Multifunctional nanocomposites reinforced with impregnated cellular carbon nanostructures

Abstract

To provide a polymer-based nanocomposite having improved mechanical properties and electrical conductivity due to effects of a novel cellular carbon phase.SOLUTION: The present disclosure is directed to multiphase dispersions and nanocomposites comprising a continuous matrix or binder and endohedrally impregnated cellular carbon filler. These nanocomposites may exhibit superior mechanical, electrical, thermal, or other properties, and may be used in a variety of products, including hierarchical fiber-reinforced composites with nanocomposite matrices.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Provisional Patent Application No. 62 / 448,129, filed January 19, 2017. This provisional application claims priority to US Provisional Application No. 2004 / 0109994, filed on May 1, 2004, which is hereby incorporated by reference in its entirety for all purposes. and is hereby incorporated by reference for all purposes.

[0002] The present disclosure provides a method for producing a cellular carbon nanotube that is endogenously impregnated in a liquid or solid matrix. A new class of liquid dispersions and solid nanocomposites composed of elementary nanostructures . [Background technology]

[0003] In recent years, sp. 2 -Hybrid carbon-filled polymer-based nanocomposites have been widely studied. sp 2 Carbon can be classified based on its dimensionality and geometry: so-called zero-dimensional carbon Nanostructures include buckminsterfullerene and carbon quantum dots. One-dimensional carbon nanostructures include carbon nanotubes and nanofibers. All of these may have in common a linear nanostructured morphology. Two-dimensional carbon includes single-layer graphene and multi-layer graphitic nanoplatelets. These are often obtained by liquid-phase exfoliation methods such as the Hummers method from bulk graphite precursors. Bulk graphite-like structures, such as carbon fibers or carbon powders, are made using s p 2 They form a three-dimensional family of carbon atoms.

[0004] Low-dimensional carbon, such as nanotubes and graphene nanoplatelets, offers excellent opportunities It has mechanical, thermal and electrical properties, but its low dimensionality makes it suitable for composite applications. It also becomes difficult to use in a liquid matrix ("matrix" as used herein refers to a carbon matrix). When blended into a continuous phase (defined as a liquid or solid phase surrounding the nanoparticles), The van der Waals interactions between carbon nanoparticles cause them to adhere to each other. The carbon clusters or "agglomerates" are then broken down into irregular clusters. Low-dimensional carbon reverts to a three-dimensional conformation with minimal surface energy when blended into tetrax. This effect can cause phase separation between the matrix and filler, resulting in the formation of composites. To address this phase separation, researchers have developed a method to create "space" between graphene particles. The spacer particles were introduced [1-3]. The spacer particles do not suppress the agglomeration itself, but , hiding the density of the agglomerates and the surface area of ​​the carbon by not allowing efficient interparticle adhesion Without the spacer, the nanoplatelets would be confined to their various sizes, as shown in Figure 1A. Figure 1A shows a cross-sectional view of a nanoplatelet and the spatial distribution of the nanoplatelets. How do both sides of the nanoplatelets interact to form dense, low-surface-area clusters? This indicates whether the nanoplatelets are accessible for attachment to other nanoplatelets.

[0005] Porous carbon nanostructures are promising alternatives that possess both two-dimensional and three-dimensional properties. Examples of such materials in the literature include ordered mesoporous carbon (OMC). C) and "3D graphene." In the case of OMC particles, the researchers Highly ordered nanoarchitectures obtainable by route-directed synthesis One of the features of OMC is its inclusive pore structure ("inclusive"). "Template-based" as used herein refers to the internal cavities or structures within the carbon created by the template. refers to the internal surface, while "exohedral" refers to the outer surface of the carbon structure. The combination of a high specific surface area (i.e., a surface area) and nanostructured walls allows for a high specific surface area. Surface area is maintained as long as the inclusion surface is not obscured by the collapse of the inclusion pores. The spacing provided by the pores is what allows nanotubes and nanoplatelets to separate in the liquid. Unfortunately, voids are larger than 10 nm in many OMC variants. The pore-to-wall diameter ratio is smaller than that of the carbon nanotubes. Compared to the conventional method, OMC is spatially dense and difficult to penetrate and wet. Current research into the application of OMCs has mostly focused on adsorption and energy storage. are.

[0006] Some 3D nanocarbons contain large inclusion cavities, which theoretically can be used to create outstanding nanocomposite structures. , aerographite, an interconnected tubular carbon network with nanostructured walls. As reported by Garlof et al., Veit writes, "Improved electrical conductivity and mechanical reinforcement of polymer-based nanocomposites." By incorporating 3D nanocarbons into polymer matrices, Therefore, in contrast to the use of dispersed carbon nanoparticles, agglomeration and controlled network topology are required. Some drawbacks, such as the lack of Specifically, liquid epoxy resin is encapsulated in Garlof by vacuum impregnation. Aerographite as a monolithic preform that can be locally and externally injected The interconnectedness of the mesh, according to Mecklenburg, is self-supporting. and in conductive polymer-based nanocomposites, as a highly extended and permeable framework. This is the "common structural motivation of the aerographite family" due to its ability to perform the functions of [6]

[0007] Similar to OMC, the non-disintegrating aerographite specimens provide spacing between nanostructured features. However, interconnected continuous carbon structures can have drawbacks. Low viscosity thermosetting resins and vacuum for efficient infusion and wetting of continuous interconnected carbon monoliths An infusion process may be required to fabricate nanocomposites, especially thick nanocomposites. Furthermore, the flow dispersion can be used in conjunction with fiber reinforcement. It can be integrated and fabricated using conventional tooling and manufacturing processes, but Continuously interconnected carbon is ideal for fabricating thick molded components or thinly applied adhesives and coatings. It is unlikely that this technology will be put to practical use anytime soon. Many nanocomposite applications require the use of discontinuous carbon nanoparticles. A flowable liquid dispersion is preferred.

[0008] The present invention provides, among other things, the practical advantages of a discontinuous filler phase having a cellular morphology. Multiphase materials composed of a continuous phase filled with glass-like porous 3D carbon nanostructures Such a cell structure has a larger inclusive cavity than most CMK-type OMCs. Its template-directed cavity and wall morphology allows for highly consistent It may be possible to create cell particles with a uniform size and shape distribution. The cracks in the pores may allow the infiltration of the polymer matrix material, which may allow other similar sub-pores to penetrate. The units are endohedrally impregnated and can self-assemble through van der Waals interactions. The cell-type subunits then enter a spatially extended multicellular multiphase network, resulting in morphological phase mixing. This can be brought about.

[0009] For illustrative purposes, Figure 1B shows a two-dimensional view of a hypothetical spherical cell. The cell is made up of discrete particles. Figure 1C shows the void created by the self-assembled clusters of such virtual cell particles. This is a two-dimensional view of the intermittently spread mesh. The filler is discontinuous, so this type of carbon (collectively referred to herein as "cellular carbon" or "cellular carbon structures" and individually as "cellular carbon" or "cellular carbon structures") Nanocomposites filled with "cells" or "cell structures" are made by using liquid resin. This can facilitate fabrication of components where a flowable precursor is required. Compared to other carbons, cellular carbon and its derivatives have larger, less elongated carbons. Cavities, nanostructured walls, template-directed geometries and topographies, and discontinuities A subsequent form factor can be obtained. Summary of the Invention [Problem to be solved by the invention]

[0010] As used herein, a matrix continuous phase and an inclusionarily impregnated cellular carbon nanostructure A novel class of multiphase dispersions and nanocomposites composed of multiple discontinuous phases is described. The matrix may be one or more thermosetting or thermoplastic polymers, prepolymers, or resins. The cellular carbon may be composed of a matrix, a monomer, a solvent, or a mixture thereof. The particles may be dispersed throughout the matrix as individual particles or clusters of particles, and may be covalently or The cellular carbon may be chemically functionalized by a liquid or non-covalent bond. The solid filler may be inclusively impregnated, and the inclusive voids are substantially absent. In addition to the cellular carbon, other fillers or reinforcements, such as fiber reinforcements, may be added to the matrix. Polymer-based nanocomposite embodiments may be co-dispersed in various curing agents. Indicates the condition, e.g., uncured, partially cured, or "B-stage" cured and fully cured. The matrix may be a solid, liquid or gel at room temperature, enhancing the utility of the present invention. It is not restrictive.

[0011] One of the objectives of the present invention is to develop a novel cellular carbon phase that provides improved mechanical and electrical properties. Another object of the present invention is to prepare polymer-based nanocomposites with electrical properties. , inks, coatings, paints, sealants, adhesives, molded plastics in a wide variety of formulations Nanocomposites that can be used in polymers, foams, fiber-reinforced composites, and other polymer applications. The purpose is to create it. [Means for solving the problem]

[0012] The nanocomposites described herein offer advantages over the prior art. can withstand the formation of spatially dense aggregates in liquids, a problem associated with low-dimensional carbons. This has an inclusive surface available for wetting by the matrix liquid. However, it is geometrically impossible for the particles to adhere to adjacent particles. Derivative particles, such as curved shreds, also have non-planar convex or concave shapes that reduce the efficiency of interparticle adhesion. Other porous nanostructured carbon networks, such as aerographs, can have a surface of a shape similar to that of a carbon nanotube. Unlike nanocomposites made using phytoliths, dispersed cellular carbon is filled Nanocomposites are easier to fabricate into various components since preforms may not be required. It can be easy.

[0013] Further advantages and applications will be readily apparent to those skilled in the art from the following detailed description. The examples and descriptions herein should be considered illustrative in nature and not limiting. .

