Hierarchical composites for enhancing the physical performance of formulation, their preparation, and final products therefrom

Abstract

Generally speaking, this invention relates to hierarchical composites or delivery systems that are used to improve the performance of sealants, coatings, composites, adhesives, and other polymeric products. Hierarchical composites are materials that combine multiple types of structures at different scales to achieve enhanced properties and performance in such compositions. Expressly, but not limited to, the hierarchal composites carrying layers filled with, or otherwise, of nanomaterials, dyes, explosives, catalysts, metals, viscosity modifiers, thickeners, rheology modifiers, toughening agents, and like structures for the benefit of improved physical, chemical, electrical, conductive, color, rheological or other like properties minimizing or reducing for example, the need for more significant amounts of said materials.

Description

HIERARCHICAL COMPOSITES FOR ENHANCINGTHE PHYSICAL PERFORMANCE OF FORMULATION, THEIR PREPARATION, AND FINAL PRODUCTS THEREFROMCROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application hereby claims the benefit of the provisional patent application of the same title, Serial No. 63 / 711,580, filed on October 24, 2024, the disclosure of which is herein incorporated by reference in its entirety.FIELD OF INVENTION

[0002] Generally speaking, this invention relates to hierarchical composites or delivery systems that are used to improve the performance of sealants, coatings, composites, adhesives, and other polymeric products. Hierarchical composites are materials that combine multiple types of structures at different scales to achieve enhanced properties and performance in such com-positions. Expressly, but not limited to, the hierarchal composites carrying layers filled with, or otherwise, of nanomaterials, dyes, explosives, catalysts, metals, viscosity modifiers, thickeners, rheology modifiers, toughening agents, and like structures for the benefit of improved physical, chemical, electrical, conductive, color, rheological or other like properties minimizing or reducing for example, the need for more significant amounts of said materials.BACKGROUND

[0003] Many desirable effects can be achieved by incorporating hierarchical composites in compositions and their subsequent realizations into final performing products. The importance of hierarchical materials lies in their unique properties and functionalities that emerge from integrating structures across different scales, namely, nanoscale, mesoscale, and microscale.

[0004] This process often involves combining materials with complementary properties to overcome the limitations of individual materials. Without wishing to be bound by any scientific theory, we surmise that the noted composite’s functional materials are formed or driven by the enthalpy and the inherent porosity of the individual components in one aspect of the invention, and that the release of the materials is entropy driven.- 1 - 120903.000059\4900-0177-6754.8

[0005] Hierarchical materials of the present invention possess structure at multiple length scales, from the nanoscale to the macroscale. This multiscale structuring can significantly influence the material's overall properties. One of the most significant advantages of hierarchical and multiscale materials is enhancing mechanical properties such as strength, toughness, and stiffness. For instance, carbon nanotubes and graphene can be integrated into polymer matrices to create composites with superior mechanical properties compared to their components. These enhancements are due to the efficient load transfer between the nanoscale reinforcements and the macroscopic material matrix, as well as the ability of hierarchical structures to dissipate energy and resist crack propagation.

[0006] The use of the individual components of the hierarchal hybrid composites on their own is fraught with incompatibility and suboptimal interfacial interactions because of the chemical, Van der Waals, and other associations. Furthermore, the complexity of the manufacturing process, controlling the size and distribution to achieve desired properties can require specialized equipment, potentially increasing the cost and time needed for production. In addition, the nano dimensions of the components lead to dramatic viscosity increases as the amount of said materials increases, for example, limiting the amount to be added, thus limiting the range of desired effects to be incorporated into a composition. Carbon nanotubes are among the nanomaterials most limited by these overall effects. This can, among other things, limit the amount of nanomaterial that can be incorporated or the amount required to achieve a particular effect. Likewise, the inorganic metal oxides of, for example, silicon, aluminum, and titanium are incompatible with the polymer matrices. The nanotubes and the like are the nano dimensional components of the hierarchical composites and possess properties that inherently lead to their physical association, such as agglomeration, attachment, and then network formation, all of which can lead to limiting deleterious effects.

[0007] The hierarchical composites as a whole or their components can enable significantly increased toughness, elasticity, strength, wear resistance, product life, environmental resistance, and the like. In particular, nanomaterials such as graphene or other platelike structures form hierarchical composites by combining with the metal oxides of, for example, silicon, aluminum, and titanium of the micro size scales. Economically, more expensive materials may need to be incorporated to achieve a desired effect, often making many applications uneconomical or limited in overall economic application in the broadest markets.120903.000059\4900-0177-6754.8 - 2 -

[0008] In summary, it would be helpful to find a more efficient, less limiting way to use hierarchical composites by combining porous thermoplastic polyurethane (TPU), polystyrene, poly(methyl methacrylate) (PMMA), polylactic acid (PLA), polyvinyl alcohol (PVA), polyether ether ketone (PEEK), polyetherimide (PEI), inorganic metal oxides of transition metals, and precipitated / fumed silica, activated carbon, porous carbon with nanomaterials such as carbon nanotubes, graphene, nano-silica, explosives, pigments.Furthermore, the use of the afore-described composites reduces the direct handling of potentially hazardous materials, thereby enhancing worker safety and improving the over-all efficiency of the manufacturing process by facilitating more straightforward incorporation into the end products or intermediate formulations.BRIEF SUMMARY

[0009] This invention relates to a hierarchical composite, comprising:(i) a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles; and(ii) a nanomaterial;wherein the nanomaterial optionally resides within the interstitial spaces between plurality of carrier material particles, or wherein the nanomaterials is bound to the plurality of carrier material particles on their surface or in between the particles through physical, mechanical, or associative forces.

[0010] In another embodiment, this invention relates to a hierarchical composite as recited above, wherein at least two particles of said plurality of particles that are not chemically bound.

[0011] In yet another embodiment, this invention relates to a hierarchical composite as recited above, wherein none of, some of, or all of the said plurality of carrier material particles have internal porosity.

[0012] In one embodiment, this invention relates to a hierarchical composite as recited above, wherein the carrier material comprises at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, and an oligomer.

[0013] In another embodiment, this invention relates to a hierarchical composite as recited above, wherein the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, sodium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium,120903.000059\4900-0177-6754.8 - 3 -yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, and combination thereof.

[0014] In yet another embodiment, this invention relates to a hierarchical composite as recited above, wherein the inorganic metal salt is silica.

[0015] In one embodiment, this invention relates to a hierarchical composite as recited above, wherein the silica is precipitated or fumed silica or quartz.

[0016] In another embodiment, this invention relates to a hierarchical composite as recited above, wherein the mesoporous carrier material is selected from TPU, polystyrene, PMMA, PLA, PVA, PEEK, PEI, Nylon, polyester, polycarbonate, polyolefin, polyglycolic acid, polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polychlorotrifluoroethylene, phenol- (Bakelite), para-aramids (Kevlar and Twaron), polychloroprene (neoprene), natural rubber, meta-aramids (Nomex), polyacrylonitrile (PAN) (Orlon), polybutadiene, styrenebutadiene, copolyamide (Technora), polyimide (Ultem), aromatic polyesters (Vectran), poly(vinyl poly-p-phenylene-2,6-benzobisoxazole idene fluoride-co-hexafluoropropylene) (Viton), poly-p-phenylene-2,6-benzobisoxazole (Zylon).

[0017] In yet another embodiment, this invention relates to a hierarchical composite as recited above, wherein the nanomaterial comprises at least one of carbon nanostructures, carbon nanotubes, graphene, nano-silica, explosives, pigments, fullerene compounds, graphite oxide, nanocrystalline cellulose, single-wall carbon nanotubes, multi-wall carbon nanotubes, carbon nanofibers, doped carbon nanotubes, carbon sheets, one or more ferrous metals, oxides of one or more ferrous metals, superparamagnetic iron oxide nanoparticles (SPIONS), one or more non-ferrous metals, oxides of one or more non-ferrous metals, transition metals, transition metal oxides, silicon carbide-based material, boron nitride, and one or more combinations thereof.

[0018] In one embodiment, this invention relates to a hierarchical composite as recited above, wherein the hierarchical composite further comprises at least one polymeric or oligomeric shell fully or partially covering the plurality of carrier material particles comprising the nanomaterial.

[0019] In some embodiments, a hierarchical composite comprises a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles, and a nanomaterial. Wherein the nanomaterial is bound within the interstitial120903.000059\4900-0177-6754.8 - 4 -spaces among the plurality of carrier material particles or bound to the surface of the plurality of carrier material particles. The binding occurs through non-covalent interactions or associative forces. The nanomaterial has at least one dimension in the nanoscale of from about 0.9 nm to about 1,000 nm and the carrier material particles have a particle size in the microscale of from about 1 to about 1,200 pm. The hierarchical composite is particles with a particle size ranging from about 1 micron to about 2,000 microns. In some embodiments, the hierarchical composite is particles with a particle size ranging from about 4 microns to about 2,000 microns.

[0020] In some embodiments, a composition comprises the hierarchical composite and an epoxy resin, wherein the nanomaterial comprises carbon nanotubes.

[0021] In some embodiments, a composition comprises the hierarchical composite and thermoset polymer precursors. In some embodiments, the thermoset polymer precursors are able to form polyester, vinyl ester, polyurethane, polyols, phenolic, or bismaleimide.

[0022] In some embodiments, a composition comprises the hierarchical composite and thermoplastic polymer precursors. In some embodiments, the thermoplastic polymer precursors are able to form polyethylene, polyvinyl chloride, polystyrene, polyethyleneterpthalate, polyacrylate, polymethyl methacrylate, ethylene-vinyl acetate, acrylonitrile butadiene styrene, polycarbonate, polyamide (nylon), polyoxymethylene, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polyether sulfone, polyetherimide, polyether ether ketone, polybenzimidazole, or poly tetrafluoroethy 1 ene.

[0023] In some embodiments, a cured composition is obtained by curing the hierarchical composite with an epoxy resin, thermoset polymer precursors, or thermoplastic polymer precursors.

[0024] In some embodiments, a method of making the hierarchical composite comprisesshear mixing a plurality of carrier material particles and a nanomaterial in a dispersion with a solvent and a surfactant. The solvent is removed to form a solid hierarchical composite.

[0025] In some embodiments, a hierarchical composite comprises a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles, and a nanomaterial. In some embodiments, the nanomaterial is bound within the120903.000059\4900-0177-6754.8 - 5 -interstitial spaces among the plurality of carrier material particles, or bound to the surface of the plurality of carrier material particles. The binding occurs through non-covalent interactions or associative forces. In some embodiments, the nanomaterial has at least one dimension in the nanoscale of from about 0.9 nm to about 1,000 nm. In some embodiments the carrier material particles have a particle size in the microscale of from about 1 to about 1,200 pm. In some embodiments, the hierarchical composite is particles with a particle size ranging from about 1 micron to about 2,000 microns.

[0026] These and other objects and advantages shall be made apparent from the accompanying drawings and the description thereof.BRIEF DESCRIPTION OF THE FIGURES

[0027] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments, and together with the general description given above, and the detailed description of the embodiments given below, serve to explain the principles of the present disclosure.

[0028] FIG. 1 shows a core-shell technology with a polybutadiene core and a PMMA shell. Similarly, the second portion of Fig. 1 shows a polyacrylic core and a PMMA shell.

[0029] FIG. 2 shows CNTs embedded on to the surface a rigid core and their subsequent incorporation in a polymeric matrix for toughening purposes. The hierarchical composite particles deliver toughening and improved performance through energy dissipation, energy absorption, and fracture / crack diffraction and bifurcation.

[0030] FIG. 3 is a transmission electron microscopy (TEM) image that shows the hierarchical composite structure in which the multi -walled carbon nanotubes (MW CNTs) are intimately associated with the primary silica particles. The higher-magnification image (Fig. 3a) and the lower-magnification image (Fig. 3b) collectively reveal the spatial distribution of the MWCNT-silica network. The background contrast originates from the TEM grid that supports the ultrathin composite sample, enabling the transmission of the electron beam required to generate the image.

