nanoparticles had a pressure drop of 0.076 cm (0.03 inches) of water. Sample 1 had a slight increase in pressure drop ranging from 0.79 to 0.84 cm (0.31 to 0.33 inches) of water.

[0094] Example 6 Meltblown fibers were used as the substrate. The substrate had an average basis weight of about 24 gsm and an average thickness of about 0.4 mm. A base sample was used that did not incorporate nanoparticles or adhesives such as PVOH. Sample 1 included meltblown fibers connected with a belt. PVOH was sprayed onto the fibers, but no nanoparticles were incorporated therein. Sample 2 included meltblown fibers with the fuzzy side up. PVOH was sprayed onto the fibers, but no nanoparticles were incorporated therein. Sample 3 included meltblown fibers sprayed with PVOH and nanoparticles incorporated into the fibers as described herein. The results of this testing are shown in Table 5 below. [Table 5] As shown, the efficiency of Sample 3 incorporating nanoparticles increased over the other three base samples for all three particle groups, especially for the E1 particle group. The overall MERV value for Sample 3 increased from MERV 13 or 14 (base samples) to MERV 15 with nanoparticles. The addition of PVOH to Samples 2 and 3 did not substantially increase the pressure drop (i.e., 0.35 inches for base samples, 0.38 inches and 0.41 inches for Samples 1 and 2). The pressure drop for Sample 3 increased from about 0.40 inches of water to about 1 inch of water. Sample 3, which incorporated nanoparticles into the meltblown fibers, had a MERV value of 15 and a pressure drop of 1.02 inches of water.

[0095] Example 7 A 5.6 dtex (5 denier) air-through carded fiber was used as the substrate. A base sample was used without nanoparticles incorporated. Seven additional samples were prepared containing 5.6 dtex (5 denier) carded fiber with nanoparticles incorporated into the substrate as described herein. The results of this testing are shown in Table 6 below. [Table 6] As shown, the efficiency of the seven samples incorporating nanoparticles increased compared to the base sample for all three particle groups, especially for the E2 and E3 particle groups. The overall MERV value of the samples increased from MERV 6 (base sample) to MERV 17 with nanoparticles and then to MERV 13. The pressure drop only increased from 0.076 cm (0.03 inches) of water to a maximum of 0.81 cm (0.32 inches) of water.

[0096] Example 8 Bulky spunbond fibers were used as the substrate for the continuous fiber line. This test included two different versions: 205-6 and 205-2, which changed the settings for the continuous fiber line to produce two substrates with different weights and thicknesses. A base sample for each version (205-6 and 205-2) was used without nanoparticles incorporated. Six additional samples were prepared including 205-6 and 205-2 fibers with nanoparticles incorporated into the substrate as described herein. The results of this test are shown in Table 7 below. [Table 7] As shown, the efficiency of the six samples incorporating nanoparticles showed substantially increased efficiency compared to the base sample for all three particle groups. The overall MERV value of the samples increased from MERV 6 (base sample) to MERV 11 with nanoparticles and then to MERV 14. The pressure drop only increased from 0.10 cm (0.04 inches) of water to a maximum of 2.2 cm (0.87 inches) of water. The pressure drop of 205-2 only increased to a maximum of 1.2 cm (0.48 inches) of water.

[0097] Example 9 Spunbond and meltblown fibers were used as the substrate. The average basis weight of the substrate was about 70 gsm for the spunbond fibers and about 24 gsm for the meltblown fibers. The average thickness of the substrate was about 0.75 mm. A base sample was used that did not incorporate nanoparticles. Five additional samples were prepared that included spunbond + meltblown fibers with nanoparticles in the fibers as described herein. In samples 1-3, the nanoparticles were sprayed onto the meltblown fibers. In samples 4 and 5, the nanoparticles were sprayed onto the spunbond fibers. Also, in samples 1 and 2, the adhesive PVOH was not sprayed onto the substrate. Samples 3-5 had PVOH sprayed onto them. The results of this testing are shown in Table 8 below. [Table 8] As shown, the efficiency of the five samples incorporating nanoparticles showed substantially increased efficiency compared to the base sample for all three particle groups. The overall MERV value of the samples increased from MERV 5 (base sample) to MERV 16 with nanoparticles. The pressure drop only increased from 0.18 cm (0.07 inches) of water to a maximum of 1.42 cm (0.56 inches) of water. For samples 3-5 (PVOH sprayed onto the substrate), the pressure drop only increased to a maximum of 1.0 cm (0.4 inches) of water.