[0014] Exemplary embodiments will be described with reference to the accompanying drawings. [Brief explanation of the drawings]

[0015] [Figure 1A] FIG. 1A is a two-dimensional cross-sectional view of a nanoplatelet with two available faces that can interact and attach with other particles, resulting in spatially dense clustering or stacking and surface hiding. [Figure 1B] FIG. 1B is a two-dimensional cross-section of a hypothetical spherical cell particle. [Figure 1C] Figure 1C is a two-dimensional view of the spatially extended network formed by self-assembled clusters of spherical cells. This spatial extension is a result of unavailable internal cavities and surfaces. [Figure 2]Figure 2 shows how cell walls can be constructed with carbon lattices (shown as solid lines) of different orientations relative to the orientation of the wall (shown as dotted lines with arrows). The first diagram shows a wall configuration where the carbon lattice is oriented more or less in the same plane as the wall orientation. The second diagram shows a wall configuration where the carbon lattice has a complex orientation. Both diagrams show how the interlayer spacing can vary. The third diagram shows how the wall thickness at different points can be measured by drawing a chord that is more or less perpendicular to the cell wall at the measurement point. [Figure 3] Figure 3 shows an SEM micrograph of a fibrous nanostructured cellular carbon structure composed of many small cells. Although the fibrous microstructure is larger than 100 nm in all dimensions, all of the bulk phases are smaller than 100 nm, so all of the features are still nanostructured in composition. [Figure 4] Figure 4 shows two hypothetical cellular carbon structures in two dimensions. The thin cell walls are shown as double black lines. The exterior of the cell is shown as a light gray region. The encapsulated cavity is shown as a white region. The scale bar at the bottom left indicates a length of 10 nm for reference. In the top structure, a 10 nm diameter circle can be drawn completely within the cavity, as indicated by the dotted reference circle. In the bottom structure, the 10 nm diameter circle cannot be drawn completely within the cavity, but two perpendicular chords, each greater than 10 nm in length, can be drawn within the cavity, as indicated by the two orthogonal segments 10 nm long. [Figure 5] Figure 5 is an illustration of a hypothetical cellular structure containing multiple cavities. The thick cell walls are shown as dark gray areas. The exterior of the cell is shown as light gray areas. The cavities inside the cell are shown as white areas. The scale bar at the bottom left indicates a length of 10 nm for reference. Most of the cavities in this hypothetical structure are larger than 10 nm, as indicated by the two dotted reference circles, both of which are 10 nm diameter. However, one cavity is smaller than 10 nm in all directions, as shown in the enlarged inset, and is completely contained within the 10 nm diameter reference circle. [Figure 6]Figure 6 is an illustration of a hypothetical lobular cell-type structure containing one extrinsic pore. The thin cell wall is indicated by a double black line. The exterior of the cell is the light gray region. The intrinsic cavity is the white region. The scale bar at the bottom left indicates a length of 10 nm for reference. As shown in this illustration, the presence of the extrinsic pore increases the complexity of the cavity morphology by creating local cavity features. In this illustration, the local cavity diameter is generally larger than 10 nm. [Figure 7] Figure 7 is an illustration of a hypothetical cellular structure similar to that of Figure 6 but containing five extrinsic pores. Thin cell walls are indicated by double black lines. The exterior of the cell is the light gray region. The intrinsic cavity is the white region. The scale bar at the bottom left indicates a length of 10 nm for reference. The structure in this illustration is also somewhat lobular, but is more dendritic due to the high spatial pore density. In this illustration, local cavity diameters are predominantly larger than 10 nm, but there are also regions where the local cavity diameter is smaller than 10 nm, as indicated by the 10 nm reference line drawn across the cavities within that region. [Figure 8] Figure 8 is an illustration of a hypothetical porous structure similar to those in Figures 6 and 7 but containing a much higher spatial density of extrinsic pores. Thin cell walls are shown with double black lines. The exterior of the cells are the light gray regions. The intrinsic cavities are the white regions. The scale bar at the bottom left indicates a length of 10 nm for reference. The high spatial density of extrinsic pores creates a dendritic structure. In this illustration, the local cavity diameter is predominantly smaller than 10 nm, as indicated by the 10 nm reference line; therefore, this structure does not meet the second criterion. [Figure 9]Figure 9 illustrates four examples of particle structures. Cell walls are indicated by double black lines or dark gray areas. The exterior of the cell is indicated by light gray areas. Containing cavities are indicated by white areas. From left to right, the first structure is an elongated, linear cavity structure with an aspect ratio greater than 5:1 and less than 10:1, where the aspect ratio is defined as the cavity's length relative to its largest diameter. The second structure is a highly elongated cavity structure (i.e., aspect ratio greater than 10:1) that is nonlinear due to branching. The third structure contains multiple discontinuous cavities, each with an aspect ratio less than 5:1. The fourth structure on the right contains a single, linear, highly elongated cavity, typical of nanotubes. [Figure 10] Figure 10 is an illustration of a ternary template-shell-matrix system. The template phase is the central gray region, the shell is the black region, and the matrix is ​​the patterned outer region. This illustration reflects a system in which cellular carbon forms deterministically. Cell walls form conformally around a well-defined template phase, with the shell separating the endophytic template from the extrinsic matrix. [Figure 11] Figure 11 shows an SEM micrograph of a cellular carbon structure grown in a double-cylinder hollow-like cylinder template. The pores within the template are carried over into the cellular carbon structure, resulting in a double-cylinder morphology flanked by two extrinsic pores. The extrinsic pores are extrinsic to the templated cell cavity and are therefore not considered part of the cellular cavity. The cell cavity spatially corresponds to the intrinsic template phase during formation, while the extrinsic pores correspond to the space occupied by the matrix phase during formation. [Figure 12] Figure 12 is an SEM micrograph of a cellular carbon structure composed of discrete cells interconnected into a sheet-like microstructure. Numerous extrinsic pores can be observed between adjacent cells, as can be seen in the white circles. [Figure 13]Figure 13 shows an SEM micrograph of the transformed cells. The as-synthesized cells were spheroidal in morphology, but post-synthesis mechanical stresses imposed by the template extraction process caused the particles to fracture into curved shreds. The concave curvature of the shreds reflects the formation of particles on a convex template. Although the shreds adhere to each other, the image also shows that the large interparticle spaces imposed by the inherited curvature of the particles are retained. [Figure 14] Figure 14 shows an SEM micrograph of a cellular particle containing in-plane lattice defects, allowing the lattice to conform to the surface of the template as it forms around it. Therefore, the cell walls in this micrograph appear smooth and seamlessly curved, showing no evidence of wrinkles or folds. The defective nature of the cell walls, and possibly the sp3 bonds interconnecting the sp2 lattice, may make them mechanically stronger, as can be inferred from the intact cellular structure and the absence of shreds after template extraction. [Figure 15] Figure 15 is an SEM micrograph of a cellular particle formed under conditions in which the lattice has no in-plane lattice defects. As a result, the cell walls exhibit numerous wrinkles and folds on the surface, reflecting the topological mismatch of the planar carbon lattice draped on the nonplanar template surface. The highly crystalline in-plane structure of the lattice allows them to shear against each other more easily, which can cause tears within the cell walls. The cellular structure appears more fragmented in this micrograph compared to Figure 14. [Figure 16] Figure 16 is a diagram showing the time versus set temperature of the CVD reactor used to synthesize each of the cellular carbon samples S1, S2, S3, S4, and S5. The top diagram is the time versus set temperature used for S1 and S3, while the bottom diagram is for S2. [Figure 17]Figure 17 shows the Raman spectra of the S1, S2, S3, S4, and S5 carbon samples. The S1 and S3 spectra show a prominent 2D peak and a high D peak. The S2 sample shows an amorphous Raman spectrum (easily distinguishable by a much higher base feature at 1500 cm). The peak intensity ratios for the carbon samples are shown below. [Figure 18] Figure 18 shows TGA curves generated in an inert atmosphere under 100 mL / min argon flow and a heating rate of 10 °C / min. The plot shows mass loss as a percentage of the initial sample mass versus temperature for S1, S2, S3, S4, S5, XC72R, and XGNP-C-750. Mass loss below 600 °C is primarily due to elements other than carbon, such as oxygen. [Figure 19] Figure 19 shows an SEM micrograph of an S3 carbon sample. The sample is composed of individual cubic cells, each with a single contained cavity. The average cavity diameter is 40-80 nm, and the average cell wall thickness is less than 10 nm. [Figure 20] Figure 20 shows an SEM micrograph of an S2 carbon sample after high-shear mixing in an epoxy resin matrix and subsequent extraction by rinsing with acetone. S2 carbon structures composed of defective carbon lattices are more intact than carbon structures composed of more crystalline carbon lattices. The S2 cells remain largely intact after mixing into the epoxy, as can be seen on the right side of the micrograph. However, some alteration is evident, as shown on the left side. [Figure 21] FIG. 21 is an SEM micrograph of the S4 carbon sample after the template extraction process. [Figure 22] FIG. 22 is an SEM micrograph of the S5 carbon sample after the template extraction process. [Figure 23]Figure 23 shows an SEM micrograph of the fracture surface of one of the epoxy nanocomposites produced in Experiment A. In this image, cellular clusters of approximately 4 μm diameter can be observed. The clusters are formed by the agglomeration of individual submicron particles in the epoxy resin, and their location can be inferred by the spheroidal pullout pattern. Clusters such as this example possess both micron- and nanoscale features, which can aid in the evaluation of various strengthening mechanisms. [Figure 24] Figure 24 shows an SEM micrograph of an epoxy nanocomposite surface created by using a cryo-ion laser to mill the nanocomposite. In this nanocomposite sample, all milled surfaces were smooth and showed little pitting due to the cutting of unfilled cavities. This particular micrograph shows a representative example of the cellular structure observable within the epoxy matrix. The presence of this cellular structure, of the form shown in Figure 8, can be inferred from the appearance of intrinsic epoxy spots. While the extrinsic epoxy showed no reaction to the cryo-ion laser, the internal phase was not stable when exposed to the laser heat. Various regions can be inferred within the cavities. The most obvious is an unstable phase that hugs the intrinsic surface of the cell walls. DETAILED DESCRIPTION OF THE INVENTION

[0016] Cellular carbon is a porous sp 2 -Constitutes a subset of a broader class of hybrid carbon structures Due to its morphological diversity, as well as the diversity of non-cellular porous carbons, we First, other carbons that may be similar in one or more specific ways but are different when viewed holistically. A consistent and meaningful set of characteristics that taxonomically differentiates cellular carbon from non-cellular carbon. Porous sp 2 Broader categories of hybrid carbon structures include, but are not limited to: Single-wall nanotubes, multi-wall nanotubes, carbon microtubes B, fullerene, petroleum coke, char, ordered mesoporous carbon, carbon cenosphere Fair, graphene aerogel, folded or crumpled Crumpled graphene nanoplatelets, cup-stacked nanotubes, and Examples include hollow carbon nanofibers and porous carbon fibers.