[0031] FIG. 4 is a TEM image that shows the hierarchical silica composite in which the multi -walled carbon nanotubes (MW CNTs) are embedded within the interstitial regions of the primary silica particles. As shown in the higher-magnification image (left image) and the lower-magnification overview (right image), the primary silica particles are closely120903.000059\4900-0177-6754.8 - 6 -associated with the MWCNT framework. This spatial association effectively shields the intrinsic van der Waals forces between neighboring CNTs, thereby preventing their reagglomeration and promoting uniform dispersion of the MW CNTs throughout the polymer matrix.

[0032] FIG. 5 shows a schematic of the hierarchical composites. The carrier material, for example, fumed or precipitated silica, in the micrometer size range of the agglomeration, with each particle being in the nanometer range, is shown. The CNTs available for dispersion are also shown. The loose agglomeration of carrier material particles is mixed under high intensity with CNTs to provide CNTs physically embedded within the interstitial spaces of the loosely agglomerated silica particles or physically attached, for example, through van der Waals forces or other associative forces such as hydrogen bonding, with the fumed silica particles, which are called hierarchical composites. The hierarchical composites, that is, the CNTs embedded in the silica, are dispersed into a matrix needing improving its properties, for example, toughness, tensile strength, or viscosity. The nanomaterials, such as the CNTs, are released into the matrix needing such dispersed nanomaterials through reversing the associative forces or through pH modification, temperature, concentration, or other physical or chemical triggers. In the alternative, and as shown, the hierarchical composite agglomerates can be fully or partially encapsulated by other polymeric or oligomeric materials or emulsions. Such encapsulated hierarchical composites are then introduced into the matrix needing dispersion of such nanomaterials and carrier materials.

[0033] FIG. 6 is the optical microscopy image of the dispersion of the toughening additives commercially available — 10% ClearStrength and 10% DuraStrength, see Fig. 1 — and the dispersion using the hierarchical composites of the recent invention (with 10% NCT3 hierarchical composites). Visually, the dispersion provided by the present invention’s composites is clearly superior to the commercially available additives.

[0034] FIG. 7 depicts the Young’s Modulus of an Epoxy sample to which the NCT3 hierarchical composites (HCs) have been added. The modulus improved by 30% over the control sample and about 20% over the commercially available additive (that is, when a commercially available additive was added).

[0035] FIG. 8 depicts the Force-at-Break measurement of an Epoxy sample to which the NCT3 hierarchical composites (HCs) have been added. The Force-at-Break improved by120903.000059\4900-0177-6754.8 - 7 -about 30% over the control sample and the commercially available additive (that is, when a commercially available additive was added).

[0036] FIG. 9 depicts the normalized toughness numbers for two systems, Epoxy and Polyurethane. To each system, 5% NC additive of the present invention is added. Also, a 10% commercial additive called paraloid is added to an equivalent sample. The Epoxy system is the Epon 862 cured with PEMP-HS (the tetrathiol curing agent, 65°C and 2 hours), and the Polyurethane system is the Pluracol 1010, Lupranate M20. In the Epoxy system, a 500% increase in toughness was found. In the Polyurethane system, a 200% increase was seen.

[0037] FIG. 10 are graphs showing toughness and elongation data from Case Study 2.

[0038] FIG. 11 are graphs showing toughness and elongation data from Case Study 3.

[0039] FIG. 12 is an optical microscopy image of a good dispersion of MWCNTs in Epon 862 delivered through NCT3.

[0040] FIG. 13 is an optical microscopy image of a poor dispersion of MWCNT in Epon 862.DETAILED DESCRIPTION

[0041] Before the present compositions, articles, devices, and / or methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific methods and may vary as such. It is also to be understood that the terminology used herein describes aspects only and is not intended to be limiting. As used in the specification and in the claims, the term “comprising” may include the embodiments “consisting of’ and “consisting essentially of.”

[0042] Disclosed are materials, compositions, and components that can be used for, in conjunction with, in preparation for, or are products of the disclosed method and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. Thus, if a class of adhesives A, B, and C are disclosed as well as a class of120903.000059\4900-0177-6754.8 - 8 -additives D, E, and F and an example of a combination A-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated. Thus, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. This concept applies to all aspects of this disclosure including, but not limited to, compositions, and steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.

[0043] Unless expressly stated otherwise, it is not intended that any method outlined herein be construed as requiring that its steps be performed in a particular order. Accordingly, where a method claim does not expressly recite an order to be followed by its steps, or where neither the claims nor the descriptions specifically state that the steps are to be limited to a precise sequence, it should not be inferred that a specific order is intended or required. This holds for any possible non-express basis for interpretation, including but not limited to: logical flow or arrangement of steps; interpretations derived from the grammatical organization, syntax, or punctuation; and the quantity or variety of embodiments detailed in the specification. The description of the invention should not be read as mandating a fixed sequence of steps, unless such a requirement is articulated explicitly.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.

[0045] Except where expressly noted, trademarks are shown in upper case.

[0046] Unless stated otherwise, all percentages, parts, ratios, etc., are by weight. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, when values are expressed120903.000059\4900-0177-6754.8 - 9 -as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0047] Unless stated otherwise, pressures expressed in psi units would be gauge, and pressures expressed in kPa units would be absolute. Pressure differences, however, are expressed as absolute (for example, pressure 1 is 25 psi higher than pressure 2).

[0048] When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values recited when defining a range.

[0049] When the term “about” is used, it is used to mean a certain effect or result can be obtained within a certain tolerance, and the skilled person knows how to obtain the tolerance. When the term "about" is used in describing a value or an endpoint of a range, the disclosure should be understood to include the specific value or endpoint referred to.

[0050] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0051] The transitional phrase "consisting of' excludes any element, step, or ingredient not specified in the claim, closing the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of' appears in a clause of the body of a claim, rather than immediately following the120903.000059\4900-0177-6754.8 - 10 -preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0052] The transitional phrase "consisting essentially of limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention. A “consisting essentially of’ claim occupies a middle ground between closed claims that are written in a “consisting of’ format and fully open claims that are drafted in a “comprising” format. Optional additives as defined herein, at a level that is appropriate for such additives, and minor impurities are not excluded from a composition by the term “consisting essentially of.”

[0053] Further, unless expressly stated to the contrary, "or" and “and / or” refers to an inclusive and not to an exclusive. For example, a condition A or B, or A and / or B, is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0054] The use of "a" or "an" to describe the various elements and components herein is merely for convenience and to give a general sense of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.

[0055] The term “predominant portion” or “predominantly,” as used herein, unless otherwise defined herein, means greater than 50% of the referenced material. If not specified, the percent is on a molar basis when reference is made to a molecule (such as hydrogen and ethylene), and otherwise is on a weight basis (such as for additive content).

[0056] The term “substantial portion” or “substantially,” as used herein, unless otherwise defined, means all or almost all or the vast majority, as would be understood by the person of ordinary skill in the context used. It is intended to consider some reasonable variance from 100% that would ordinarily occur in industrial -scale or commercial-scale situations.

[0057] All parts, percentages and ratios used herein are expressed by weight unless otherwise specified.120903.00005914900-0177-6754.8 - 11 -

[0058] In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0059] “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0060] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification. Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which they pertain. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein may be different from the actual publication dates, which can require independent confirmation. In the context of the present description, all publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth.

[0061] PCT Patent Application, PCT / US2024 / 025251 to Malofsky et al. is fully incorporated into this document, as if that patent reference were set forth, fully, here.

[0062] Generally speaking, and in one embodiment, this invention relates to hierarchical composite additives, comprising:120903.00005914900-0177-6754.8 - 12 -(i) a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles; and(ii) a nanomaterial;

[0063] wherein the nanomaterial optionally resides within the interstitial spaces between plurality of carrier material particles, or wherein the nanomaterials is bound to the plurality of carrier material particles on their surface or in between the particles through physical, mechanical, or associative forces.

[0064] In some embodiments, a hierarchical composite comprises a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles; and a nanomaterial. Wherein the nanomaterial is bound within the interstitial spaces among the plurality of carrier material particles, or bound to the surface of the plurality of carrier material particles. The binding occurs through non-covalent interactions or associative forces. The nanomaterial has at least one dimension in the nanoscale of from about 0.9 nm to about 1,000 nm and the carrier material particles have a particle size in the microscale of from about 1 to about 1,200 pm. The hierarchical composite are particles with a particle size ranging from about 1 microns to about 2,000 microns. In some embodiments, nanomaterial has at least one dimension from about 1 to about 100 nm. In some embodiments, carrier material particles have a particle size from about 1 to about 1,000 pm or from about 1 to about 100 pm.

[0065] In some embodiments, a hierarchical composite comprises a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles, and a nanomaterial. In some embodiments, the nanomaterial is bound within the interstitial spaces among the plurality of carrier material particles, or bound to the surface of the plurality of carrier material particles. The binding occurs through non-covalent interactions or associative forces. In some embodiments, the nanomaterial has at least one dimension in the nanoscale of from about 0.9 nm to about 1,000 nm. In some embodiments the carrier material particles have a particle size in the microscale of from about 1 to about 1,200 pm. In some embodiments, the hierarchical composite is particles with a particle size ranging from about 1 micron to about 2,000 microns.

[0066] The hierarchical composite comprises particles. In some embodiments, the hierarchical composite particles range in size from about 1 micron to about 2,000 microns, such as about 1 micron to about 1,500 microns, about 1 micron to about 1,000 microns, about120903.000059\4900-0177-6754.8 - 13 -1 micron to about 750 microns, about 1 micron to about 500 microns, about 5 microns to about 2,000 microns, about 10 microns to about 2,000 microns, about 25 microns to about 2,000 microns, about 50 microns to about 2,000 microns, about 100 microns to about 2,000 microns, about 200 microns to about 2,000 microns, and about 500 microns to about 2,000 microns.

[0067] The hierarchical composite comprises nanomaterials. In some embodiments, the nanomaterial comprises from about 0.05 wt.% to about 50 wt.% of the hierarchical composite, such as from about 0.05 wt.% to about 2 wt.%, from about 0.05 wt.% to about 10 wt.%, from about 2 wt.% to about 5 wt.%, about 2 wt.% to about 10 wt.%, from about 2 wt.% to about 20 wt.%, from about 2 wt.% to about 30 wt.%, from about 2 wt.% to about 40 wt.%, from about 5 wt.% to about 20 wt.%, from about 5 wt.% to about 30 wt.%, from about 5 wt.% to about 40 wt.%.

[0068] By “carrier material particles” is meant a loose or a physical agglomeration or collection or plurality of particles that form the base material in a hierarchical composite material, wherein the carrier material particles adhere to each other through van der Waals forces, hydrogen bonding, or other associative forces that allow for interstitial spaces in between the particles. The associative forces are such that they can be reversed or mitigated by external impact such as shear, mechanical force, pH, temperature, pressure, and the like. The base material can be inorganic such as inorganic salts— for example silica, alumina, titania— or oligomeric, or polymeric.

[0069] By “nanomaterial” is meant the particles that reside in between and are affixed in the interstitial spaces between the carrier material particles and / or are embedded or attached on the surface of the carrier material particles physically, mechanically, or via associative forces (generally not chemically), and / or are affixed in the porous channels of the carrier material particles of such particles have porosity.

[0070] By “reside,” “attached,” “embedded,” or “affixed” is meant that the nanomaterial particles are connected to the carrier material particles in a physical manner, and not chemically. For example, the connection could be as a result of weak attraction forces such as van der Waals, hydrogen bonding, or other such associative forces.120903.000059\4900-0177-6754.8 - 14 -

[0071] By “hierarchical composite” is meant the combined moiety comprising a plurality of loosely agglomerated carrier material particles having nanomaterials reside in the interstitial spaces, on the surface, or in the porous channels of the carrier material particles.