[0098] Example 10 A 5.6 dtex (5 denier) air-through carded glass fiber was used as the substrate. A base sample was used without nanoparticles incorporated. Three additional samples were prepared containing 5.6 dtex (5 denier) carded glass fiber with nanoparticles incorporated. The results of this testing are shown below in Table 9. [Table 9] As shown, the efficiency of the three samples incorporating nanoparticles showed substantially increased efficiency compared to the base sample for all three particle groups. The overall MERV value of the samples increased from MERV 6 (base sample) to MERV 12 or MERV 13 with nanoparticles. The pressure drop only increased from 0.076 cm (0.03 inches) of water to a maximum of 0.69 cm (0.27 inches) of water.

[0099] Example 11 Air-through carded glass fibers of 5.6 dtex (5 denier) and 7.8 dtex (7 denier) were used as the substrate. The media was air-through bonded. A base sample was used without nanoparticles incorporated. Nineteen additional samples were prepared containing fiber blends of 5.6 dtex (5 denier) and 7.8 dtex (7 denier) carded glass fibers with incorporated nanoparticles. The results of this testing are shown below in Table 10. [Table 10] As shown, the efficiency of all 19 samples incorporating nanoparticles showed substantially increased efficiency compared to the base sample for all three particle groups. The overall MERV value of the samples increased from MERV 6 (base sample) to MERV 10 with nanoparticles and even to MERV 13 (most samples were rated MERV 13). The pressure drop only increased from 0.076 cm (0.03 inches) of water to a maximum of 0.79 cm (0.31 inches) of water. While the devices, systems and methods have been described in detail herein in accordance with certain preferred embodiments thereof, numerous improvements and modifications therein may be made by those skilled in the art, and the foregoing description should therefore not be construed as limited thereby, but should be construed to include such obvious modifications as set forth above, and should be limited only by the spirit and scope of the following claims.

[0100] For example, in a first aspect, a first embodiment includes a method of making a product including a fibrous material, the method including isolating discrete nanoparticles in a gaseous medium having at least one dimension less than 1 micron, and mixing the discrete nanoparticles with fibers to form the product. A second embodiment is the first embodiment, further comprising dispersing the individual nanoparticles on a first surface of a substrate comprising fibers, whereby the nanoparticles penetrate through at least the first surface of the substrate. A third embodiment is any combination of the first two embodiments, further comprising mixing the first stream of discrete nanofibers with one or more fiber streams to form a product. A fourth embodiment is any combination of the first three embodiments, wherein the substrate has a thickness from a first surface to a second surface opposite the first surface, and further comprising dispersing the nanoparticles within the substrate at least 25% of the width from the first surface to the second surface. A fifth embodiment is any combination of the first four embodiments, further comprising dispersing nanoparticles within the substrate for at least 50% of the thickness from the first surface to the second surface. A sixth embodiment is any combination of the first five embodiments, wherein individual nanoparticles are incorporated substantially throughout said substrate to form a composite material. A seventh embodiment is any combination of the first six embodiments, further comprising dispersing discrete nanoparticles from the first surface to the opposing second surface of the substrate. An eighth embodiment is any combination of the first seven embodiments, where the individual nanoparticles form a gradient within the substrate such that the density of the individual nanoparticles decreases from the first surface to the second surface. A ninth embodiment is any combination of the first eight embodiments, wherein the gas is compressed air. A tenth embodiment is any combination of the first nine embodiments, further comprising mechanically separating the nanofiber macro-clusters into smaller nanofiber clusters. An eleventh embodiment is any combination of the first ten embodiments, further comprising converting the nanofiber clusters into individual nanoparticles. A twelfth embodiment is any combination of the first eleven embodiments, further comprising applying a reduced pressure to the nanofiber clusters to draw the nanofiber clusters into the compressed air stream. A thirteenth embodiment is any combination of the first twelve embodiments, further comprising advancing the nanofiber clusters against a surface to break up at least some of the nanofiber clusters into individual nanoparticles. A fourteenth embodiment is any combination of the first thirteen embodiments, further comprising separating individual nanoparticles from the nanofiber clusters. A fifteenth embodiment is any combination of the first fourteen embodiments, further comprising applying a vortex to the nanofiber clusters and the individual nanoparticles and applying a reduced pressure to pull the nanofiber clusters from the individual nanoparticles. A sixteenth embodiment is any combination of the first fifteen embodiments, further comprising spraying the discrete nanoparticles onto the first surface of the substrate comprising fibers. A seventeenth embodiment is any combination of the first sixteen embodiments, further comprising applying an attractive force to a second surface of the substrate opposite the first surface to draw said individual nanoparticles through the substrate. An eighteenth embodiment is any combination of the first seventeen embodiments, further comprising applying a binder to the fibers in the substrate. A nineteenth embodiment is any combination of the first eighteen embodiments, further comprising spraying a binder onto the fibers. A twentieth embodiment is any combination of the first nineteen embodiments, further comprising crosslinking the binder. A twenty-first embodiment is any combination of the first twenty embodiments, further comprising heating the substrate to bond the fibers into individual nanoparticles. A twenty-second embodiment is any combination of the first twenty-one embodiments, further comprising drying the fibers and nanoparticles within the substrate. A twenty-third embodiment is any combination of the first twenty-two embodiments, further comprising converting the fibrous material into a filter. A twenty-fourth embodiment is a fibrous material formed from any combination of the first twenty-three embodiments. A twenty-fourth embodiment is a filter medium formed from any combination of the first twenty-three embodiments.