[0017] Cellular carbons vary in size and shape of the cavities, thickness of the bulk features, and number of particles. Based on the structure and distribution characteristics of the populations made up of such particles, These characteristics determine the suitability for various applications. A cyclohexyl carbon is defined as one that exhibits at least some of the following criteria: 1. The bulk phase of cellular carbon is typically nanostructured, i.e., at least Individual cells are composed of features that average less than 100 nm in one measurement axis. The bulk phase of the sample is the cell wall, and its thickness is measured relative to the wall at the measurement point, as shown in Figure 2. In multi-cell particles, adjacent cell walls are Cellular carbon forms a nanostructured, monolithic bulk phase. However, it has a continuous multicellular microstructure but no bulk phase thicker than 100 nm. Not microstructured as exemplified by the cellular microfibers in Figure 3 There may be cases like this.

[0018] 2. The cavities of cellular carbon can be 10 nm or larger. Geometrically, this can be expressed as 10n This is shown in Figure 4 by fitting a circle of diameter m inside the 2D image of the cavity. As shown in Figure 4, a circle with a diameter of 10 nm is not fitted into the cavity. However, if the cavity is larger than 10 nm in any two perpendicular chords, this criterion In a structure with many cavities, most of them are larger than 10 nm. Therefore, the structure shown in FIG. 5 has a cavity smaller than 10 nm. Regardless, this criterion is met. In such structures, the cavities are generally localized. Therefore, the cavity diameter shown in Figs. The structure is applicable, but the structure in Figure 8 is not.

[0019] 3. The cavities of cellular carbon are not both highly elongated and linear. When defined as a "very elongated linear cavity", an aspect ratio greater than 10:1 is wherein the aspect ratio is the ratio of the length to the maximum diameter of the linear structure. As defined herein, "linear" means an aspect ratio greater than 5:1. For clarity, four examples are included in Figure 9. The first three structures on the left side of are linear structures according to this definition. However, The structure on the far right is both linear and very elongated, similar to a carbon nanotube. Therefore, this structure does not demonstrate criterion #3.

[0020] 4. Cellular carbon structures are discontinuous at length scales longer than 1,000 μm Therefore, the aggregate shape factor of cellular carbon aggregates is typically determined by dispersing them in a liquid. It is a powder or fine granular powder that can be

[0021] 5. Cellular carbons can be used in gas, liquid or liquid phases due to their cavity morphology and inclusion surface features. The template is a solid This is inherited from the cell wall contact at the interface between two different internal and external phases. This is achieved by conformal synthesis (as shown in Figure 10). The cellular structure formed on the perforated template may inherit the external pores. An example is a double-cylinder hollow cell with two external holes that are not part of the internal cell cavity. Another example is the cellular carbon shown in Figure 11, which is derived from the cylindrical template. The cellular carbon shown in Figure 12 is a cellular sheet in which numerous external holes can be observed between the cells. It is natural.

[0022] 6. "Cellular carbon derivatives" are not susceptible to mechanical, thermal, electrical or chemical processes after synthesis. As a result of this process, the derivative is may be subjected to fragmentation, deformation, collapse or other structural changes. Nevertheless, such derivatives , which share several morphological characteristics with their cell type precursors. A shred of a cellular carbon precursor is shown. The shred still shows the basic shape of the precursor. Although it is a more open configuration, it has concave and convex surfaces rather than inner and outer cell wall surfaces. It has a convex curve.

[0023] The classification of cellular carbons herein should show the first five criteria, or the sixth criteria. The derivative structure should be consistent with the sixth criterion. are generally derived from precursor structures that can be classified as cellular carbons. Evaluate criteria 1-5 Measurements for this purpose are performed using electron microscopy or other suitable high-resolution imaging techniques. Measurements performed using two-dimensional micrographs, e.g., SEM or TEM, can Although a complete three-dimensional mapping of the structure of cellular carbon cannot be obtained, such The measurements can be used to determine general features for a population of cellular structures. All measurements made or shown in are based on the analysis of two-dimensional micrographs. It is something.

[0024] Criterion #1 distinguishes cellular carbon from porous carbon, which lacks nanostructured walls. The smaller the specific surface area of ​​the carbon, the smaller the particle density (i.e., the mass of the carbon divided by the number of voids surrounded by it) The thin walled cellular carbon increases the total volume of the thick-walled hollow Allows for hollow configurations that can match the low particle density of carbon but have much smaller contained cavities Thinner and more two-dimensional walls also contribute to the formation of fluids in nanocomposites. The key properties of fillers are their larger interfacial surface area and their secondary structure relative to bulk carbon materials. Other properties exhibited by the original carbon material (e.g., excellent electrical conductivity and mechanical properties) ) is brought about.

[0025] Criterion #2 relates to the size of the cavity in the cellular carbon. It is distinguished from other porous carbon morphologies by its cavities, which are smaller in size. These are porous nanostructured carbons (nanotubes, fullerenes, ordered mesoporous carbons) The larger sizes are larger hollow carbon structures (e.g., cenospheres). Porous morphologies between the small and large sizes are more common. The polarized particles have an average pore diameter of less than 10 nm or greater than 1,000 nm. This is a cavity size range rarely seen in carbon fiber. The range is a cube function of the pore diameter, e.g., 10 nm and 1,000 nm, respectively. The volume between two virtual spherical holes with a diameter of 10 6 There is a difference. The small pores in nanostructured carbons reduce the limitations on their particle density and specific porosity. For example, fullerenes with diameters less than 1 nm are hollow, but their cavities are It is only a little more than twice the space between two graphite planes. Carbon nanotubes are permeated with a very long central void, the typical void diameter of which is a few nanometers. Some cellular carbons are significantly larger than one order of magnitude and are not very dense.

[0026] Criterion #2 is important for several reasons. Density reduction is a key factor in the development of synthetic foams such as syntactic foams. This is a desirable feature in materials used for buoyancy or weight reduction. Most carbons with voids are not particularly buoyant. Even if the pores are impregnated with a liquid or solid matrix material rather than a gas, Its low spatial density is advantageous. For example, cellular carbon is a material that can be leached into a matrix. Thin-walled cells are a superior structure for achieving low percolation thresholds. The mesh can be densely and continuously filled, which means that most of the cost is spent on obtaining conductivity. Nanocomposite products, such as conductive inks, are often made by the amount of carbon required to produce them. This can be an attractive feature for the cell. The type carbon provides a high nanocomposite volume fraction at a low weight percentage in the overall composite. Finally, cellular structures with larger inclusive ranges can occupy more potential areas. Potentially, they can undergo greater elastic or plastic deformation in response to mechanical stress.

[0027] Criterion #3 classifies cellular carbons with linear cavity morphology based on elongation. Distinguish from nanotubes and microtubes. Generally, carbon nanotubes, etc. Very elongated linear particles tend to entangle due to insufficient packing density, bundling efficiency [7], and and the disadvantage of increased viscosity in colloidal dispersions. Fibers are often milled, even in high-energy milling processes. There are practical limitations. For example, how much particle deficiency can be caused by milling? There is a limit to what can be achieved, and dramatic shortfalls can require long processing times. The milling process can cause problems with particle size distribution and morphological consistency by creating debris. In contrast, cells with linear structures and large truncated shape factors The cleaved structures can be less prone to entanglement and are superior. These may result in a higher packing density and may not increase viscosity as severely as highly elongated structures. Also, a large truncated cavity shape may be desirable when impregnation is required. This may be beneficial in preventing the arrival of very elongated nanostructures into diffusive fluid flows. Alternatively, the elongated structures may be used as nanocomponents. Branched (i.e., non-linear) cell shapes may be used if desired for leaching in the composite. Such morphologies allow the clustered particles to interpenetrate with each other. This allows for a spatially extended mesh that is potentially less prone to entanglement.

[0028] Criterion #4 allows cellular carbon to be fabricated into monolithic or This is to be distinguished from porous or interconnected carbon preforms, such as aerographite. This is because cellular carbon is easily incorporated into flowable nanocomposite dispersions due to its structural discontinuity. Dispersibility can be of practical importance in many product realizations, e.g. This is suitable for ejecting ink, spreading paint, infusible resin, etc. Impregnation becomes less critical, making it easier to wet and impregnate the cavity.

[0029] Criterion #5 defines cellular carbon as a composite of its templated cavities and internal topography. As used herein, the term "templated porous carbon" is used to distinguish it from other porous carbons based on its " is a nested template-shell-matrix (1-2-3) system, etc. As shown in Fig. 1, a shell of cellular carbon (or its carbon-based precursor) is conformally synthesized around the The inner region of an organized solid, liquid, or gas. In this ternary system, carbon or carbon The shell of the precursor (2) exists at the interface between the internal template (1) and the external matrix (3). The geometry, size and inclusive topography of the shell are all determined by the template during shell formation. An example of a template-shell-matrix system is the outer matrix of a gas. A carbonaceous droplet (2) suspended in a gas (3) blowant template (1); graphene oxide in aqueous matrix (3) An oil droplet (1) coated with nanoplatelets (2); and a carbon-based gas matrix The carbon shell (2) inside the nucleus (3) and the metal oxide template (1) inside the nucleus (3) are examples of the metal oxide template. do.