[0072] By “encapsulation” is meant that the hierarchical composite comprises at least one additional shell layer fully or partially covering the carrier materials particles with the nanomaterials embedded therein.

[0073] In one aspect, the hierarchical composite of the present invention with or without the encapsulation can be added a matrix that is in need for a desired improvement in physical or chemical property. And the desired improvement is achieved by release of the nanomaterials from the carrier material particles within the hierarchical composite by an external trigger or a force.

[0074] For example, physical properties that could be improved or tailored— increased or decreased— is the toughness, tensile strength, elongation-at-break, rheological properties, other flow properties, elasticity, plasticity, dilution, pH, lap shear, enthalpy, thermal conductivity, electrical conductivity, insulation, chemical and environmental resistance, and the like of the matrix to which such hierarchical composites are added.

[0075] The external trigger or force to release the nanomaterials in the matrix can be pH, temperature, mechanical force such as shear, UV light, other radiation triggers, electromotive force, and the like. In essence, the external force or the trigger act as a remover or mitigator of the associative forces, which allows for a release for the nanomaterial as a function of time or instantaneously to produce a desired effect.

[0076] Surprisingly, it has been found that microporous and mesoporous inorganic oxides, for example, of silicon, aluminum, and titanium function as essential components in assembling hierarchical composites with the likes of carbon nanotubes (CNTs), graphene, and other carbon nanomaterials. The hierarchal composites are effective in delivering the performance in sealants, coatings, composites, adhesives, and other polymeric products compared to the currently available additives. Of particular interest are where physical properties of an end composition and or physical product are achieved, including, but not limited to, thermal and electrical conductivity. Improved or controlled strength, toughness, elasticity, chemical resistance, environmental resistance, energy dampening, improved color, improved or controlled product life, improved or controlled failure and the like.120903.000059\4900-0177-6754.8 - 15 -

[0077] The invention relates specifically to, but is not limited to, particles carrying layers filled with or otherwise of nanomaterials, including metals and their chemical products, graphene, nanotubes and like structures for the benefit of improved physical, electrical, conductive, and other like properties minimizing by example the need for more significant amounts of said nanomaterials.

[0078] As used herein, “hierarchical composite” refers to a material that is capable of removing or mitigating the associative force in such a way as to release the nanomaterials. The hierarchical composite particle may have almost any geometric configuration, geometry, or size. For example, the HC particle may be formed in a shape including one or more of a sphere, thin plate, ribbon, sheet or coating, a rod or distended fiber, a porous structure including for example a foam, or one or more irregular or amorphous shapes.

[0079] Carrier Materials

[0080] The carrier materials can be composed of any suitable material as understood in the art. In some embodiments, the carrier material comprises at least one of an inorganic metal salt, activated carbon, porous carbon, a polymer, and an oligomer. Furthermore, the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, sodium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, and combination thereof. The carrier material can be multimeric, oligomeric, or polymeric. For example, the carrier material can comprise methyl methacrylate. In some embodiments, the carrier material is composed of polymeric microparticles. For example, the polymeric microparticles can be made from polymethyl methacrylate (PMMA), styrene, and / or one or more polymers or copolymers thereof. The microparticles can also be blends, alloys, and mixtures of polymers.

[0081] In some embodiments, the carrier material particles are porous. In some embodiments, the carrier material particles are non-porous.

[0082] Carrier materials can be organic, organ-metallic, inorganic, silicon derivatives, clear alumina, and the like.

[0083] The polymeric microparticles can include polymeric microspheres and microcapsules. The microcapsules can be porous or can be partially open. In some embodiments, the microparticles are spherical microparticles. The microparticles can have an effective diameter of from about 0.1 pm to about 1000 pm. As used herein, “effective120903.000059\4900-0177-6754.8 - 16 -diameter” refers to the diameter of an equivalent spherical microparticle of the same volume or weight. For example, the microparticles can have an effective diameter of from about 0.1 pm to about 0.5 pm, from about 0.5 pm to about 1 pm, from about 1 pm to about 5 pm, from about 5 pm to about 10 pm, from about 10 pm to about 50 pm, from about 50 pm to about 100 pm, from about 100 pm to about 200 pm, from about 200 pm to about 300 pm, from about 300 pm to about 400 pm, from about 400 pm to about 500 pm, from about 500 pm to about 600 pm, from about 600 pm to about 700 pm, from about 700 pm to about 800 pm, from about 800 pm to about 900 pm, from about 900 pm to about 1000 pm, and any and all increments therebetween.

[0084] In one embodiment, the effective diameter of the microparticle is one of the numbers as measured in pm, or one of the numbers within a range defined by any two numbers below, including the endpoints, in pm: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, and 1,000.

[0085] In one embodiment, the carrier materials as referred to herein, are microparticles composed of a homogeneous and solid polymer carrier material, while microcapsules are core-shell microparticles where the core may be solid, liquid, or even hollow spaces. The microparticles can also be prepared as a porous carrier material composed of interconnected microspheres. The porous carrier material can include pores that form on the surface or that are external and / or pores that form internally. The pores can be isolated or interconnected. The pores lead to extremely low mass density matrix material. The pores are suitable for entrapping nanomaterials, such as activators, catalysts, co-catalysts, co-reactants, oxidizers, reaction inhibitors, accelerators, and / or one or more other releasable ingredients.

[0086] In some embodiments, the carrier material is composed of monodispersed polymeric particles. In some embodiments, the carrier material is composed of polydispersed polymeric particles. The poly dispersion may include a narrow dispersion of particle sizes, for example, a monomodal distribution, a bimodal distribution, or a trimodal distribution. In some embodiments, the polydispersion includes a middle-dispersion of particle sizes. In some embodiments, the polydispersion includes a wide dispersion of particle sizes. In some embodiments, the polydispersion includes particle sizes ranging from about 1 nm to about 10 nm, from about 10 nm to about 50 nm, from about 50 nm to about 100 nm, from about120903.000059\4900-0177-6754.8 - 17 -100 nm to about 200 nm, from about 200 nm to about 400 nm, from about 400 nm to about 600 nm, from about 600 nm to about 800 nm, from about 800 nm to about 1000 nm, about 1 pm, from about 1 pm to about 1.5 pm, from about 1.5 pm to about 2 pm, from about 2 pm to about 2.5 pm, from about 2.5 pm to about 3 pm, from about 3 pm to about 3.5 pm, from about 3.5 pm to about 4 pm, from about 4 pm to about 4.5 pm, from about 4.5 pm to about 5 pm, and any and all increments therebetween. In some embodiments, the average particle size is up to about 0.1 pm. In some embodiments, the average particle size is in the range of from about 0.1 pm to about 0.5 pm, from about 0.5 pm to about 0.8 pm, from about 0.8 pm to about 1 pm, from about 1 pm to about 1.2 pm, from about 1.2 pm to about 1.5 pm, from about 1.5 pm to about 1.8 pm, from about 1.8 pm to about 2 pm, from about 2 pm to about 4 pm, from about 4 pm to about 6 pm, from about 6 pm to about 8 pm, from about 8 pm to about 10 pm, from about 10 pm to about 20 pm, from about 20 pm to about 40 pm, from about 40 pm to about 60 pm, from about 60 pm to about 80 pm from about 80 pm to about 100 pm, from about 100 pm to about 200 pm, from about 200 pm to about 400 pm, from about 400 pm to about 600 pm, from about 600 pm to about 800 pm, from about 800 pm to about 1000 pm, and any and all values therebetween.

[0087] In some embodiments, the carrier material in the hierarchical composite particles has a molecular weight of up to 10 kDa. In some embodiments, the carrier material in the carrier materials particles have a molecular weight of from about 10 kDa to about 25 kDa, from about 25 kDa to about 50 kDa, from about 50 kDa to about 75 kDa, from about 75 kDa to about 100 kDa, from about 100 kDa to about 125 kDa, from about 125 kDa to about 150 kDa, from about 150 kDa to about 175 kDa, from about 175 kDa to about 200 kDa, from about 200 kDa to about 225 kDa, from about 225 kDa to about 250 kDa, and any and all increments therebetween. Carrier materials, with much higher molecular weight, for example, that of branched or crosslinked polymers such as rubber is also within the scope of this invention.

[0088] In some embodiments, the carrier material has a molecular weight as provided by any number below, in kDa, or by a number within a range defined by any two numbers below, including the endpoints of such a range, in kDa: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000, and 1000000.120903.000059\4900-0177-6754.8 - 18 -

[0089] In some embodiments, the dispersion of polymeric particles includes particles with a low level of crosslinking. In some embodiments, the dispersion of polymeric particles includes particles with a standard or intermediate level of cross-linking. In some embodiments, the dispersion of polymeric particles includes particles with a high level of cross-linking.

[0090] In one embodiment, the hierarchical composite comprises, the inorganic metal salt, which is silica, fumed or precipitated silica, quartz, alumina, zirconia, titania, a combination of one or more of such substances. The carrier material can be one or more of TPU, polystyrene, PMMA, PLA, PVA, PEEK, PEI, Nylon, polyester, polycarbonate, polyolefin, polygly colic acid, PTFE, PVC, polychlorotrifluoroethylene, phenol -formaldehyde (Bakelite), para-aramids (Kevlar and Twaron), polychloroprene (neoprene), natural rubber, meta-aramids (Nomex), PAN (Orlon), polybutadiene, styrene -butadiene, copolyamide (Technora), polyimide (Ultem), aromatic polyesters (Vectran), poly(vinyl poly-p-phenylene-2,6-benzobisoxazole idene fluoride-co-hexafluoropropylene) (Viton), poly-p-phenylene-2,6-benzobisoxazole (Zylon).

[0091] In some embodiments, the hierarchical composite comprises an inorganic metal salt. In some embodiments, the inorganic metal salt is silica. In some embodiments, the silica has an agglomerated d50 particle size of from about 3 to about 100 microns and a primary particle size of about 5 to about 200 nm. In some embodiments, the silica has an agglomerated d50 particle size of from about 3 to about 200 microns, such as from about 3 to about 150 microns, from about 3 to about 100 microns, from about 3 to about 20 microns, from about 5 to about 10 microns, from about 3 to about 10 microns, and from about 10 to about 100 microns.

[0092] In some embodiments, the silica is precipitated or fumed silica or quartz. In some embodiments, the silica is silane-functionalized precipitated silica. Examples of functionalized silica include those where the silane is functionalized with alkylsilane, fluoroalkylsilanes, methyltrimethoxysilane (MTMS), hexamethyldisilazane, phenyltrimethoxysilane, phenyltri ethoxysilane, vinylphenyltrimethoxysilane, bis[3 -(triethoxysilyl)propyl]tetrasulfide, or combinations thereof. In some embodiments, the silica is functionalized with an alkylsilane which is octadecyltrimethoxysilane for long-chain hydrophobic coverage.

[0093] Nanomaterials120903.000059\4900-0177-6754.8 - 19 -

[0094] The nanomaterial as recited above comprises at least one of carbon nanostructures, carbon nanotubes, graphene, nano-silica, explosives, pigments, fullerene compounds, graphite oxide, nanocrystalline cellulose, single-wall carbon nanotubes, multiwall carbon nanotubes, carbon nanofibers, doped carbon nanotubes, carbon sheets, boron nitride, one or more ferrous metals, oxides of one or more ferrous metals, SPIONS, one or more non-ferrous metals, oxides of one or more non-ferrous metals, transition metals, transition metal oxides, silicon carbide-based material, boron nitride, and one or more combinations thereof.

[0095] In some embodiments, the nanomaterial comprises carbon nanotubes. In some embodiments, the carbon nanotubes are single walled carbon nanotubes. In some embodiments, the carbon nanotubes are multiwalled walled carbon nanotubes. In some embodiments, the carbon nanotubes are branched carbon nanotubes. In some embodiments, the nanomaterial comprises graphene. In some embodiments, the nanomaterial comprises nanocellulose.