[0101] In a second aspect, a first embodiment includes a system for a product comprising a fibrous material, the system including a first apparatus for isolating discrete nanoparticles in a gas, the discrete nanoparticles having at least one dimension less than 1 micron, and a second apparatus for mixing the discrete nanoparticles with fibers to form the product. A second embodiment is the first embodiment, where the second apparatus includes a nozzle for dispersing individual nanoparticles onto a first surface of a substrate comprising fibers, whereby the nanoparticles penetrate through at least the first surface of the substrate. A third embodiment is any combination of the first two embodiments, wherein the second apparatus includes a feeder for forming a first stream of discrete nanoparticles and mixing the first stream with one or more streams of fibers to form the fibrous material. A fourth embodiment is any combination of the first three embodiments, wherein the substrate has a thickness from a first surface to a second surface opposite the first surface, and further comprising dispersing the nanoparticles within the substrate at least 25% of the width from the first surface to the second surface. A fifth embodiment is any combination of the first four embodiments, further comprising dispersing nanoparticles within the substrate for at least 50% of the thickness from the first surface to the second surface. A sixth embodiment is any combination of the first five embodiments, where individual nanoparticles are incorporated substantially throughout the substrate to form a composite material. A seventh embodiment is any combination of the first six embodiments, wherein the substrate has a thickness from a first surface to a second surface opposite the first surface, and the nozzle is configured to disperse the nanoparticles within at least 25% of the thickness of the substrate from the first surface to the second surface. An eighth embodiment is any combination of the first seven embodiments, wherein the nozzle is configured to disperse within the substrate at least 50% of the thickness from the first surface to the second surface. A ninth embodiment is any combination of the first eight embodiments, wherein the nozzle is configured to disperse the individual nanoparticles substantially throughout the substrate to form a composite material. A tenth embodiment is any combination of the first nine embodiments, wherein the nozzle is configured to disperse individual nanoparticles from a first surface to an opposing second surface of the substrate. An eleventh embodiment is any combination of the first ten embodiments, wherein the nozzle is configured to disperse the individual nanoparticles to form a gradient within the substrate, whereby the density of the individual nanoparticles decreases from the first surface to the second surface. A twelfth embodiment is any combination of the first eleven embodiments, wherein the gas is compressed air. A thirteenth embodiment is any combination of the first twelve embodiments, further comprising a separator for mechanically separating the nanofiber macro-clusters into smaller nanofiber clusters. A fourteenth embodiment is any combination of the first thirteen embodiments, further including a compressed air source, a pump, a first passageway connecting the compressed air source to the pump, and a second passageway connecting the separator to the pump. A fifteenth embodiment is any combination of the first fourteen embodiments, including an eductor, wherein the pump is configured to generate a reduced pressure to draw small clusters of nanofibers from the separator and through the second passage. A sixteenth embodiment is any combination of the first fifteen embodiments, further comprising a reactor having an internal chamber connected to the third passage, the reactor configured to separate individual nanoparticles from the nanofiber clusters. A seventeenth embodiment is any combination of the first sixteen embodiments, wherein the interior chamber of the reactor includes one or more inlets coupled to the passageway, and the pump is configured to advance the individual fibers and nanofiber clusters through the inlets with a velocity vector that creates a vortex within the reactor. An eighteenth embodiment is any combination of the first seventeen embodiments, wherein the internal chamber substantially comprises a central tube and the velocity vector is oriented perpendicular to a longitudinal axis of the tube. A nineteenth embodiment is any combination of the first eighteen embodiments, wherein the central tube includes a substantially cylindrical outer surface having an upper opening, and the individual fibers and nanofiber clusters are advanced in a spiral manner around the outer surface of the central tube. A twentieth embodiment is any combination of the first nineteen embodiments, where the individual nanoparticles are drawn into the top opening of the central tube. A twenty-first embodiment is any combination of the first twenty embodiments, wherein the internal chamber includes one or more outlets at an opposite end of the internal chamber from the one or more inlets, and the system further includes an energy source coupled to the outlets and configured to apply reduced pressure to the chamber to draw the nanofiber clusters through the outlets. A twenty-second embodiment is any combination of the first twenty-one embodiments, further comprising a nozzle fluidly connected to the central tube for dispersing the individual nanoparticles onto the substrate comprising the fibers. A twenty-third embodiment is any combination of the first twenty-two embodiments, further including a feeder for advancing the substrate adjacent the nozzle, the feeder having an upstream end and a downstream end. A twenty-fourth embodiment is any combination of the first twenty-three embodiments, further comprising a coating apparatus for dispersing a binder on the fibers in the substrate. A twenty-fifth embodiment is any combination of the first twenty-four embodiments, wherein the coating apparatus includes a spray apparatus having an outlet adjacent the upstream end of the feeder and the nozzle. A twenty-sixth embodiment is any combination of the first twenty-five embodiments, wherein the feeder includes first and second opposing surfaces, the substrate is advanced along the first surface, and the system further includes a reduced pressure source adjacent the second surface. A twenty-seventh embodiment is any combination of the first twenty-six embodiments, further comprising a dryer disposed proximate the feeder between the housing and the downstream end of the feeder for heating the nanoparticles and fibers. A twenty-eighth embodiment is any combination of the first twenty-seven embodiments, wherein the article comprises a filter medium.