[0030] The templated cavity is a key feature that differentiates cellular carbon from other porous carbons. This is a characteristic feature because the cell cavity morphology is not random in the particle population, and The conformal, two-dimensional nature of the particle cell walls allows for highly uniform particle populations (But it's not necessary; in fact, one of the benefits of a uniform particle population is that when you blend them, The ability to create controlled polydisperse particle distributions for tailored composite properties In contrast, most cavity-containing carbons are carbon-matrix structures with no distinct template phase. Because it is synthesized in a binary system of tetratrices, it has a random and irregular cavity morphology. For example, few-layer graphene nanoplatelets (GNPs) prepared by liquid-phase exfoliation These may be the result of folding, wrinkling, interparticle adhesion, or random interactions with the surrounding matrix. However, there is no clear template phase. Therefore, such cavities can be irregular. The irregular cavities in the aerogels allow the formation of graphene oxide nanoparticles in an aqueous matrix. This system may be the result of random self-assembly of platelets. It can be free of carbon phase and consist of only carbon and matrix. The element is that none of these three phases falls under the "template" defined in this specification. For example, petroleum coke or char can be formed in a ternary system where the inner volatile species (phase 1) Random particles generated as they move through the carbon-based structure (phase 2) in the external gas atmosphere (phase 3). The pore structure of the dam is shown. However, these volatile species are not readily absorbed by the surrounding com- forts. Rather than the carbon structure being synthesized or organized normally, volatile species are released from the inside out. This results in random etching of the carbon structure, which may not meet the criteria of the template. There is a possibility that this is the case.

[0031] Criterion #6 is derived primarily from cellular carbon precursors but with post-synthesis processing. cellular carbon and non-cellular carbon. carbon that has been morphologically modified to either exhibit features related to both carbon types For example, cellular carbon fabricated with a metal oxide template can be fabricated by using the metal The cell may be subjected to an acid extraction process that dissolves the oxide template. Random damage and alteration of the structure may occur. An example is shown in Figure 13, which is an SEM micrograph of a modified cell. The morphology was spheroidal, but the post-synthesis mechanical stress caused by template extraction The particle broke into curved shreds due to the cracking. The fragments adhere to each other, but the image also shows the formation of particles. The large interparticle spaces caused by the inherited curvature are also preserved. Another common derivative is one in which the cell walls are thin enough to collapse while remaining intact, and Due to the flattening of the cavities, the resulting derivative appears to be shrunk. When such a derivative is impregnated with a liquid or solid filler, the cavity Dimensionality can be restored.

[0032] The derivative structure is important because it possesses many of the properties of its cellular carbon precursor. The body may, for example, no longer have internal porosity, but instead have a dense mass and surface area. It may possess a high degree of curvature that makes obscuration geometrically impossible. may result in the preservation of interparticle spacing and surface area within the nanocomposite. In some specific cases, the derivative may even be preferable to its cell type precursor. As with two-component resin systems with short pot lives, the liquid matrix in the cell cavity If rapid impregnation of the material is desired, a shredded surface with open recesses is more suitable. The more easily and quickly the more intact the closed-cell structure of the inclusion surface is wetted, The nanocomposite matrix is ​​impregnated with multiple liquid components blended in sequential steps. In Ricks, the composition of the components is equilibrated inside and outside the more intact cellular structure. This can be difficult, especially if the multi-component composition is highly reactive.

[0033] Another reason that cellular derivatives are important is that they are often In this case, a plurality of carbon particles are contained in the nanocomposite dispersion. In this context, the criteria for cellular carbons in this disclosure often require a strict structural definition of nanocarbons. The present invention may be applied to precursors of derivative structures actually found in composites.

[0034] Cellular carbon structure One of the reasons for the diversity of cellular carbon types is the diversity of compositions at the lattice and cell levels. The cell walls are made up of carbon single-atom-thick layers attached to each other in an overlapping patchwork configuration. The lamellar structure is composed of elementary lattices. The lattices are the building blocks of the cell walls, and have various sizes and Depends on shape, orientation, molecular tiling and surface chemistry. Lattice and cell level By adjusting the composition in the cells, it is possible to obtain cells with the same grain size, the same geometry, and even the same wall thickness. The two virtual cells involved could have dramatically different properties.

[0035] One of the origins of the lattice variation is its molecular tiling. In some cases, the crystallinity is high and the crystallinity is poor. In the crystalline case, it can be hexagonally tiled (e.g., graphene lattice) ) or some other tiling (e.g., haeckelite (tiling). Different configurations at the grid level result in different behaviors. For example, an amorphously tiled lattice composed of 5-, 6-, and 7-membered rings can be can be electrically insulating, while the defect-free graphene lattice is highly conductive

[10] . A graphene lattice consisting of % defective rings undergoes ductile fracture and crazing under tension. Although this is possible, brittle fracture occurs in a relatively defect-free lattice, and the material has excellent strength and elastic modulus. [11-12]. Also, fully crystalline graphene sheets are planar, and therefore It may not be topologically possible to perfectly fit a curved surface. Therefore, cellular carbon composed of graphene lattices formed on curved templates can be wrinkled and The cell walls may be composed of more defective crystalline structures ( In the case of rings containing five, six, seven, etc., the lattice conforms to the curved template. Finally, multi-layer cell walls potentially have overlapping There may be sp3-hybridized bonds interconnecting the sp2 lattice.

[0036] Visual evidence of such topology differences can be seen in Figures 14 and 15. In the SEM image shown in Figure 14, the cell walls are clearly visible with their smooth surfaces and intact cells. Defective carbon structures can be interconnected by sp3-hybridized bonds in the base The SEM image shown in Figure 15 shows that the cell walls are sheared and delaminated. After template extraction, wrinkled or folded surfaces are likely to occur (linear surfaces). It is composed of a crystalline carbon lattice whose cell structure may become less intact as it takes on a shape It has been done.

[0037] The wall can also vary depending on the surface chemistry. i.e., relatively defect-free) graphene lattice has substantially no basal plane functionalization However, reduced graphene oxide or graphene oxide lattices have oxygen moieties. Application methods can be used to graft oligomers and polymers onto the cell walls. The overlapping lattices that make up the wall are oriented based on both their lattice chemistry and their orientation relative to each other. Based on the thickness, it can have various interlayer spacings (eg, AB vernal lamination or turbostratic lamination).

[0038] In addition to having a variety of molecular tilings, functionalities, stacking patterns, and interlayer spacings, The grid may vary in lateral dimensions, i.e., in its shape and area. It can be an important determinant of the mechanical, electrical, thermal and chemical properties of the polymer and cell walls. For example, a larger lattice may allow electron transport with less tunneling than a smaller lattice. , potentially reducing the electrical resistance of the carbon structure.

[0039] Additionally, the cell-level organization can be tailored to alter the properties of nanocomposites. The thicker the wall, the greater the density, specific surface area, and specific porosity of the carbon. Also, the structure of the cell walls may vary internally due to the lattice orientation relative to the walls. If the orientation is parallel to the cell wall surface, the chemistry at that edge is hidden by other lattices. However, if the grating is oriented such that the edges are exposed, The edge chemistry can have a significant effect on the properties of the cell wall surface. This principle is consistent with other Non-cellular carbons have also been demonstrated. For example, cup-stacked nanotubes are similar to graphene. The tube wall configuration has most of the edges of the tube exposed. This orientation allows for the overall The reactivity of the cup-stacked nanotubes is enhanced compared to the wall surfaces where the basal planes of the lattice are dominant. The dispersion of the lattice structure is easier in many systems

[13] . Indicates the wall.

[0040] Another way in which cell walls can differ is their porosity. Multilayer cell walls are characterized by the porosity of graphite. It probably has sub-nanometer interlayer voids, so that it is suitable for the The lateral voids that run through the membrane can be more variable and very important. This may be the result of incomplete wall formation during template extraction or a crack formed during template extraction. The number and size of the lateral holes affect the rate of diffusion flow into and out of the cell cavity. The fewer and smaller the pores in the cell walls, the easier it is for the matrix liquid to penetrate. It can take a long time.

[0041] Overview of the procedure All carbon cells and cellular derivatives described herein are based on chemical vapor deposition in powder templates. However, these are only examples and are not included in the present specification. It will be understood that the synthetic procedures described are also This process is described in more detail in US Provisional Patent Application No. 62 / 294,751. Several carbon generation protocols were used to provide physical and mechanical properties to polymer-based nanocomposites. To demonstrate the utility of cellular carbon for imparting electrical and mechanical properties, various samples were Cellular carbons and derivatives of various sizes, shapes, and wall compositions were synthesized.

[0042] All templates used were magnesium oxide (MgO) powder grades. MgO is a well-known catalyst for the thermocatalytic decomposition of carbon-based precursor gases. was carried out using several hydrocarbon precursors in a tube furnace at various temperatures.

[0043] After the CVD was completed, the obtained MgO / C core-shell heterostructure was dissolved in dilute hydrochloric acid (HCl ) to dissolve the MgO template particles, leaving the carbon shell intact. The carbon was then filtered with an aqueous MgCl2 solution to produce an aqueous carbon paste. The yeast was rinsed thoroughly with deionized water and then filtered again. The water was replaced with acetone using an exchange method to obtain an acetone paste. The materials were either directly blended into the nanocomposite formulation or were added by evaporation. and drying to form a dry powder which can be blended into a nanocomposite, if desired. The thin film may then be subjected to further CVD growth.

[0044] To create the nanocomposites for testing, the cellular carbon and derivatives were mixed with a commercially available comparative The thermosetting nanocomposite was dispersed in a matrix along with other non-cellular carbons. Thermoset specimens were formed by pouring, casting, curing, and machining. The composite was molded using a hot press system to form thermoplastic test specimens. The sample was prepared by coating the nanocomposite dispersion onto a polyethylene terephthalate (PET) film. It was made by

[0045] Synthesis of cellular carbon Three samples of cellular carbon (S1-S3) were prepared by CVD on 100 mm OD stones. English pipe, stainless steel flange, gas inlet and single bath outlet The synthesis was carried out in an MTI rotary tube furnace equipped with a gas outlet. All were manufactured by Praxair.

[0046] In S1, a methane / argon mixture was used as the feed gas. A 0.00 gram sample of Elastomag 170 MgO ("EL170") was placed in a furnace. The sample was loaded into a quartz tube (OD 100 mm) inside the heated zone. No rotation was used. The reactor was heated linearly and gradually from room temperature to the set temperature of 1050°C over 50 minutes. The temperature was maintained for 30 minutes under an Ar flow of 0 sccm. Then, the Ar flow was kept unchanged. With the temperature kept constant, a flow of 500 sccm of CH4 was started and continued for 30 minutes. The flow of Ar was stopped and the reactor was cooled to room temperature under a continuous flow of Ar. The MgO was then acidified with HCl. Extraction was performed by etching to obtain a slurry containing carbon in aqueous MgCl2 brine. The carbon was then filtered from the brine, rinsed three times with deionized water, and dissolved in an aqueous paste. The water was then replaced with acetone using a solvent exchange method, and the acetone in S1 was A cell-type carbon paste was obtained.