[0096] In one embodiment, the hierarchical composite as recited above, wherein the hierarchical composite further comprises at least one polymeric or oligomeric shell fully or partially covering the plurality of carrier material particles comprising the nanomaterial. In some embodiments, the shell comprises a polymer. In some embodiments, the polymer is a synthetic polymer comprising urea-formaldehyde (UF), melamine-formaldehyde (MF), polyurea, polyurethane, polyacrylates, polystyrenes (such as styrene methyl methacrylate, or styrene), polylactide (such as poly-L-lactic acid (PLLA) or poly(lactic-co-glycolic acid) (PLGA)), polycaprolactone (PCL), hydrocarbon, polyethylene, polytetrafluoroethylene (PTFE), or combinations thereof. In some embodiments, the polymer comprises polyacrylate polymers, such as polyacrylate, poly(methyl acrylate), poly(ethyl acrylate), and poly(methyl methacrylate). In some embodiments, the polymer is a natural polymer comprising chitosan, alginate, gelatin, starch, and combinations thereof. In some embodiments, the polymer comprises chitosan or chitosan derivatives.

[0097] In some embodiments, the hierarchical composite further comprises at least one polymeric or oligomeric shell fully or partially covering the plurality of carrier material particles comprising the nanomaterial.

[0098] In some embodiments, the hierarchical composite particle of the present disclosure includes one or more nanomaterials. The nanomaterials as contemplated herein120903.000059\4900-0177-6754.8 - 20 -are particles that can be activated or released to improve — increase or decrease — a physical or a chemical property. In one embodiment, for example, the nanomaterials are composed of materials that create higher heating rates or lower thermal capacity than the surrounding or adjacent carrier materials. The higher heating rates of the nanomaterials result in the altering of the hierarchical composites upon application of an external force or a trigger. In other words, the associative force that binds the nanomaterials to the carrier materials is disrupted and catalysts, rheology modifiers, tougheners, other agents, for example, bioagents, corrosion inhibitors can participate in one or more physical changes or chemical reactions of the polymeric matrix. Embodiments of the nanomaterials that can be heated include one or more carbon-based or silicon-carbide-based materials. The nanomaterial may include one or more ferrous or non-ferrous metals, including for example, one or more transition metal oxides, ferrites, and the like, and / or one or more combinations thereof. Transition metals include Ti, V, Cr, Mn, Fe Co, Ni, Cu, and Zn.

[0099] Embodiments of ferrous nano materials include one or more ferrite powders, superparamagnetic iron oxide (SPION) particles, and the like, including one or more combinations thereof. Embodiments of the nanomaterials include one or more of graphene, graphite oxide, fullerenes, single-wall carbon nanotubes, multi-wall carbon nanotubes, carbon nanofibers, filled or doped carbon nanotubes, carbon sheets, bucky paper, nanocrystalline cellulose, nanoclays, and the like, including one or more combinations thereof.

[0100] The nanomaterials can be encased or entrapped within the hierarchical composite material which can be inorganic, for example silica, titania, alumina, zirconia, or can be polymeric, oligomeric, or monomeric or a mixture of the three. For example, the nanomaterials can be physically entrapped or encased within one or more mesoporous or interstitial spaces of the carrier material particles. The nanomaterials can include one or more catalysts, co-catalysts, co-reactants, oxidizers, reaction-inhibiting compounds, chelators, initiators, accelerators, activators including surface activators, modifiers, fuels, explosives, and / or one or more combinations thereof. The nanomaterials can include any chemical, combination of chemicals, organic or inorganic, as understood in the art. In some embodiments, the one or more nanomaterials can include one or more compounds capable of initiating polymerization, for example, anionic, cationic, or free radical polymerizations.

[0101] In some embodiments, the one or more nanomaterials can initiate one or more reactions including redox reactions such as that in anaerobic adhesion. For example,120903.000059\4900-0177-6754.8 - 21 -the nanomaterials can include one or more of a hydroperoxide and one or more transition metals. The one or more nanomaterials can be contained within different carrier material particles within the HCs, within different pores, entrapped within the carrier material, bound to one or more components of the carrier material.

[0102] In one embodiment, the one or more nanomaterials include one or more of a metal accelerator or catalyst such as ferrocene or other metallocenes. The one or more catalysts can be combined with peroxides and / or other compounds for activating or deactivating polymerization. In some embodiments, the catalyst includes one or more of Cu-acetyl acetonate, Cu-2-ethyl hexanoate, ferrocene, dimethyl aminomethyl ferrocene, and / or one or more combinations thereof. In some embodiments, the one or more releasable ingredients include one or more free radical stabilizers such as hydroquinone or p-methoxyphenol.

[0103] In some embodiments, including for example compositions that include anionic cyanoacrylate and / or methylene malonate, the one or more nanomaterials can include one or more inorganic bases or organic bases (e.g., sodium propionate). In yet another example, for cationic polymerization of epoxy resins, one or more ingredients such as diaryliodonium and triarylsulfonium, blocked super acids, cationic catalysts are released. In some embodiments, such as in condensation polymerization, the nanoparticles can include one or more catalysts such as antimony, germanium, titanium, and aluminum compounds.

[0104] Fuels and explosives and the like are another example of where such materials could be used. Specifically, one could utilize individually or in combination a fuel or other explosive material with or without additional materials as described to initiate a chemical reaction releasing in various forms a large amount of energy either individually or in combination with other reactive materials to facilitate an event, for example, from powering a piston in an engine, to an explosive device to an incendiary event to a simple high-speed heating event.

[0105] In one embodiment, the nanomaterial can modify physical characteristics of the bulk reaction mixture, for example increase or decrease its viscosity, or provide color or other optical property to the bulk reaction mixture, especially once it reaches its chemical equilibrium to a product, for example.120903.000059\4900-0177-6754.8 - 22 -

[0106] It should be noted that carbon nanostructures act as nanomaterials. Embodiments of the nanomaterials include one or more of graphene, fullerenes, single-wall carbon nanotubes, multi-wall carbon nanotubes, carbon nanofibers, filled or doped carbon nanotubes, nanoclay, carbon sheets, bucky paper, and the like, including one or more combinations thereof. In one embodiment, the number of carbon nanotubes attached at a given location in a cluster inside the matrix particle is 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0107] In some embodiments, the size of the nanomaterial’s component is one of the numbers below as measured in nm, or within a range defined by any two numbers below including the endpoints of such range, in nm, or an addition of any two numbers, in nm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000, and 1000000.

[0108] The nanomaterials component may include carbon nanotubes, carbon nanostructures, ferrous particles including superparamagnetic iron oxide nanoparticles (SPIONs), and the like. In some embodiments, the nanomaterials component concentrations may vary from 0.005% to as much as 10% with the application itself and its requirements the final arbiter.

[0109] In another embodiment, better pigment dispersion using hierarchical pigment composites allows for achieving optimal pigment dispersion and distribution at the lowest possible loading levels. The hierarchical pigment composites allow for lower pigment usage while still achieving the desired color properties. The pigments entrapped in the composites would allow direct addition to the polymer during compounding. The present embodiment offers the flexibility of an in-line coloring system. Introducing the hierarchical pigment composites directly into the molding or extruder offers flexibility for color changes and the economics of simplifying the introduction of pigments. Keeping the low loadings in the hierarchical pigment delivery system can offset the higher costs when using nano-sized pigments.

[0110] Specifically, and in one embodiment, one incorporates within microporous and mesoporous inorganic particles derived from the oxide of silicon, aluminum, titanium, and other transition and refractory oxides, while coating the said inorganic particles with nanomaterials such as nanotubes or similar structures. Specifically,120903.000059\4900-0177-6754.8 - 23 -by example, carbon nanotubes, graphene, their mixtures, or like structures, wherein, without wishing to be bound by theory, the nanomaterials interact with said microporous and mesoporous inorganic particles through a combination of enthalpic and entropic effects. The first step in assembling these hierarchal composites is the dispersion of said nanomaterials in a medium such as water or solvents, after which, said inorganic particles are mixed with the disentangled or exfoliated nanomaterials, in water or solvents. The enthalpy-driven phenomena such as van der Waals and hydrogen bonding lead to the entrapment of the nanomaterials in the mesopores and micropores of the said inorganic materials to form the hierarchical composites. For example, the strong hydrophobic interaction between the components leads to the separation of the formation of hierarchical composites from water. Nanomaterials are entropically constrained in the mesoporous-micropores. When the hierarchal composites are mixed with sealants, coatings, composites, adhesives, and other polymeric products, the entropic effects dominate the enthalpic impact, leading to the release of the nanomaterial from the hierarchical composites.

[0111] Thermosets, including epoxies, vinyl esters, cyanate esters, and benzoxazines, are known for their excellent chemical and thermal resistance, dimensional stability, high modulus, and good adhesion to various substrates. However, while their high crosslink density benefits specific properties, it renders them highly brittle, making them prone to premature fracture and failure. On the other hand, those thermoplastics below the glass transition temperature (Tg), are brittle and deform by elastic deformation.

[0112] Toughening agents are crucial in enhancing the mechanical properties of both thermosets and thermoplastics, addressing their inherent brittleness, and improving their applicability. Toughening agents include reactive liquid polymers (RLP), core-shell particles, block copolymers, high-temperature thermoplastics, phenoxy resins, and hard particles such as nano-silica, carbon nanotubes, and graphene platelets, high-impact polystyrene (HIPS) and acrylonitrile butadiene styrene (ABS)

[0113] Toughening is typically achieved by introducing a secondary phase into the primary matrix phase. The secondary phase is formed during curing through reaction-induced phase separation or by self-segregation during the melt compounding. The toughening agents mentioned above can improve the fracture toughness of materials, but achieving a balance between enhanced toughness and retained mechanical strength can be120903.000059\4900-0177-6754.8 - 24 -challenging. The interaction between the matrix and the toughening agents must be carefully managed to optimize toughness and mechanical properties.

[0114] The toughening agents can also affect the base material and add complexity to the manufacturing process. Controlling the size and distribution to achieve desired properties can require specialized equipment and processes, potentially increasing the cost and time required for production.

[0115] Due to their unique nanoscale dimensions, nanomaterials, particularly carbon nanotubes (CNTs) and graphene, exhibit exceptional mechanical, electrical, and thermal properties. However, their commercial application has been limited by challenges associated with their dispersion. The robust van der Waals forces among nanoparticles lead to aggregation, making uniform dispersion in solvents or polymer matrices challenging to realize in terms of properties.

[0116] To address these challenges, the nanomaterials are combined with other mesoporous substance, such as silica, alumina, and TiO2, and polymeric particles as referenced in the US 2023 / 0285948A1, Malofsky et al., such are-shell materials, to create composites that leverage the properties of the individual components. By carefully selecting and processing the components, composites that combine the best characteristics of both nanomaterials and host matrices can be created, leading to materials with superior performance for specific applications.

[0117] Silica, for instance, is versatile with a controlled porosity and can be functionalized to alter its hydrophobicity, making it an excellent candidate for forming hierarchical hybrid materials with nanomaterials like CNTs and graphene.

[0118] In some embodiments, a composition comprises the hierarchical composite and an epoxy resin, wherein the nanomaterial comprises carbon nanotubes. In some embodiments, the epoxy resin comprises one or more of: (i) glycidyl ether resins (including diglycidyl ethers of bisphenols and novolacs), (ii) cycloaliphatic epoxy resins, (iii) glycidyl amine resins, (iv) glycidyl ester resins, (v) aliphatic epoxy resins, and any combination thereof. In some embodiments, the epoxy resin comprises diglycidyl ether of bisphenol-A (DGEBA) and / or bisphenol-F (DGEBF). In some embodiments, the epoxy resin comprises cycloaliphatic epoxies comprising3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexane carboxylate. In some embodiments, the120903.000059\4900-0177-6754.8 - 25 -epoxy resin comprises glycidyl amine resins comprising tetraglycidyl methylene dianiline (TGMDA). In some embodiments, the composition with the epoxy resin comprises about 5% to about 15% hierarchical composite, such as about 5% to about 10% hierarchical composite or about 10% to about 15% hierarchical composite.