Claims

1. A system for manufacturing products containing fibrous materials, A first apparatus for receiving a first group of nanofibers having a first dimension and separating the first group of nanofibers in a gas into nanoparticles having a second dimension smaller than the first dimension, wherein the nanoparticles have at least one dimension of less than 1 micron, and A system comprising a second apparatus for mixing the nanoparticles with fibers to form the product.

2. The system according to claim 1, wherein the second apparatus includes a nozzle for dispersing the nanoparticles on a first surface of a fiber-containing substrate such that the nanoparticles penetrate at least through a first surface of the substrate.

3. The system according to claim 1, wherein the second apparatus includes a feeder for forming a first stream of nanoparticles and mixing the first stream with one or more streams of fibers to form the fibrous material.

4. The system according to claim 2, wherein the substrate has a thickness from the first surface to the second surface opposite the first surface, and the nozzle is configured to disperse the nanoparticles within the substrate to a width of at least 25% of the width from the first surface to the second surface.

5. The system according to claim 4, wherein the nozzle is configured to disperse the nanoparticles in the substrate to a thickness of at least 50% from the first surface to the second surface.

6. The system according to claim 4, wherein the nozzle is configured to disperse the nanoparticles from the first surface of the substrate to the second surface on the opposite side.

7. The system according to claim 1, wherein the gas is compressed air.

8. The system according to claim 1, further comprising a separator for mechanically separating nanofiber macroclusters into a first group of nanofibers.

9. Compressed air source, pump, A first passage connecting the compressed air source to the pump, The system according to claim 8, further comprising a second passage for connecting the separator to the pump.

10. The system according to claim 9, wherein the pump includes a discharge device configured to generate a reduced pressure for drawing the first group of nanofibers from the separator through the second passage.

11. The system according to claim 10, further comprising a reactor having an internal chamber connected to a third passage, the reactor being configured to separate a second group of nanofibers into nanoparticles, wherein the second group of nanofibers has a third dimension greater than the second dimension and smaller than the first dimension.

12. The system according to claim 11, wherein the internal chamber of the reactor includes one or more inlets connected to the passage, and the pump is configured to advance the second group of nanofibers through the inlets with a velocity vector that creates a vortex within the reactor.

13. The system according to claim 12, wherein the internal chamber substantially includes a central tube, and the velocity vector includes a direction perpendicular to the longitudinal axis of the tube.

14. The system according to claim 13, wherein the central tube includes a substantially cylindrical outer surface having an upper opening, and the nanoparticles are propelled in a spiral manner around the outer surface of the central tube.

15. The system according to claim 14, wherein the nanoparticles are drawn into the upper opening of the central tube.

16. The system according to claim 12, wherein the internal chamber includes one or more outlets from one or more inlets to the opposite end of the internal chamber, and the system further includes an energy source connected to the outlets and configured to apply reduced pressure to the chamber to draw out the nanoparticles through the outlets.

17. The system according to claim 16, further comprising a nozzle fluidly connected to the central tube for dispersing the nanoparticles on the fiber-containing substrate.

18. The system according to claim 17, further comprising a feeder for advancing the substrate adjacent to the nozzle, the feeder having an upstream end and a downstream end.

19. The system according to claim 18, further comprising a coating apparatus for dispersing a binder on the fibers in the substrate.

20. The coating apparatus includes a spraying device having an outlet adjacent to the upstream end of the feeder and the nozzle, according to claim 19.

21. The system according to claim 1, wherein the product includes a filter medium.

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