[0047] In S2, a propylene / argon mixture was used as the feed gas. A 500 gram sample of EL170 was loaded into a quartz tube inside the heating zone of the furnace. The reactor was heated from room temperature to 1050°C under a 500 sccm Ar flow. The temperature was increased linearly to the set temperature over 50 minutes, and then increased to 750°C over 30 minutes. The temperature was then linearly decreased to 0.25°C, and maintained at that temperature for 30 minutes. While maintaining the temperature constant, a 250 sccm flow of C3H6 was initiated and continued for 60 minutes. The C3H6 flow was then discontinued and the reactor was cooled to room temperature under a continuous Ar flow. Extracted by acid etching with HCl and slurried with carbon in aqueous MgCl2 brine. The carbon was then filtered from the brine, rinsed three times with deionized water, and washed with water. The solution was collected as a soluble paste. The water was then replaced with acetone using a solvent exchange method, and the S Two acetone / cell-type carbon pastes were obtained.

[0048] In S3, a methane / argon mixture was used as the feed gas. A 0.05 gram sample of magnesium oxide smoke (obtained by burning metallic magnesium) The sample (prepared) was loaded into a quartz tube inside the heating zone of the furnace. No rotation was used. 500 s Under a flow of Ar at 0.50 ccm, the reactor was heated from room temperature to the set temperature of 1050°C in a linear gradient over 50 min. The temperature was gradually increased and maintained at that temperature for 30 minutes. Then, while the Ar flow was kept unchanged, A CH4 flow of 800 sccm was started and continued for 30 minutes. Then the CH4 flow was stopped. The reactor was cooled to room temperature under a continuous Ar flow. MgO was removed by acid etching with HCl. The carbon was extracted with MgCl2 brine to give a slurry containing the carbon. It was filtered from the brine, rinsed three times with deionized water, and collected as an aqueous paste. Then, a solvent exchange method was used to replace the water with acetone, and the acetone / cell-type carbon paper of S3 was used. Got a strike.

[0049] In S4, a methane / argon mixture was used as the feed gas. A 0.00 gram sample of EL170 was placed in a quartz tube (OD 100 mm) inside the heating zone of the furnace. The reactor was heated from room temperature to a temperature setting of 1050°C. The temperature was increased linearly over 50 minutes to the desired temperature, and the temperature was then measured under a 500 sccm Ar flow. The temperature was maintained for 30 minutes. Then, while the Ar flow was kept unchanged, 1000 sccm of C The H4 flow was started and continued for 45 minutes. The CH4 flow was then discontinued and the reactor was placed in continuous A The mixture was cooled to room temperature under a stream of fluorine. The MgO was then extracted by acid etching with HCl and washed with water. A slurry of carbon in MgCl brine was obtained. The carbon was then extracted from the brine. It was filtered, rinsed three times with deionized water, and collected as an aqueous paste. The chlorine content was 10-15% in sodium hypochlorite solution (NaOCl). The ratio of carbon to OCl solution was 1:40. The mixture was stirred at room temperature for 24 hours. The carbon is then filtered from the bleach, rinsed three times with deionized water, and washed with an aqueous paste. The water was then replaced with acetone using a solvent exchange method, and the acetone in S4 was A carbon paste of the cell type was obtained.

[0050] In S5, a propylene / argon mixture was used as the feed gas. A 500 gram sample of EL170 calcined at 900°C overnight was placed inside the heating zone of the furnace. The reaction mixture was loaded into a quartz tube. No rotation was used. The reaction mixture was stirred under a 500 sccm Ar flow. The temperature of the vessel was gradually increased linearly from room temperature to a set temperature of 750°C over 30 minutes, and then The temperature was maintained for 30 minutes. Then, while the Ar flow was kept unchanged, 1000 sccm of C The C3H6 flow was started and continued for 30 minutes. The C3H6 flow was then stopped and the reactor was re-opened. The mixture was then cooled to room temperature under a continuous Ar flow. The MgO was then extracted by acid etching with HCl. This resulted in a slurry of carbon in aqueous MgCl brine. The mixture was filtered from the flask, rinsed three times with deionized water, and collected as an aqueous paste. The water was replaced with acetone using a solvent exchange method. The resulting acetone / cell-type carbon paste The mixture was dried to produce a carbon powder. This powder was then subjected to the 1,3 dipolar cycloaddition protocol. For this purpose, equivalent parts of N-methylglycine and 4-formylammonium chloride were used. To this solution, cellular carbon powder was added and the mixture was stirred under a N2 atmosphere for 9 h. After refluxing, the functionalized carbon was thoroughly washed with acetone three times and then added to S5 Acetone / functionalized cellular carbon paste was obtained.

[0051] For reference, the graph in Figure 16 shows the CVD time versus the amount of carbon used to synthesize each cellular carbon sample. Indicates the set temperature used.

[0052] Carbon characterization After extraction, each cellular carbon sample was analyzed by Raman spectroscopy, TGA, SEM, and T EM image processing and ash content tests were used to characterize the material.

[0053] Raman spectral analysis was performed using carbon cells (S1, S2 and S3) after extraction of the template material. 3) and are shown in Figure 17. Three main spectral features are typically associated with sp2 bonds. Associated with carbon complexes: G band, 2D band (also called G band) and The G band is present in all sp2 carbons and therefore in sp2 carbon crystals. A peak within this band was observed at 1585 cm-1. The 2D or G' band exists between 2500 cm-1 and 2800 cm-1. The D band is associated with continuous sp2 carbon structuring in the 2-dimensional direction. ~1400 cm-1 and are associated with lattice defects. The peak intensity can reach a maximum, after which the peak broadens and decreases in height due to the increase in defects. When this broadening occurs, the bottom between the D and G peaks becomes shallower ( Therefore, when measuring the base intensity, the broadening of the D peak is observed. Therefore, in this disclosure, the bottom between the D peak and the G peak, the "T band" The intensity of the T band is determined by the wavenumber associated with the D peak and the G peak. The minimum intensity value that exists between the wavenumbers associated with the G, 2D, D and T bars is defined as the minimum intensity value that exists between the wavenumbers associated with the G, 2D, D and T bars. In this specification, the intensities of the bands are referred to as I G , I 2D (or I G’ ), I D and I T and Display.

[0054] Raman spectra can be analyzed for a variety of reasons, some of which are not directly related to the structural features of interest. ) and may vary from location to location within the sample. To ensure representative characteristics of the templated carbons used, the following procedure was used: For each carbon sample, 60 different point spectra were measured. This is done on a rectangular grid of 6 × 10 points spaced 50 μm apart. The different point spectra were averaged to obtain a composite spectrum. All intensity ratios are for the composite spectrum obtained from the measurement of these 60 point spectra. is.

[0055] The spectra of samples S1 and S3 in Figure 17 show moderate to high two-dimensional ordering ( This is indicated by its prominent 2D peak (greater than 0.46). Key I 2D / I G In contrast, sample S2 shows virtually no 2D peak. (I less than 0.10 2D / I G ratio), showing a very broad D peak and more defects. This indicates that the crystal structure is crystalline.

[0056] TGA analysis shows that the carbon nanotubes after extraction of the template material and after covalent functionalization (S4) The TGA curve (Figure 18) shows the mass retention versus the initial sample mass. The values ​​are expressed as a percentage of the total volume of the sample taken at an argon flow rate of 100 mL / min in an inert argon atmosphere. and a heating rate of 10°C / min.

[0057] SEM analysis of template-extracted carbon grown using S1, S2 and S3 procedures The results for carbon grown using the S1 procedure are shown in Figure 15. The results for carbon grown using the S2 procedure are shown in Figure 14. Carbon grown using the S3 procedure The results for bare carbon are shown in Figure 19. The results for carbon grown using the S4 procedure are shown in Figure 20. Results for carbon grown using the S5 procedure are shown in FIG.

[0058] Experiment A One of the most promising uses of carbon nanostructures in polymers is the application of carbon nanostructures to brittle thermoset polymers. Low-dimensional carbon is a reinforcing agent for polymers due to its high aspect ratio, high surface area and Its strength makes it a good candidate for many other reinforcements in a variety of thermoplastics. Unlike carbon, it has been shown that carbon does not lower the glass transition temperature of polymers, making it suitable for aviation applications. This is important for high temperature applications in industries such as aerospace. A cellular morphology can be advantageous for reinforcement purposes for several reasons. First, its structure The structure results in a three-dimensional cavity surrounded by two-dimensional walls, which is occupied by cellular carbon. In fact, the volume fraction per unit carbon weight is much higher than that of other low-dimensional carbons. The cellular structures described in this disclosure have a matrix The nanocomposite is internally impregnated with the silicon material, so that the impregnated cells are Second, cellular carbon and its related materials are used to form a kind of nested nanocomposite filler. The derivatives tend to cluster into multicellular structures, exhibiting microscale features and nanostructures. This results in a spatially extended reinforcement framework with both multi-scale features. This allows us to identify the specific reinforcement modes characteristic of microfillers in addition to the reinforcement modes characteristic of nanofillers. For example, a theoretical model of micron-scale silica reinforcement shows The main strengths are crack pinning, grain bridging, microcrack initiation and crack deflection. While the model for nanoscale reinforcement suggests that the reinforcement effect is Particle debonding (which then leads to void growth) and the associated shear banding In particular, the decomposition of high surface area nanostructures from a matrix is ​​being investigated

[14] . The bonding dissipates the fracture energy in the reinforced nanocomposite. Therefore, fillers that offer both micron-scale and nano-scale aspects are suitable for reinforcement. It should be fascinating along the way.