[0119] In some embodiments, a composition comprises the hierarchical composite and thermoset polymer precursors. In some embodiments, the thermoset polymer precursors are able to form polyester, vinyl ester, polyurethane, polyols, phenolic, or bismaleimide.

[0120] In some embodiments, a composition comprises the hierarchical composite and thermoplastic polymer precursors. In some embodiments, the thermoplastic polymer precursors are able to form polyethylene, polyvinyl chloride, polystyrene, polyethyleneterpthalate, polyacrylate, polymethyl methacrylate, ethylene-vinyl acetate, acrylonitrile butadiene styrene, polycarbonate, polyamide (nylon), polyoxymethylene, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polyether sulfone, polyetherimide, polyether ether ketone, polybenzimidazole, or poly tetrafluoroethy 1 ene.

[0121] In some embodiments, the composition comprises inorganic metal salt, wherein the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, sodium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof. In some embodiments, the inorganic metal salt is silica. In some embodiments, the silica is precipitated or fumed silica or quartz. In some embodiments, the nanomaterial comprises carbon nanotubes.

[0122] In some embodiments, the composition comprises hierarchical composite particles, and at least one polymeric or oligomeric shell fully or partially covers each of the hierarchical composite particles.

[0123] In some embodiments, a cured composition is obtained by curing the hierarchical composite with an epoxy resin, thermoset polymer precursors, or thermoplastic polymer precursors. The cured composition can have improved properties, such as a lap shear strength of about 15% to about 60% greater than that of an otherwise identical cured composition lacking the hierarchical composite. In some embodiments, the cured120903.000059\4900-0177-6754.8 - 26 -composition exhibits a tensile strength about 100% to about 600% greater than that of an otherwise identical cured composition lacking the hierarchical composite.

[0124] Example

[0125] The method of making the hierarchical composite comprise shear mixing the plurality of carrier material particles and the nanomaterial in a dispersion with a solvent and a surfactant, then removing the solvent to form a solid hierarchical composite. In some embodiments, the carrier material particles are in a carrier dispersion and the nanomaterial is in a separate nanomaterial dispersion.

[0126] The dispersion comprises a solvent and a surfactant. An example solvent comprises water. Example surfactants include sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, sodium deoxy cholate, Triton X-100, Pluronic F-127, and Brij S-100, cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA), or combinations thereof. In some embodiments, the PVP comprises K-grade homopolymers selected from K-17, K-30, K-60, or K-90. In some embodiments, the surfactant comprises a vinylpyrrolidone / vinyl acetate copolymer (PVP / VA). In some embodiments, the surfactant further comprises anionic, cationic, or nonionic dispersants selected from sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, cetyltrimethylammonium bromide, or alkylphenol ethoxylates, alone or in combination with PVP.

[0127] Creating these hierarchical materials typically involves dispersing the nanomaterials in a medium and adding silica particles. The interaction between the hydrophobic CNTs / graphene-treated silica surfaces facilitate the formation of a composite material. This interaction is driven by hydrophobic forces, which help in binding the nanomaterials to the silica. Various techniques, such as shear mixing, sonication, and centrifugal mixing, are employed to ensure a good dispersion of the nanomaterials within the silica matrix.

[0128] These methods help maintain the separation of the nanomaterials and enhance the interaction between the different components of the hierarchical. Once formed, these composites can be incorporated into other matrices, such as polymer resins or plastics.

[0129] During mixing or extrusion, the shear forces can separate the hierarchical structure, releasing the embedded nanomaterials into the matrix. This process120903.000059\4900-0177-6754.8 - 27 -allows the unique properties of the nanomaterials, such as improved mechanical strength or electrical conductivity, to be imparted to the final product.

[0130] Toughening agents such as CNTs, core-shell polymers and rubbers, precipitated silica, nano silica, and other metal oxide of aluminum and titanium are shown to effectively enhance the fracture toughness and / or impact properties of thermosets and thermoplastics. However, balancing enhanced toughness / impact properties and retained mechanical strength can be challenging. For instance, the addition of toughening agents has been shown to decrease the tensile strength and elastic modulus of the epoxy.

[0131] The toughening agents mentioned above can improve the fracture toughness of materials, but achieving a balance between enhanced toughness and retained mechanical strength can be challenging. The interaction between the CSR (Core Shell Rubber) particles and the epoxy matrix must be carefully managed to optimize toughness and mechanical properties.

[0132] The addition of the Core-shell particles can also affect the thermal properties of the base material. For example, while some studies have shown that CSR incorporation does not significantly affect the glass transition temperature (Tg) of the epoxy, others have indicated improvements in Tg with the addition of CSR nanoparticles. This variability can complicate the use of CSR in applications where thermal stability is critical.

[0133] Incorporating CSR particles into polymers or resins can add complexity to the manufacturing process. Controlling the size and distribution of the CSR particles to achieve desired properties can require specialized equipment and processes, potentially increasing production costs and time.

[0134] The toughening of polymers using core-shell rubber (CSR) particles rely on phase separation, which creates a secondary phase to enhance impact resistance. However, although this approach increases toughness, it can also negatively affect other material properties and performance. Therefore, ensuring compatibility between the core, shell, and polymer matrix is essential to mitigate such adverse effects.

[0135] These drawbacks highlight the need for careful design and optimization of core-shell toughening agents to maximize their benefits while minimizing adverse effects on the material properties and processing.120903.000059\4900-0177-6754.8 - 28 -

[0136] A particular group of materials, both precipitated and fumed silica, has gained tremendous traction in a variety of applications. Combining silica and nanomaterials would help create hierarchy composites with certain unique properties.

[0137] Silica assists in forming both thermoset and thermoplastic products by enhancing their mechanical strength, dimensional stability, and thermal resistance. In thermoplastics, silica fillers or nanoparticles improve stiffness and reduce shrinkage, which helps maintain precise part geometry during processing. In thermoset systems such as epoxy, polyurethane, or silicone, silica aids in controlling viscosity, promoting uniform curing, and minimizing thermal expansion mismatches. Its reinforcement effect also improves wear resistance and ensures better performance under mechanical and thermal stress.

[0138] Silica is uniquely positioned in the materials for a range of applications. Silica can be modified to impart hydrophobicity by functionalizing the surface range of chemistries currently available to fine-tune the hydrophobic and hydrophilic properties. Silica functions as a delivery mechanism for delivering CNTs or graphene into the matrices, where they are helpful for changing physical and / or chemical properties such as mechanical, electrical, and thermal abrasion.

[0139] The first step in the process is to disperse the nanomaterials into a medium and blend the silica particles in that medium, driving the hydrophobic interactions for the association of CNTs or nanomaterials. The critical step is to disperse the nanomaterials into appropriate media so that they remain separated. Using a range of mixing processes involving shear mixing, sonication, and centrifugal mixing forces the components of the hierarchical composite to intimately associate, leaving behind the media (solvent or water).

[0140] Choosing a hydrophilic media such as water and dispersing CNTs in it and adding hydrophobic silica, and processing under the above-described methods will leave the water behind and help to precipitate and separate the hierarchical hybrid composite. The separated water can be removed from the rest of the hierarchical composite through conventional heating or microwave drying processes.

[0141] Hydrogen bonding among surface silanol (Si-OH) groups plays a role in shaping the microstructure of precipitated silica. The density, surface area, and pore size distribution of precipitated silica are largely dictated by the extent and dynamics of hydrogen120903.000059\4900-0177-6754.8 - 29 -bonding. The precipitated silica is a suitable precursor to the hierarchical composite. Silica has a high surface area and microporosity into which the CNT gets entrapped because of the favorable interactions. Porosity present in the silica helps CNTs to be stuck in between the individual parts (or particles) of the precipitated silica. The carbon nanotubes remain separated on the silica, in between the so-called grapes of the grapevine or grape clusters on the grapevine. The carbon nanotubes in the hybrid are adhered through possible van der Waals forces in between the individual particles of the precipitated silica.

[0142] For example, a carbon nanotube silica hierarchical hybrid composite, when mixed into epoxy resin and sheared, separates the individual parts of the hybrid, and delivers CNTs into the matrix.

[0143] Similarly, the hierarchical composite can be added into plastics and compounded using conventional twin-screw extruders. The sheer forces in the extruder help to break apart individual particles and deliver the CNTS into the plastics.

[0144] The CNTs are loosely or weakly held — much weaker than a chemical bond, for example— in the hierarchical hybrid composite, so they are delivered effectively into the plastics.

[0145] In another embodiment, leveraging the porosity, a PVC — CNT hierarchical composite is made by mixing the PVC powder and CNT water dispersion. Water evaporation results in the entrapment of CNTs in the porous network of the PVC structure. The porosity arises mainly from the agglomeration of precipitated polymer particles during polymerization. The internal structure of PVC particles consists of sub-grains, agglomerates, primary particles, domains, and crystallites. The voids between the particles and connected pores within the particles offer an open architecture to entrain CNTs into PVC. The PVC — CNT hierarchical composite provides an improved process for delivering the CNTs into PVC for superior electrical conductivity, thermal stability, mechanical properties, and glasstransition temperature.EXAMPLESExperimental Procedure

[0146] Hierarchical composites are amenable to a combination of porous TPU, polystyrene, PMMA, PLA, PVA, PEEK, PEI, inorganic metal oxides of transition120903.000059\4900-0177-6754.8 - 30 -metals, and precipitated / fumed silica in combination with nanomaterials such as carbon nanotubes, graphene, and nano-silica.

[0147] In some embodiments, the hierarchical composites can be further encapsulated through different techniques such as spray drying, emulsification, emulsion polymerization, coacervation, layer-by-layer assembly, and interfacial polymerization. The choice of technique depends on the core and coating materials, desired particle properties, the scale of production, and other factors. Many of these methods can be adapted to create micro-or nanoparticles.Toughening Additives

[0148] Toughening can simply be the ability to increase a polymeric system’s ability to absorb energy without failing. While polyurethane systems deliver versatile performance, they still struggle to meet high-tensile, and shear demands in the current market space. Similarly, while epoxy systems deliver great chemical, heat resistance, and high tensile strength, they often are very brittle and fail to meet the ever -increasing demands of the technology. It would be desirable to improve polyurethane and epoxy systems through toughening without increasing viscosity and other key properties. In one embodiment, the particles of the present invention deliver toughening and improved performance through energy dissipation and absorption.

[0149] As it relates to fracture / crack diffraction and bifurcation and force at break or break strength, the additives of the present invention will help withstand expected loads with an adequate safety margin. It will allow for materials with higher break strengths to be selected for applications requiring greater load-bearing capacity. The embodiments, of the present invention will ensure products are designed to operate well below their failure point identifying the maximum load capacity that a product can safely specify.