[0059] Thermosetting nanocomposites reinforced with cellular morphology and those reinforced with non-cellular morphology A two-component epoxy formulation was used to model the thermosetting nanocomposite (vs. To make the fairest comparison between carbons based purely on their morphology, chemical functional groups were used. No enhancements were introduced. A total of five nanocomposite samples were fabricated and tested. A control epoxy sample was prepared without carbon ("A0"). For control, two cellular carbon samples with different crystallinity (S1 and S2) were prepared. S1 carbon sample was selected as it was composed of a more crystalline carbon lattice structure. whereas the S2 carbon sample was composed of a more defective carbon lattice structure. These carbons were then divided into two nanocomposite samples (“A1” and “A2”), respectively. 2”).

[0060] The other carbon samples were chosen to balance several potential factors. In particular, it is desirable to test carbons with both planar and non-planar morphologies. Second, carbon containing micron-scale particles and carbon containing submicron particles Third, it was desired to examine carbon containing oxygen moieties and Fourth, it was desirable to test carbon that is crystalline and does not contain defects. Finally, it was desirable to test carbons that are comparable in quality to the cellular carbons used. It was desirable to test carbons containing 0.1 or greater surface areas. To make it as simple and easy as possible, a commercially available carbon black (Cabot Vulcan) was used. and XC72R) samples and commercially available graphene nanoplatelets (XG Sci The samples selected were: ence X-GNP-C-750. Table 1 below shows the results of these samples. Here is a summary of the pull characteristics: [Table 1]

[0061] After preparing the epoxy dispersions of A1 and A2 (following the procedure described below), the nanocomposite The particle shape of the cellular carbon sample in the jet was confirmed by rinsing with acetone. The S1 and S2 carbons were extracted and analyzed by SEM. Analysis showed curved fragments such as those seen in Figure 13. Defective or altered The cell structure was dominant over the intact cell structure. On the other hand, the SE of the S2 carbon M analysis showed a largely intact cell population with some fragmentation in some cases. , a micrograph of S2 carbon after rinsing with acetone, showing the dominance of intermetallic compounds. A normal cell structure can be seen on the right, while an example of a minority altered cell structure is seen on the left. The fragmented nature of the S1 carbon and the largely intact nature of the S2 carbon can be observed indefinitely. This is consistent with theoretical predictions that the lattice of crystalline carbon is more ductile than that of crystalline carbon. We assumed that the particle shape of R and X-GNP-C-750 would not change due to dispersion. Each was derived from the literature and manufacturer's data sheets.

[0062] Surface oxidation of samples held at 600 °C from their original mass measured using TGA The mass of the XC72R and The mass loss in X-GNP-C-750 is calculated based on the oxygen data for XC72R reported in the literature (0 0.3%) and the oxygen data for X-GNP-C-750 reported on the manufacturer's data sheet. This is in reasonable agreement with the variance (greater than 6%).

[0063] The crystalline structure of the S1 and S2 carbon samples was confirmed by Raman spectra as shown in Figure 17. CV with subduction and quenching of lattice nuclei Due to the structural effects of carbon growth, the Raman spectra of cellular carbons such as S1 show a large difference in the cell walls. The spectral signal for the more crystalline outer layer of the This reflects the composite of the spectral signals for the inner layer. The spectrum of S1 shows the presence of crystalline carbon in the outer layer and is therefore designated as crystalline. In S2, despite the appearance of large lattices in the outer layer, these large lattices are not in-plane defects. The Raman spectrum of XC-72R shows that the crystallinity is not observed. Although the carbon content was not significant, it reflected amorphous carbon as expected. The Mann spectrum is not shown, but can be seen in the data sheet, and shows a relatively crystalline lattice. The structure is confirmed. However, the characterization guidelines provided by the spectrometer manufacturer In the case of nanoplatelets, the crystalline structure is composed of both large and small nanoplatelets. It has been shown that Raman scattering is difficult to detect due to the presence of

[0064] The specific surface area of ​​the sample was investigated using BET analysis. The surface area indicated by the manufacturer is 750m 2 / g, but the guide for characterization is that this , small (<100 nm) high surface area nanoplatelets and large (1-2 μm) low surface area nanoplatelets. It is explained that the surface area is the average value obtained for a mixture of nanoplatelets. Therefore, in a nanocomposite, there are actually two nanoplates with significantly different surface areas. A tret filler phase is present.

[0065] Using such carbon samples, the nanocomposite samples A1 to A4 were subjected to the following tests: Star badge, Momentive Epon 828 (“828”) and Huntsm an Araldite LY1556 ("1556") difunctional epoxy resin: The preblend was prepared with 1.33 wt% carbon in a volume ratio of 1. The carbon was mixed with a high shear rotor. Disperse for 90 minutes using a stator mixer at 15,000 rpm and distribute over four master batches. A sample was obtained.

[0066] Each masterbatch sample was then mixed with 828 / The carbon was diluted by mixing with the 1556 preblend. The loading was adjusted so that the final carbon weight fraction of the nanocomposite was 0.3% (see Table 1). The temperature of the masterbatch and 828 / 1556 preblend during mixing was 60°C. In this case, the mixture was mixed in a Thinky double planetary mixer for 3 minutes at 2,000 rpm and sealed. A vacuum of 25 kPa was applied to remove air.

[0067] Each resulting Component A sample was then mixed with Component B (Aradur 34055 epoxy curing agent) The blend was made with the agent "34055" in a two-step mixing process. In the first step, component B was added to component A at 1,100°C. The mixture was added under Cowles blade mixing at 100 rpm for 1.5 minutes. This was followed by a double planetary A second mixing step using a Lee mixer was performed for 3 minutes at 2,000 rpm to remove entrapped air. The test was carried out under a vacuum of 25 kPa to achieve this.

[0068] Then, each of the resulting A+B mixtures (at 40°C + / - 5°C) was pretreated with a release agent. These were allowed to gel at room temperature for 20 minutes and then heated to 60°C. The sample was then cured at 60°C for 2 hours and then quickly removed from the mold. The mold was demolded and cured at 60°C for a further 2 hours, then the oven was heated to 80°C for 15 minutes. The temperature was increased linearly. The sample was cured at 80°C for an additional 6 hours and then cooled to room temperature. I made him turn away.

[0069] For the carbon-free epoxy sample A0, the 828 / 1556 preblend was heated to 35°C. The 34055 hardener was then added under Cowles blade mixing at 1,100 rpm. This mixture was then mixed in a double planetary mixer for 3 minutes at 1000kJ / min for 1.5 minutes. Blending was carried out at 2,000 rpm and a vacuum of 25 kPa to remove entrapped air. The resulting mixture was then poured into the same pre-treated mold to form a nanocomposite sump. Samples A0-A5 were subjected to the same gel / cure cycle as Samples A1-A4. The weight ratios used for: [Table 2]

[0070] Each of the samples A0 to A4 was subjected to fracture toughness (K Ic ) The test was carried out using a three-point bending (SENB) test piece. A slit was machined into the center of the epoxy block. A razor blade was then inserted through this slit. Insert the insert into the slot and tap it with a hammer until a crack appears at the bottom of the machined slot. The dimensions of the test piece were W = 19.05 mm, L = 83.82 mm, and B = 7.5 mm to 8.5 mm. The horizontal slits were 4 mm deep, and the cracks were 3.6 mm to 7 mm in size. The length is 0.4 mm, the “a” value is 7.6 to 11.4 mm, and the “a / W” value is 0.4 to The test specimen was a SENB manufactured by Wyoming Test Fixtures. Hydraulic universal test system with three-point bending test fixture and 1001b (445N) load cell The stem was mechanically tested on a universal testing system with a constant crosshead speed of 10 mm / min. The data was then transferred to a National Institute of Standards and Technology (NIS) connected to a Windows PC. The measurements were recorded using a USB-6341 data acquisition system. The specimen dimensions were Measurements were taken using a Mitutoyo digital caliper.

[0071] Table 3 below shows the fracture toughness and tensile test results for samples A0 to A4. [Table 3]

[0072] This result was obtained using the same loading, no additional dispersant, and the exact same mixing protocol. In the blends with cellulose, graphene nanoparticles were observed in the cellular morphologies of S1 and S2. The toughness of the epoxy was significantly improved compared to that of the graphite and carbon black. This result was obtained despite the elemental nature of the model formulations described herein, Even at low loadings and without any surface treatment, cellular carbon and its derivatives exhibit brittle thermal It is suggested that it may provide a significant toughening effect to curable resins, such as epoxies. This may be due to its unique morphological structure. Fractographic analysis of the fracture surfaces of both A1 and A2 revealed multi-cell fractures such as those shown in Fig. 23. The individual subunits are submicron in size, but the structure is three-dimensional. In contrast to dense agglomerates, the structure of cellular carbon is characterized by the impregnation of cells. Therefore, most of the volume is matrix material.

[0073] Impregnation can be demonstrated by making a planar cross section of the nanocomposite and looking for voids. Figure 24 shows the results of milling an A2-type sample using a cryo-ion laser. The milled surface is smooth and the frame is not visible. It can be inferred that there is a cell of the shape shown in Figure 8 at the center of the nanocomposite described in Experiment A. Analysis of the milled surface revealed that there were no unfilled cavities, and the cross section The openness of the altered cell structure may be observable as holes in the milled surface. and the liquid resin nanocomposite is widely used in a continuous process to prepare the final nanocomposite. Given the vigorously blended nature of the blend, good impregnation is expected.

[0074] Interestingly, however, nanocomposite structures incorporating mostly intact cellular structures are SEM analysis of the cryo-ion milled surface of composites, e.g., A2, is shown in Figure 24. This indicates the existence of a phase difference between the interior and exterior of the cell, as can be observed. The contours of the epoxy matrix are thermally unstable and cryogenically stable, unlike the surrounding epoxy matrix. Poorly crosslinked or poorly plasticized epoxy that visibly liquefies when exposed to an ion laser. It can only be identified in Figure 24 due to the appearance of discernible internal phase spots. do.

[0075] The presence of such a phase likely reflects the degree of encapsulation of the largely intact S2 cells and the presence of the pores in Experiment A. This is related to the relatively short pot life of the two-component epoxy system described in Before mixing together, the carbon is presumably impregnated and wetted by the resin matrix. However, the blending time of the two reactive components is such that the rapid onset of the curing reaction occurs. Limited by the start of the blending process due to the short pot life of the polymer system. Considering the constraints, to obtain a perfect balance between the infiltration and exudation flows inside and outside the cell, In other words, the cell membrane may not be able to separate the material inside the cell. This strengthens the barrier that prevents the material from quickly equilibrating with the mixture outside the cell. Localized shear mixing effects and isolation from turbulence in the surrounding fluid at the membrane of the cell For example, fluid exchange with the outer matrix may occur. The bridging only within the cell wall opening where the exchange occurs is more pronounced compared to the deeper interior regions of the cavity. This early onset of hardening in the wall openings may be due to the mass transfer The balance can be further constrained by creating bottlenecks precisely where movement is required. Asynchronous curing also results in distinct polymer phases in different regions within the cell cavity. Such clear phases can be seen in all of the images, such as Figure 24. An example of this is the patchy regions that hug the inner wall of the cell. Peripheralization of uncrosslinked liquid resin as crosslinking and solidification occur Alternatively, the use of solvents such as acetone in the preparation of cellular carbon powders may result in the formation of cellular carbon. If a solvent is used, it may not be completely removed from the inside of the cell in an insufficient drying process. Regardless of the true mechanism behind the formation of such an internal phase, which is probably very complex, It is not the purpose of this disclosure to be bound by theory.

[0076] The presence of a secondary encapsulated polymer phase with low crosslink density contained within the carbon cells is unique and has been reported in the literature. Such a complex structure is due to the plasticity of the inner polymer phase and the carbon structure within the wall. The mechanical properties of thermosetting polymers, especially their toughness and elongation, are improved by combining the lubricity of the matrix lattice. This could potentially be beneficial for improving long-term performance, for example, in cells with encapsulated silicon cores. The carbon shells are formed by the interaction of carbon lattices in response to tensile stress during lithiation and delithiation. The sliding ability of the inner silicon allows for over 200% volumetric expansion and contraction.

[19] Mechanically similar "telescopic" pullout The effect is that the nanotube / matrix interface transfers mechanical stress to the outermost tubular lattice. This is known to occur in multi-walled carbon nanotubes when the force is strong enough to cause [20-21]. The stress transfer between the outermost lattice of the cell and the outer polymer phase is ensured by the Considering the full stress transfer between the innermost lattice and the plasticized inner polymer phase, a complex local Composite fillers could be formed that could expand or contract isotropically in response to a given stress. For best results, cellular carbon must be well integrated with the outer matrix and inner polymer. It may need to be chemically functionalized for good binding.

[0077] Experiment B In addition to toughening the epoxy, low-dimensional carbon nanostructures also improve tensile properties, such as ultimate tensile strength and Cellular carbon nanostructures, in particular, can improve the mechanical properties and tensile modulus of elasticity of polymers by combining an external carbon surface with The interface between the matrix is ​​strong enough to allow stress transfer from the matrix to the carbon. If the interface is insufficient, it should provide tensile strength to the polymer. In this case, cellular carbon nanostructures are worse than nanoplatelets and nanotubes. It can be predicted that the polymer will perform worse than the polymer alone. This is due to the dimensionality of the nanoplatelets, for example, due to insufficient bonding with the matrix. Therefore, when the interface fails under tensile stress, the polymer delaminates from the carbon and a 2D crack forms. On the other hand, the binding of the 10 μm multicellular tissue to the matrix is ​​insufficient, Therefore, when the interface breaks under tensile stress and the polymer peels off from the cluster, A discontinuity is formed in the polymer that tracks the size and shape of the The effect of this is, in other words, a 10 μm three-dimensional discontinuity, essentially a carbon cluster. It introduces voids into the matrix that exist but do not provide reinforcement or connectivity. The more carbon microstructure is loaded into the core, the more discontinuities are introduced, and the more the tensile properties improve. It will progressively deteriorate.

[0078] To alleviate this concern, we have developed nanocomposites in which cellular carbon is chemically functionalized. It was desired to test S4 and S5 to prepare nanocomposite samples. Cellular carbon was selected. A multifunctional (>2) epoxy system was selected to improve the cellular carbon. The automotive and aerospace industries, as well as polymers, offer greater dimensional stability throughout their service life. Elevated tensile strength and glass transition temperature are commonly used in other demanding applications where high The bridge density was investigated in the system.

[0079] The S4 and S5 carbon samples were used to prepare two masterbatches using epoxy resin pre-blended polymers. The preblend was prepared with 1.33 wt% carbon in the blend. The preblend was prepared with 35 wt% difunctional M omentive Epon 828 (“828”) resin, 35% by weight concentration of bifunctional M omentive Epon 862 ("862"), and tetrafunctional at 30% by weight Constructed from Huntsman Araldite LY9721 (“9721”) The carbon was mixed at 90°C using a high shear rotor-stator mixer at 15,000 rpm. The mixture was dispersed for 1 minute to obtain two masterbatch samples.

[0080] Each masterbatch sample was then mixed with 828 / The carbon was diluted with the 862 / 1556 preblend. The final carbon weight fraction of the nanocomposites after addition was 0.5% for B1 and B2, respectively. and 0.3% (see Table 4). The temperature of the 8 / 862 / 9721 preblend was 70°C. Mix in a planetary mixer for 3 min at 2,000 rpm and 2 min to remove trapped air. The test was carried out under a vacuum of 5 kPa.

[0081] Each resulting Component A sample was then mixed with Component B (Aradur 3473 epoxy hardener) or "3473") in a two-step mixing process. In the first step, 5°C) Component B is added to Component A (approximately 60°C) using a Cowles blade at 1,100 rpm. The mixture was added for 1.5 minutes under mixing. After this, the mixture was added in the second mixing step using a double planetary mixer. The process was carried out for 3 minutes at 2,000 rpm and a vacuum of 25 kPa to remove trapped air. Then, each of the resulting A+B mixtures (at 45°C + / - 5°C) was pretreated with a release agent. The sample was then poured into a rectangular mold preheated to 60°C. The sample was then heated at 120°C for 2 hours. The mixture was then cured at 160°C for 2 hours, 200°C for 2 hours, and finally at 220°C for 4 hours. The sample was allowed to cool to room temperature. Once cooled, the sample was demolded from the mold and placed on a CNC mill. Tensile specimens were cut using a

[0082] For the carbon-free control sample B0, the 828 / 862 / 9721 preblend was heated to 60°C. The 3473 hardener (25°C) was then heated at 1,100 rpm in a Cowles blower. This mixture was then added under grade mixing for 1.5 minutes. for 3 minutes at 2,000 rpm and a vacuum of 25 kPa to remove trapped air. The resulting mixture was then poured into the same pre-treated and preheated mold, and The composite samples were subjected to the same cure cycle as B1 and B2.

[0083] Table 4 below shows the weight ratios used for samples B0-B2: [Table 4]

[0084] Tensile tests were performed according to ASTM D638 using Type IV specimen dimensions. The tensile specimens were prepared using an Epsilon 3542 extensometer and a 5001b (2224N) Mechanical testing was carried out using a hydraulic universal testing system with a load cell. The universal testing system was 5 m The crosshead speed was constant (m / min). Data were recorded on a Windows PC. A National Instruments USB-6341 data acquisition system was used. The dimensions of the test specimen were measured using a Mitutoyo digital caliper.

[0085] Table 5 below shows the average ultimate tensile strength (UTS), average tensile modulus and average The average elongation at break is given as: [Table 5]

[0086] For each of the functionalized cellular carbon samples, all three tensile properties were The performance was improved compared to the epoxy baseline. This was due to the low-dimensional carbon reinforced polymer. This is particularly noteworthy because the α-based nanocomposites generally exhibit a significant reduction in elongation at break. By optimizing surface chemistry, blending procedures, loading levels and other factors, the presently disclosed It is expected that tensile data on model nanocomposite systems will be further improved. will be done.

[0087] Experiment C The cellular carbon structure can be advantageous for improving the mechanical properties of the polymer, and the multi-cell structure can be advantageous for improving the mechanical properties of the polymer. The formation of a permeable network of hexagonal structures can also improve electrical conductivity at low weight fractions. A total of nine nanocomposite samples (C1 to C2) were prepared using the formulation. C9) were used with S1 cellular carbon, Cabot Vulcan XC72R and XG Sci Sheets were fabricated using ence X-GNP-C-750 at various carbon loading levels. Resistance was tested.

[0088] First, three masterbatch samples (one for each carbon type) were mixed in Epon 828 (“828”) and Araldite LY1556 (“1556”) bifunctional It was prepared with 1.33 wt% carbon in a 1:1 volume ratio preblend of epoxy resin. Disperse the mixture in an IKA high shear rotor-stator mixer at 15,000 rpm for 90 minutes. made him do so.

[0089] Each masterbatch was then diluted with 828 / 1 The carbon was mixed with the 556 preblend and diluted. The final carbon weight fraction of the composite was 0.3%, 0.6%, and 0.9% by weight. The masterbatch and 828 / 1556 preprene were mixed as shown in Table 1. The temperature of the mixture was 60°C. Mixing was carried out in a Thinky double planetary mixer for 3 minutes. , 2,000 rpm and a vacuum of 25 kPa to remove trapped air.

[0090] Each resulting Component A sample was then mixed with Component B (Aradur 34055 epoxy curing agent) The blend was made with the agent "34055" in a two-step mixing process. In the first step, component B was added to component A at 1,100°C. The mixture was added under Cowles blade mixing at 100 rpm for 1.5 minutes. This was followed by a double planetary A second mixing step using a Lee mixer was performed for 3 minutes at 2,000 rpm to remove entrapped air. The test was carried out under a vacuum of 25 kPa to achieve this.

[0091] Then, each of the resulting A+B mixtures (at 40°C + / - 5°C) was pretreated with a release agent. These were allowed to gel at room temperature for 20 minutes and then heated to 60°C. The sample was then cured at 60°C for 4 hours. The curing oven was then turned on at 80°C. The temperature was ramped linearly to 80°C over 15 minutes. The sample was then cured at 80°C for a further 6 hours. Then, the mixture was cooled to room temperature and released from the mold.