[0150] As to the property of Young’s modulus (improvement in), it quantifies a material's resistance to elastic deformation. Specifically, materials with higher Young's modulus values are stiffer and deform less under applied loads. The CNTs delivered through the additives of the present invention will provide stronger bonds between the atoms. In addition, the additives would allow for strong interfacial bonding because of nanoscale dimensions of CNTs.120903.000059\4900-0177-6754.8 - 31 -

[0151] The embodiments of the present invention allow for a simultaneous improvement of both the Young's modulus and toughness. The materials of the present invention better resist deformation while also absorbing more energy before fracture.Typically, increasing stiffness tends to reduce toughness and vice versa. Materials with higher stiffness and toughness can better withstand repeated loading and impact forces without failing, leading to longer component lifetimes. The CNTs delivered through the additives and the process of the present invention simultaneously overcome the limitation and expand material design possibilities.Epoxy hierarchical composite - Young ’s Modulus

[0152] Epoxy nanocomposite specimens (designated as NC-T0003) were formulated using precipitated silica (DIO, Evonik) and multi-walled carbon nanotube (MWCNT, LG Chem) aqueous dispersions. The dried NC-T0003 powders were dispersed into EPON 862 epoxy resin using a FlackTek speed mixer at 1000 RPM for 5 minutes to ensure homogeneous distribution. The blended epoxy matrix was then catalyzed with a mixed curing system consisting of an Epoxy-Thiol Adduct (Gabro GPN 890, Huntsman) and PEMP-HS (Kowa Chemical Industries), followed by curing at 55 °C for 2 hours. The loading of NC-T0003 in the epoxy formulation was 10 wt%, corresponding to approximately 0.25 wt% MWCNT content. Tensile specimens were cast in silicone molds and tested according to ASTMD638 to determine Young’s modulus and other tensile properties.Control samples (without nanofiller) and comparison samples containing 10 wt% Paraloid (Competitor) were prepared following the same procedure, excluding the NC-T0003 additive in the control formulation. The output from Tensile testing is reported as Force of Break, Youngs modulus and the area under the stress strain curve is reported as shown in the tables below and in FIGs. 7, 8, and 9.Case Study 1

[0153] A basic 2-component polyurethane (2K PUR) was formulated using polymeric MDI and ppg 1000 diol. Three formulations were made that contained no tougheners, one with 10% of a traditional rubber toughener, and one with 10% of proprietary120903.000059\4900-0177-6754.8 - 32 -toughener of the present invention. One inch diameter discs were cast and tested on a TA Instruments rheometer to determine the tan delta value. A higher tan delta (loss tangent) and a broader tan delta peak near or above the glass transition temperature (Tg) suggest more efficient energy dissipation, often correlated with improved toughness at the molecular level.

[0154] Three formulations were made that contained: 1) no tougheners (control), 2) one with 10% of a traditional rubber toughener (core shell), and 3) one with 10% Nano Catalytic toughener (NCT3). One-inch diameter discs were cast and tested on a TA Instruments rheometer to determine tan delta. They were cured at 65 °C for 120 minutes. A higher tan delta (loss tangent) and a broader tan delta peak near or above the glass transition temperature (Tg) suggest more efficient energy dissipation, often correlated with improved toughness at the molecular level.

[0155] A 10% Nano Catalytic toughener (NCT3) or 0.25% CNTs showed a 25% improvement over the core shell and 48% improvement over the control.Case Study 2

[0156] An off-the-shelf EVA and 10% of Nano Catalytic toughener (NCT3) of the present invention were compounded and pelletized using a commercial twin-screw extruder and pelletizer. Dog bones were molded from the resulting pellets and tested on an Instron under tensile mode. The area under the stress-strain curve was used to measure toughness. In the presence of 10% NCT3, the area under the curve increased by 35%, signifying the increase in toughness. At the same time, the % elongation remained unchanged. See FIG. 10.Case Study 3

[0157] An off-the-shelf TPU and 10% of Nano Catalytic toughener (NCT3) of the invention were compounded and pelletized using a commercial twin-screw extruder and pelletizer. Dog bones were molded from the resulting pellets and tested on an Instron. The area under the stress -strain curve was used to measure toughness. It was found that in the presence of 10% NCT3, the area under the curve increased by 2%, signifying an increase in the toughness. The % elongation, however, increased by many folds, and in fact, the sample simply did not break and even exceeded the test limit. See FIG. 11.120903.000059\4900-0177-6754.8 - 33 -Al: Pigments Delivered Through Precipitated Silica

[0158] 100 ml Naphthol Red (W-3022, pigment red 2) from BASF is mixed with 1000 g of SIPERNAT® D 10— which is a milled, hydrophobic, precipitated silica obtained from Evonik Co.— and agitated using FlackTek, a bladeless high-speed mixer -commonly known as a planetary or dual asymmetric centrifugal mixer at 1000 - 2000 RPM for 5 -10 min. Alternatively, the Henshawel mixer can also be used for intimately mixing the Napthol Red and the silica SIPERNAT® D 10.

[0159] In the case of the FlackTek, the mixing container rotates on two axes simultaneously. A central axis spins the entire container holder, and a secondary axis rotates the container itself in the opposite direction; this dual rotation creates powerful shear forces and fluidization of the Napthol Red to migrate into the interstitial spaces in the silica or SIPERNAT® D 10.

[0160] In the Henshawel mixer, the primary mixing action comes from a centrally mounted impeller that rotates at high speeds, typically ranging from 500 to 3000 rpm. The rapid rotation creates strong centrifugal forces that push materials outward towards the vessel walls. The high-speed rotation generates intense turbulence within the mixing chamber, promoting thorough mixing of materials. As the materials are forced between the impeller and the vessel walls, they experience significant shear forces, which help break down agglomerates and disperse the Napthol Red into the interstitial spaces in between the precipitated silica particles. The combination of centrifugal force and turbulence creates a fluidized bed of material, ensuring all particles are in constant motion and interaction.

[0161] After the Napthol Red is entrapped in the interstitial spaces of silica, water is evaporated using microwave or conventional heating to obtain a dry powder of Napthol Red- Silica carrier.

[0162] The other carriers include mesoporous minerals, metals, metal oxides.A2: Nanoclays Delivered Through Precipitated Silica

[0163] Nanoclay dispersions are created by mixing clay and water in a mechanical homogenization device. This process includes alternating between laminar and turbulent flow conditions to produce a stable dispersion of nanoclay particles in water. The clay particles are reduced to nanometer-sized flakes, which are then stabilized by the surrounding water molecules due to their cationic nature.120903.000059\4900-0177-6754.8 - 34 -

[0164] 100 ml of 1% by weight of nanoclay in water is blended with 100 g of SIPERNAT® D 10— which is a milled, hydrophobic, precipitated silica obtained from Evonik Co.— using a FlackTek or Henshaw blender and subsequently dried using the process conditions described above.

[0165] The other carriers include mesoporous minerals, metals, metal oxides of transition and inner transition elements, carbon, metal-organic frameworks, mesoporous zeolites — porous metal hydroxides of nickel, cobalt, iron, manganese, and mixed metal hydroxides.

[0166] In one embodiment, thermoplastic cores are used, preferably with a soft core. Their temperature sensitivity can be used advantageously for storage, processing, and blending.

[0167] References WO 2022 / 229962 Al and WO 2023 / 199328 Al disclose a composition of a polymeric matrix, surfactant, and a plurality of CNTs homogenously dispersed within the polymeric matrix. The drawback of the soft cores comprising of polymeric matrix makes it difficult to disperse the CNTs. Van der Waals forces between the soft core -CNTs and CNTs- CNTs make it difficult to achieve good dispersion. The lack of driving force for the CNTs to separate from the soft core makes it difficult to achieve good dispersion without aggressive mixing. The need for aggressive mixing results in the breakdown of the polymer and therefore, a loss in machinal performance.

[0168] Precipitated, fumed silica and other mesoporous carriers contain complex structures composed of particles with sizes ranging from 5-100 nm in diameter. Primary particles fuse to form larger aggregates. Aggregates can further combine into larger agglomerates, reaching sizes of 1-40 pm. The particles are porous, with an average pore size greater than 30 nm. This porosity contributes to the high specific surface area. These surface groups allow for further modifications and functionalization. The particles form a three-dimensional network structure through hydrogen bonding and van der Waals forces.

[0169] The advantage of the individual particle agglomerate is that more rigid particles can enhance the toughness of polymer composites through several mechanisms. Hard particles can induce localized plastic deformation in the surrounding matrix, effectively dissipating the energy. Particles can cause cracks to deviate from their original path, increasing the total fracture surface area and energy absorption.120903.000059\4900-0177-6754.8 - 35 -

[0170] Combined with the CNTs, the carrier particles function as obstacles that impede crack propagation, forcing cracks to dissipate out between particles. When stress is applied, particles can detach from the matrix, creating voids that absorb energy and promote plastic deformation.

[0171] The additive composition comprising a carrier can be prepared through, chemical vapor deposition, in which precursor gases are introduced into a reaction chamber. These gases react or decompose on the carrier surface, and the reaction forms a solid in the mesoporous cavities of the carrier particulates. Also, optionally reactive additives, mixtures that are reactive or not can be used as nanomaterials.

[0172] The encapsulated reactive additives in the carrier particles ensure they are activated only under specific conditions such as elevated temperatures, mechanical stress, or exposure to certain environmental factors. Reactive additives are not limited to phosphorus-containing compounds, which chemically bond to polymer chains for improving fire resistance. Nitrogen-containing compounds, often used in combination with phosphorus, these additives can create intumescent char layers when exposed to heat. Organic peroxides like dicumyl peroxide create crosslinks between polymer chains, improving heat resistance and mechanical properties. Silane additives can form covalent bonds between inorganic fillers and polymer matrices, enhancing material strength and durability. Organosilanes, for improving adhesion between organic polymers and inorganic surfaces and enhancing composite material properties. Maleic anhydride-grafted polymers to improve the compatibility between different polymer blends, enhancing overall material properties.

[0173] Hindered amine light stabilizers (HALS) chemically bond to polymer chains, providing long-term protection against UV degradation. Antioxidants, chemically bound to polymer chains, offering improved thermal stability and longevity. Reactive plasticizers for providing flexibility without the risk of migration. Reactive impact modifiers, used to improve impact resistance by chemically bonding to the polymer matrix.

[0174] Compositions contain additives — as concentrates, pellets, liquids, or paste used in composites, adhesives, and coatings. For example, the additives such as plasticizers, antioxidants, and pigments are used in pressure-sensitive adhesives. The pressure-sensitive filler can be a carrier for plasticizers, antioxidants, and dyes.120903.000059\4900-0177-6754.8 - 36 -

[0175] The composition is used, for example, for articles, like parts or a whole product, like an automotive, cosmetic, package, or electronic device, like a phone or a medical device, clinical or not, and so on.

[0176] The composition improves strength, toughness, color and reflectivity, malleability, and hardness.

[0177] The composition of the HC comprises different loadings of CNTs. Higher CNT loadings with lower silica concentrations would allow for delivering improved performance at lower loadings of HC because of the lower relative ratio of silica to CNT. Two compositions of HC, represented as NCT3 (NC-T003) and NCT4, containing 2.5% and 3.5% CNT loadings, respectively.Bl. Preparation o f the HC, NCT3 or Precipitated Silica Carriers Containing Carbon Nanotubes

[0178] The following steps are used to prepare silica carriers containing nanomaterial, CNTs in particular.1. Add 10g Sipernat D10 (sourced from Evonik) to a 100 long FlackTek container; 2. Add 10g 2.5% Multiwalled CNT dispersed in water to the same container;3. Mix in the FlackTek mixing machine for 5min at 2,500 rpm;4. In the fume hood, remove the cap and scrape down the sides of the container. This is a crucial step as it helps keep the CNTs well distributed and gives the sample time to cool down - the sample will pack if it gets too hot while mixing;5. Mix in the FlackTek mixing machine for 5min at 2,500 rpm; and6. If there is still some uncoated D10, scrape down the sides and mix for 1 more minute.B2: Drying the HC, NCT3 from Bl

[0179] The purpose of this step is to remove water from procedure Bl so that the CNTs can attach to the D10 particles and so that the particles can disperse better in certain adhesives and yest the most efficient way to dry NC-T0003 particles.

[0180] Microwave Drying Procedure1. Transfer wet NCT3 powder to 150mm crystalizing dish;120903.000059\4900-0177-6754.8 - 37 -2. Microwave 1 min-on and 1 min-off until 12 minutes at 4V. The reason for turning one minute off is to let the powder cool down as the powder starts to decompose at higher temperature;3. The door of the microwave should be left open when cooling the powder as it also helps the moisture to evaporate;4. The temperature should reach 100-110°C when it is turned on;5. After 12 min on-off run, let powder cool to room temperature; and6. Optional step: Place in 110-120°C oven to remove residual moisture overnight.

[0181] Conventional Drying Procedure1. Place the wet powder in conventional at 110°C for at least 24 hours to remove all the water. It was seen that:- particles microwaved for 12min at -100-110°C show very similar results as particles left in the 110°C oven overnight therefore could be a significantly more efficient way to dry the toughening particles;- microwave drying the toughening particles is significantly faster than oven drying; and- micro wave-dried particles have the better dispersion.B3: Dispersion Analysis

[0182] The purpose of this step is to examine how well the NCT3 particles deliver CNTs into epoxy resin.

[0183] Procedure1. Add 4.5g Epon 862 (an epoxy resin) to a ½ oz cup;2. Add 0.5g of the NCT3 powder to it;3. Mix in the FlackTek mixing machine for 5min at 2,500 rpm;4. From the above step, take about 0.01 g and add to microscope slide; and5. Observe sample at lOx magnification under optical microscope. See FIGs. 12 and 13 which show examples of good and poor dispersions in Epon 862.Cl: Protocol for Makins Tensile and Lap-Shear Test Specimen

[0184] Procedure for making Tensile Test Specimen1. Weigh the Epoxy and the NCT3 particles into appropriate FlackTek container;120903.000059\4900-0177-6754.8 - 38 -2. Seal and mix in FlackTek for 5 min at 2000 RPM;3. Check to make sure all powders are fully incorporated;4. If particles are not fully incorporated scrape sides and repeat step 2 until all powder is fully incorporated;5. Add hardening agent and mix them again at 2000RPM for 5 minutes;6. Place stir bar into the flask;7. Place flask in vacuum chamber on hotplate stir plate and connect to vacuum;8. Turn on stir plate to max mixing;9. Turn on hot plate to approximately 100C;10. Turn on vacuum to begin degassing and drying process;11. Vacuum dry for minimum 2 hours;12. After 2 hours take your flask off the vacuum, hotplate, and stir plate;13. Weigh the catalyst into the mixture;14. Seal container and mix in FlackTek for 5 minutes at 2000 RPM;15. Pour sample into silicone dog bone mold and allow to cure;16. Cure the epoxy sample at required temperature; and17. Test the cured samples using ASTM D638 on an Instron

[0185] Procedure for Making Lap Shear Specimen1. On 1" x 4" clear aluminum coupons, mark a half inch line from the bottom of the coupon;2. Add 0.05g of the sample to the testing area;3. Use the other coupon's testing area to evenly spread the sample across both testing areas;4. Place the two testing areas on top of each other with the adhesive between;5. Use small binder clips to hold the coupons together while it cures; and6. Test on Instron using ASTM DI 002Principle of Encapsulation

[0186] In one embodiment, mesoporous particles are used as a core and loaded with different dispersible materials, including solid nanomaterials, for example, CNTs, graphene, and other similar pigments, minerals, clays, glasses, and metal catalysts. Inorganic mesoporous particles are commercially available and provided by the supplier in a powder form. The mesoporous particles contain unique porosity in their structure, which allows the loading of different ingredients and use as a carrier system. The particles can be120903.000059\4900-0177-6754.8 - 39 -doped with ingredients dissolved in the solution when dispersed following the diffusion mechanism.

[0187] Shell composition is determined by measuring the melting point of the selected resin, polymer, or mixture of both. The particle’s shell melting temperature needs to be adjusted for a specific temperature range to be stable at a certain temperature and release of ingredients at another temperature range. This can be achieved by studying the melting point of the encapsulated particles using differential scanning calorimetry (DSC). Sometimes, the shell composition must be a mixture of two or three polymers or resins, which can be determined using the DSC analysis and the Fox equation.

[0188] After determining the shell composite, the ingredients loaded particles in dry powder or wet form dispersed in the shell composition at 50°C and mixed until it formed homogenized dispersion. In addition, it will help thermal fusion on particle surfaces and increase encapsulation efficiency. Encapsulation can occur in surfactant solutions including PVA or SDS in DI water or PVP in IPO at room temperature. The particle mixture with coating composition needs to be added to the surfactant solution slowly to avoid particle aggregation and phase separation while stirring vigorously. After adding the particles to the solution, the shell will deposit on the carrier particles or the shell chemistry start curing if it includes epoxy resin, or it can be triggered by UV light if there is a light-curing composition.Cl. Cu Catalyst Loaded into Mesoporous Inorganic Particles and Encapsulated with an Epoxy Shell

[0189] Here, mesoporous inorganic particles are used as a core and loaded with different catalysts. Inorganic mesoporous particles are commercially available and provided by the supplier in a powder form. The particle is prepared using the top-down and precipitation method, which requires lower energy and cost to prepare on a large scale than other standard techniques. The silicon dioxide particles contain unique porosity in their structure, allowing different ingredients to be loaded and used as a carrying system. The particles can be doped with ingredients dissolved in the solution when it is dispersed following the diffusion mechanism. However, applying other techniques such as vacuum or sonication can accelerate the air bubble loss and particles further loading with the solution containing ingredients.

[0190] In addition, since the particles are prepared using a top-down approach, some portion of the porosity might be blocked by smaller particles, which can be opened120903.000059\4900-0177-6754.8 - 40 -using initial washing with a proper solvent, such as alcohol, to increase the particles' loading capacity.

[0191] Cleaned particles should slowly be dispersed in the ingredient solution to avoid particle coagulation and particles flying in the air for safety. The ingredient loading percent of the particles can also change with the concentration of it in the solution. However, the exact loading percentage needs to be analyzed at the end. Another factor here is the ingredient miscibility in specific solutions that particles can be dispersed.

[0192] Catalyst-loaded particles precipitated and dried to provide enough physical interaction in the pores and reduce catalyst losses in the silanization step.Silanization changes catalyst-loaded particles from hydrophilic to hydrophobic, which is important in the encapsulation process. The silanation percentage can be changed from 1 to 25% depending on reaction time and silane concentration. However, the particles showed enough hydrophobicity at 10% to be compatible with the shell composition and followed the encapsulation process. This step can be skipped if the porous core particles and catalyst are both hydrophobic and compatible with the shell composition since core particles hydrophilicity triggers its separation during coating.

[0193] After silanization, hydrophobic particles are separated and preserved as dry powder for the encapsulation step. Particles can also be preserved as wet paste in this step to help dispersion in shell composition. However, if the shell composition reacts with the alcohol of the silanization solvent, it probably needs to be dried and used as dry powder.

[0194] Encapsulation of catalyst-loaded and silanated particles is the most important part of this process since it needs to include some critical properties or controlling parameters such as glass transition temperature, melting point, waive susceptor, cross-linking degree, stability at higher temperature, etc.

[0195] The procedure below covers all the steps for making particles from silica and AhCh. Na, loaded with a copper catalyst — copper-2-ethyl hexanoate (Cu2EH) — is divided into three main steps.

[0196] Step 1: A12O3, Na loading with Cu2EH

[0197] Before everything, we wash the particles to increase the catalyst loading capacity and modify them with silane. For this, add 100 g of powder AhCh. Na containing 300 ml ethanol in a big bottle. The mixture should be stirred for at least 8 h,120903.000059\4900-0177-6754.8 - 41 -followed by 10 minutes of sonication (40%) and another 15 min of mixing to finish the washing. After washing, separate particles using a centrifuge and dry them in an oven.

[0198] Measure the desired amount of AhCh. Na (or SiCh), disperse it in Q12EH solution in ethanol (2.5% by weight), and stir it for 12 h. Then, sonicate the particle dispersion for 10 for 20 minutes to remove all air bubbles from porous particles and increase the loading of Q12EH 1 (this can also be done using stirring under a vacuum chamber for 2-3h). After sonication, leave it stirring for another 2h. At the end, stop stirring and let particles precipitate in the bottle. After precipitation, collect the supernatant solution for use next time and take the wet particles for the next step.

[0199] Notes:• Sonication or vacuum helps Q12EH loading significantly.• Larger particle aggregate should be removed from SiCE / AhCE. Na powder received from supplier before adding it to the Q12EH solution.

[0200] Step 2: AhCh. Na / Q^EH (or SiC>2 / Cu2EH) Modification with Silane

[0201] After copper loading, add 20% weight silane solution in 150 ml ethanol to the 100g particles container while stirring. In a separate vial, prepare 10 ml DI and adjust pH at 8-9 using NH4OH, then add it to the system. At the end, add 150 ml more ethanol, raise the temperature to 60C, and leave it stirring for at least 8h to the silanation is complete. In the end, let the particles precipitate to remove the supernatant and collect it in plastic bottles for the next step.

[0202] Step #3: AhCh. Na / Q^EH-Silane (or SiO2 / Cu2EH-Silane) coating with Epoxy resins

[0203] Measure 100g of a modified particle with silane. Add 60g resin solution (1007F, O.lg / ml THF)

[0204] In a big container, prepare 600 ml %1 PVA solution. Slowly add particles / resin / mixture using the pump at room temperature while stirring. After adding all the mixture, leave the system stirring for at least 6h to complete the particle coating and THF acetone. Ultimately, the product is collected in bottles and transferred for filtration.120903.000059\4900-0177-6754.8 - 42 -C2. Mesoporous Inorganic particles and CNTs Encapsulated with an Epoxy and PMMA Core

[0205] Step 1: AhCh. Na / Q^EH (or SiCh / Cu EH) modification with Silane

[0206] Add 20 wt.% silane solution in 150 ml ethanol to the 100g AhO3. Na / Cu2EH (or SiO2) particles container while stirring. In a separate vial, prepare 10 ml DI and adjust pH at 8-9 using NH4OH, then add it to the system. At the end, add 150 ml more ethanol, raise the temperature to 60C, and leave it stirring for at least 8 h to the silanation to complete. Finally, let the particles precipitate to remove the supernatant and collect it in plastic bottles for the next step.

[0207] Step 2: AhOs. Na / Q^EH-Silane coating with Epoxy and PMMA

[0208] Measure 100g of a modified particle with silane. Add 60g resin solution (1007F, O.lg / ml THF) and 20g PMMA (O.lg / ml) while stirring at 60C. Finally, 20 gm of 2.5 wt. %CNT water dispersion is added slowly to the THF containing silanated particles. Add additional THF (300 ml) and leave it starting for at least 4 hours.

[0209] In a big container, prepare 600 ml %1 PVA solution. Slowly add particles / resin / PMMA / CNT mixture using the pump at room temperature while stirring. After adding all the mixture, leave the system stirring for at least 6 h to complete the particle coating and THF acetone. Finally, the product is collected in bottles and transferred for filtration to obtain the solid particles as residue.C3. Addition of Particles to Polymeric, Oligomeric or Monomeric Systems

[0210] In this experiment, particles prepared above, core-shell or nanomaterials loaded into carrier particles, are added to polymeric systems, thermoplastics, or thermosets. The particles can also be added to oligomeric systems or monomeric systems.Lap Shear Testing procedure (ASTM D1002)

[0211] Lap shear sample surface preparation and conditioning:

[0212] The adhesive testing length should be 12.5mm from the bottom of the coupon and the grip length should be 25.4mm drawn from the other side of the coupon.

[0213] First step of this process is taking 1 x 4 inch Aluminium Coupon and draw lines differentiate the testing area and grip area.120903.000059\4900-0177-6754.8 - 43 -

[0214] Wipe the area with acetone followed by isopropyl Alcohol to remove grease

[0215] Take 60 grit sand paper and roughen the surface (rubbing 10 times )

[0216] Spray compressed air on it for half second just to remove and small particulates present on top of the area

[0217] Add Chemical Etching solution on the surface of roughened area using pipette and spread evenly. 100ml of the etch solution is made by adding 24.51 grams of Sulfuric Acid (96%) and 6.6 grams of Sodium Dichromate to 68.83 grams of DI water. After 20 minutes, the effected area is washed with tap water and then with DI water. Now the washed coupons are placed at 70 C for 30 minutes to remove all the water

[0218] Lapshear specimen preparation

[0219] 0.05 grams of the adhesive is then applied to the 12.5mm area and another coupon attached on top of it and spread evenly. Small paper clips are attached on both ends and excessive adhesive is wiped. The samples are cured at 110c for 2 hours.

[0220] Both aluminum and steel substrates were used for testing lapshearEpoxy adhesive Formulations with NCT3 at 1 and 5 t % NCT3120903.000059\4900-0177-6754.8 - 44 -37.89Lapshear Performance improvements in epoxy adhesive at 1 and 5 t % NCT3:Epoxy adhesive Formulations with NCT4 at 5 and 5.62 wt%Lapshear Performance improvements in epoxy adhesive at 1 and 5 t % NCT4

[0221] Lap shear improvements in commercial adhesive120903.000059\4900-0177-6754.8 - 45 -

[0222] NCT3 was tested in a two-part commercial adhesive (Loctite 219298, Henkel)

[0223] Experimental procedure: 1 % NCT3 was blended into the two-part adhesive, and lap shear was tested.Lapshear Performance improvements in Loctite 219298 epoxy adhesive at 10 wt % NCT4120903.000059\4900-0177-6754.8 - 46 -

Claims

CLAIMS1. A hierarchical composite, comprising:(i) a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles; and(ii) a nanomaterial;wherein the nanomaterial is:(1) bound within the interstitial spaces among the plurality of carrier material particles, or(2) bound to the surface of the plurality of carrier material particles, wherein such binding occurs through non-covalent interactions or associative forces, wherein the nanomaterial has at least one dimension in the nanoscale of from about 0.9 nm to about 1,000 nm and the carrier material particles have a particle size in the microscale of from about 1 to about 1,200 pm,wherein the hierarchical composite are particles with a particle size ranging from about 1 microns to about 2,000 microns.

2. The hierarchical composite of claim 1, wherein the nanomaterial has at least one dimension from about 1 to about 100 nm and carrier material particles have a particle size from about 1 to about 100 pm.

3. The hierarchical composite of claim 1, wherein the nanomaterial comprises from about 0.05 wt.% to about 20 wt.% of the hierarchical composite.

4. The hierarchical composite of claim 1, wherein the nanomaterial comprises about 0.05 wt.% to about 2 wt.% of the hierarchical composite.

5. The hierarchical composite of claim 1, wherein the nanomaterial comprises about 2 wt.% to about 20 wt.% of the hierarchical composite.

6. The hierarchical composite of claim 1, wherein the carrier material particles are porous.

7. The hierarchical composite of claim 1, wherein the carrier material particles are non- porous.120903.000059\4900-0177-6754.8 - 47 -8. The hierarchical composite of any one of the previous claims, wherein the carrier material comprises at least one of an inorganic metal salt, activated carbon, porous carbon, polymer, and an oligomer.

9. The hierarchical composite of claim 8, wherein the carrier material comprises an inorganic metal salt, wherein the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, sodium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof.

10. The hierarchical composite of claim 9, wherein the inorganic metal salt is silica.

11. The hierarchical composite of claim 10, wherein the silica has an agglomerated d50 particle size of from about 3 to about 200 microns and a primary particle size of from about 5 to about 100 nm.

12. The hierarchical composite of claim 11, wherein the silica has an agglomerated d50 particle size of from about 5 to about 10 microns, about 3 to about 20 microns, or about 10 to about 100 microns.

13. The hierarchical composite of claim 10, wherein the silica is precipitated or fumed silica or quartz.

14. The hierarchical composite of claim 10, wherein the silica is silane-functionalized precipitated silica.

15. The hierarchical composite of claim 10, wherein the silica is silane-functionalized with alkylsilane, fluoroalkylsilanes, methyltrimethoxysilane (MTMS), hexamethyldisilazane, phenyltrimethoxysilane, phenyltriethoxysilane, vinylphenyltrimethoxysilane, bis[3-(triethoxysilyl)propyl]tetrasulfide, or combinations thereof.120903.000059\4900-0177-6754.8 - 48 -16. The hierarchical composite of any one of the previous claims, wherein the nanomaterial comprises carbon nanostructures, carbon nanotubes, graphene, nanosilica, explosives, pigments, fullerene compounds, graphite oxide, nanocrystalline cellulose, single-wall carbon nanotubes, multi-wall carbon nanotubes, carbon nanofibers, doped carbon nanotubes, carbon sheets, one or more ferrous metals, oxides of one or more ferrous metals, SPIONS, one or more non-ferrous metals, oxides of one or more non-ferrous metals, transition metals, transition metal oxides, silicon carbide-based material, boron nitride, or combinations thereof.

17. The hierarchical composite of any one of the previous claims, wherein the nanomaterial comprises carbon nanotubes.

18. The hierarchical composite of claim 17, wherein carbon nanotubes are single walled carbon nanotube.

19. The hierarchical composite of claim 17, wherein carbon nanotubes are multiwalled carbon nanotubes.

20. The hierarchical composite of claim 17, wherein carbon nanotubes are branched carbon nanotubes.

21. The hierarchical composite of any one of the previous claims, wherein the nanomaterial comprises graphene.

22. The hierarchical composite of any one of the previous claims, wherein the nanomaterial comprises nanocellulose.

23. The hierarchical composite of any one of the previous claims, wherein the hierarchical composite comprises particles, and at least one polymeric or oligomeric shell fully or partially covers each of the hierarchical composite particles.

24. The hierarchical composite of claim 23, wherein the shell comprises a polymer.120903.000059\4900-0177-6754.8 - 49 -25. The hierarchical composite of claim 24, wherein the polymer is a synthetic polymer comprising urea-formaldehyde (UF), melamine-formaldehyde (MF), polyurea, polyurethane, polyacrylates, polystyrenes, polylactide, polycaprolactone (PCL), hydrocarbon, polyethylene, polytetrafluoroethylene (PTFE), or combinations thereof.

26. The hierarchical composite of claim 24, wherein the polymer is a natural polymer comprising chitosan, alginate, gelatin, starch, and combinations thereof.

27. A composition comprising the hierarchical composite of claim 1 and an epoxy resin, wherein the nanomaterial comprises carbon nanotubes.

28. The composition of claim 27, wherein the epoxy resin comprises one or more of: (i) glycidyl ether resins (including diglycidyl ethers of bisphenols and novolacs), (ii) cycloaliphatic epoxy resins, (iii) glycidyl amine resins, (iv) glycidyl ester resins, (v) aliphatic epoxy resins, and any combination thereof.

29. The composition of claim 28, wherein the epoxy resin comprises diglycidyl ether of bisphenol-A (DGEBA) and / or bisphenol-F (DGEBF).

30. The composition of claim 28, wherein the epoxy resin comprises cycloaliphatic epoxies comprising 3, 4-epoxycyclohexylmethyl-3’,4’-epoxy cyclohexane carboxylate.

31. The composition of claim 28, wherein the epoxy resin comprises glycidyl amine resins comprising tetraglycidyl methylene dianiline (TGMDA)32. The composition of claim 27, wherein the composition comprises about 5% to about 15% hierarchical composite.

33. A composition comprising the hierarchical composite of claim 1 and thermoset polymer precursors.

34. The composition of claim 33, wherein the thermoset polymer precursors are able to form polyester, vinyl ester, polyurethane, polyols, phenolic, or bismaleimide.120903.000059\4900-0177-6754.8 - 50 -35. A composition comprising the hierarchical composite of claim 1 and thermoplastic polymer precursors.

36. The composition of claim 33, wherein the thermoplastic polymer precursors are able to form polyethylene, polyvinyl chloride, polystyrene, polyethyleneterpthalate, polyacrylate, polymethyl methacrylate, ethylene-vinyl acetate, acrylonitrile butadiene styrene, polycarbonate, polyamide (nylon), polyoxymethylene, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polyether sulfone, polyetherimide, polyether ether ketone, polybenzimidazole, or polytetrafluoroethylene.

37. The composition of any one of claims 27 to 36, wherein the carrier material comprises an inorganic metal salt, wherein the inorganic metal salt comprises silicon, aluminum, titanium, zirconium, sodium, vanadium, chromium, manganese, iron, copper, nickel, zinc, gallium, yttrium, lanthanum, cerium, neodymium, tin, hafnium, thallium, indium, or combinations thereof.

38. The hierarchical composite of claim 37, wherein the inorganic metal salt is silica.

39. The hierarchical composite of claim 38, wherein the silica is precipitated or fumed silica or quartz.

40. The composition of any one of claims 27 to 39, wherein the nanomaterial comprises carbon nanotubes.

41. The composition of any one of claims 27 to 40, wherein the hierarchical composite comprises particles, and at least one polymeric or oligomeric shell fully or partially covers each of the hierarchical composite particles.

42. A cured composition obtained by curing the composition of any one of claims 27-41.

43. The cured composition of claim 42, wherein the cured composition exhibits a lap shear strength of about 15% to about 60% greater than that of an otherwise identical cured composition lacking the hierarchical composite.120903.000059\4900-0177-6754.8 - 51 -44. The cured composition of claim 42, wherein the cured composition exhibits a tensile strength about 100% to about 600% greater than that of an otherwise identical cured composition lacking the hierarchical composite.

45. A method of making the hierarchical composite of claim 1 comprising:shear mixing the plurality of carrier material particles and the nanomaterial in a dispersion with a solvent and a surfactant,removing the solvent to form a solid hierarchical composite.

46. The method of claim 45, wherein the plurality of carrier material particles are in a carrier dispersion and the nanomaterial is in a separate nanomaterial dispersion.

47. The method of claim 45, wherein the solvent comprises water.

48. The method of claim 46, wherein the nanomaterial dispersion comprises the nanomaterial and a surfactant, wherein the surfactant comprises sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, sodium deoxycholate, Triton X-100, Pluronic F-127, and Brij S-100, cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA), or combinations thereof.

49. The method of claim 48, wherein PVP comprises K-grade homopolymers selected from K-17, K-30, K-60, or K-90.

50. The method of claim 48, wherein the surfactant comprises a vinylpyrrolidone / vinyl acetate copolymer (PVP / VA).

51. The method of claim 48, wherein the surfactant further comprises anionic, cationic, or nonionic dispersants selected from sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium cholate, cetyltrimethylammonium bromide, or alkylphenol ethoxylates, alone or in combination with PVP.120903.000059\4900-0177-6754.8 - 52 -52. A hierarchical composite, comprising:(i) a plurality of carrier material particles comprising interstitial spaces in between the carrier material particles; and(ii) a nanomaterial.

53. The hierarchical composite of claim 52, wherein the nanomaterial is bound within the interstitial spaces among the plurality of carrier material particles54. The hierarchical composite of claim 52, wherein the nanomaterial is bound to the surface of the plurality of carrier material particles, wherein such binding occurs through non-covalent interactions or associative forces.

55. The hierarchical composite of claim 52, wherein the nanomaterial is:(1) bound within the interstitial spaces among the plurality of carrier material particles, or(2) bound to the surface of the plurality of carrier material particles, wherein such binding occurs through non-covalent interactions or associative forces.

56. The hierarchical composite of any one of claims 52 to 55, wherein the nanomaterial has at least one dimension in the nanoscale of from about 0.9 nm to about 1,000 nm.

57. The hierarchical composite of any one of claims 52 to 56, wherein the carrier material particles have a particle size in the microscale of from about 1 to about 1,200 pm.

58. The hierarchical composite of any one of claims 52 to 57, wherein the hierarchical composite are particles with a particle size ranging from about 1 microns to about 2,000 microns.120903.000059\4900-0177-6754.8 - 53 -

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