[0092] The bottom surface of the sample (the surface in contact with the mold) was then sanded with 600 grit sandpaper. The nanocomposite was then polished with a polishing cloth to reveal a completely clean surface. Apply two parallel 1cm long lines 1cm apart and measure in ohms per square meter. After the silver mud was completely dried, the test piece was placed on the bus bar for electrical resistance measurement ( The test was carried out using a probe set for a two-terminal wire type multimeter for the HT-1000 series. ,One probe was attached to each silver busbar and tested.

[0093] Table 6 below shows the sample compositions and results of the nanocomposite samples prepared in Experiment C. Shows. [Table 6] TIFF2025183292000007.tif77164

[0094] In terms of electrical conductivity, C1 and C6 are electrostatic dissipative materials (i.e., 10 6 ~10 12 Ω / sq), while C2 and C3 are conductive materials (i.e., 10 1 ~10 6 Ω / sq). R s All specimens marked "NR" are Conductive enough to allow conductivity measurements to be taken using a small wire multimeter probe It wasn't.

[0095] The overall result is that cellular carbon is a key component of this simple blending process in model formulations. Uses XC72R carbon black and XGnP-C-750 graphene nanoplates This performance is significantly superior to both the MgO template and the ZnO template. and the recycling of cellular carbon using methods such as those disclosed herein. The cost is theoretically much lower than the manufacturing cost of nanoplatelets or nanotubes. Furthermore, the S3 sample is composed of discrete nanocell particles, On the other hand, some cellular carbons have much larger grain structures with much higher aspect ratios. As an example, nanoarchitects with fibrous or sheet-like morphologies may be used. The carbon foam can be highly conductive based on its aspect ratio.

[0096] There are many potential applications for cellular carbon-filled thermosetting nanocomposites, including printed electrodes. Electronics, multifunctional paints, sensors, conductive composites, and more are possible. The multifunctional combination of mechanical properties and electrical conductivity is useful for some applications, e.g., piezoresistive sensing. It may be beneficial in composites having

[0097] Experiment D In addition to thermosetting polymers, thermoplastics are also used in some applications, especially in conductive coatings. The ability of cellular carbon nanostructures to impart electrical conductivity to thermoplastic resins can be exploited. To demonstrate this capability, a model system was created using chlorinated polyolefin ("CPO"). CPO is a composite of automotive plastics such as polycarbonate, polyester, and polypropylene. Commonly used as a conductive primer for polyethylene, polyurethane, polyamide or blends Such conductive coatings are used by manufacturers to apply paints and coatings electrostatically. This allows for application to plastic parts, thus increasing transfer efficiency. Three nanocomposite samples (D1 to D4) were prepared in the section and applied as coating materials. The wire resistance was tested.

[0098] To prepare the masterbatch carbon dispersion, first disperse 0.75 grams of S3 carbon in 0.75 grams of water. A solution of 98.5 grams of preprene in toluene with a solvent (Byk Chemie, BYK-145) was added. Toluene and BYK-145 were mixed together on a magnetic stirrer. In a 120 ml wide-mouth glass bottle with a stir bar and magnetic stirrer, The S3 powder was added to the preblend and mixed at 0 rpm for 10 minutes. The bottle was then capped and placed in a Branson 3510 Sonication bath. After 1 hour, the lid was opened and the magnetic stirrer was returned to 400 rpm. An ultrasonic probe with a 1 / 2 inch tip was submerged 1 inch below the liquid surface. Attached to the Sonics Vibra-Cell control unit, this probe The amplitude was analyzed until a total energy reading of 75 kilojoules was reached.

[0099] The masterbatch dispersion was then mixed with the CPO solution to give 1%, 2%, 5% and 10% by weight. Four samples (D1-D4) of S3:CPO solid were obtained (see Table 3). Eastman 730-1 20% CPO in xylene. Dispersion and CPO solution The solution was mixed using a magnetic stirrer at 400 rpm for 30 minutes, and then placed in a bath for 1 The mixture was sonicated for 15 minutes and then magnetically stirred again at 400 rpm for another 15 minutes.

[0100] Pipette each coating onto a PET membrane (.007" DuPont Melinex 453) The coatings were then heated at 60°C for 2 hours to form cylindrical coatings of various thicknesses. The samples were oven dried and left at room temperature overnight before testing. Albert Instrument Company Model 89-100 The thickness was measured using a thickness tester. In the comparison test of sheet electrical resistance, A dry film thickness (dft) of 40 um was used for each sample (see Table 2 for results). ) Sheet resistance was measured using a Keithly 2400 SourceMeter 4-terminal probe. was measured using

[0101] Table 7 below shows the sample composition and measurements of the nanocomposite samples prepared in Experiment D. The measured sheet resistance is shown. [Table 7]

[0102] Experiment E A common application for which low-dimensional carbon nanostructures are being investigated is as electrical They are widely used in conductive thin films, anti-fogging films for car windows, and sensors in a variety of applications. The following examples demonstrate how such novel carbon structures formulated in inks can form conductive thin films. Shows the possibility of generating.

[0103] The solution for dispersing carbon was placed in a 20 ml glass scintillation vial. Mix 11 grams of DI water with 5.5 grams of ethanol (industrial grade) Then, modified urea (BYK Chemie GmbH BYK-420 ) was added and the mixture was bath sonicated for 1 hour. TEGO Dispers 760W, add dispersing additive, and set on magnetic for 15 minutes. Stirred.

[0104] Next, 0.3 grams of S3 carbon was added to the mixture. The mixture was then magnetically After stirring, the mixture was sonicated in a bath for 1 hour. The vial was then placed in a water / ice bath. High shear IKA immersion mixer (Ultra-Turrax T) with 8G mixing generator 25) was immersed 1 inch into the mixture. The sample was then heated at 20 kPa min. Mix at -1 for 1 hour in a water bath to prevent the mixture from overheating (approximately <60°C). Ice was replenished.

[0105] The sample was then magnetically stirred at 200 rpm while being sonicated with a 1 / 2 inch tip. The wave probe was immersed 1 inch below the surface. The probe was a Sonics Vibra- Attached to the Cell control unit, this probe measures the total energy at 20% amplitude. The analysis was continued until a reading of 4.5 kilojoules was reached. Capstone FS-63 fluorosurfactant was dissolved in a 1:1 mixture of DI water and ethanol. 0.05 grams of a 5% solution in water was added. Sonication was performed by heating the sample to approximately 60°C. Add ice again to the water bath to maintain below 13.5 kJ total. It continued until.

[0106] The resulting ink was applied to a PET film (0.007" DuPont Teijin Melinex 453) with a pipette, and then using a Meyer Rod RDS8 Spread it into a very thin wet film, and place the wet film in an oven at 120°C for 1 hour to dry the film thoroughly. I did.

[0107] The dried membranes were tested the next day. Total transmittance was calculated using Thermo Scientific Evol ution 60S UV-Visible Spectrophotometer The transmittance reading of the bare substrate was measured to be 64.5% at 550 nm wavelength using a The transmittance of the carbon coating was 73% at 550 nm. The sheet resistance was measured using a 4-point probe (Guardian Industries model The average sheet resistance was measured using a quartz crystal (SRM232-1000). It was measured that.

[0108] Various embodiments The methods and materials presented herein have many potential embodiments. Size, morphology, and surface chemistry templates (e.g., oxide templates) Any carbon-based precursor that can be converted to carbon can be used. can be used as a carbon source. In embodiments involving chemical vapor deposition, various carrier gases can be used. It can be used in combination with precursor gases. Various gas pressures, temperatures, flow rates, reaction times and A reactor type can be used. Templated carbon can be used in multiple CVD reactions, e.g., extraction followed by autocatalysis. Cellular carbon nanostructures may be grown using catalyzed reactions. can be chemically functionalized by, for example, oxygen groups generated by exposure to various oxidizing agents. Such process parameters, including those not shown herein, may be used. Numerous combinations of data may be used in various embodiments of the present invention.

[0109] One embodiment comprises a dispersion of carbon nanostructures in a liquid matrix phase. The phase is one of the following: monomer, resin, prepolymer, polymer, hardener, catalyst, and solvent. The carbon nanostructures include those having a cellular structure, e.g., a cavity, Each cavity is substantially surrounded by one or more walls of the cellular structure. The cavity has a diameter of 10 nm or more. Most of the cavity contains either a liquid or a solid. The chemical composition of the matrix may be similar to or different from that of the external matrix. It may be possible.

[0110] Another embodiment includes a nanocomposite of carbon nanostructures in a liquid matrix phase. The matrix phase is composed of monomers, resins, prepolymers, polymers, hardeners, and catalysts. The carbon nanostructures include one or more of the following: Each cavity is substantially surrounded by one or more walls of the cellular structure. Most of the cavities have diameters of 10 nm or more. Most of the cavities contain either liquid or solid matter. The chemical composition of the matrix may be similar to that of the external matrix. They may be different.

[0111] The following embodiments, numbered consecutively from 1 to 47, are illustrative of various embodiments described herein. A non-exhaustive list of

[0112] Embodiment 1: A liquid matrix phase and nanostructured carbon dispersed in the liquid matrix phase and a dispersion comprising a liquid matrix phase, the liquid matrix phase being a monomer, a resin, a prepolymer, the nanostructured carbon comprising one or more of a polymer, a curing agent, and a catalyst; : One or more walls having a structure formed by a template; One or more cavities and each cavity is substantially surrounded by one or more walls. and a dispersion in which a portion of the matrix phase is impregnated.

[0113] Embodiment 2: A majority of the one or more walls have a thickness of 100 nm or less; The majority of cavities have diameters of 10 nm or more; linear structures and asperities smaller than 10:1. non-linear structures and aspect ratios greater than 10:1; or non-linear structures and 1 and an aspect ratio of less than 0:1; and a majority of the cellular structure is 1 mm 2. The dispersion of embodiment 1, having the following diameter:

[0114] Embodiment 3: The structure of the one or more walls is formed by the template. Any of embodiments 1 and 2, wherein the portion is physically or chemically modified to be different from the portion One dispersion.

[0115] Embodiment 4: The physical alteration disrupts or deforms the structural portion of the one or more walls. The dispersion of embodiment 3, wherein

[0116] Embodiment 5: The deformation of the structure substantially collapses the one or more cavities. The dispersion of embodiment 4.

[0117] Embodiment 6: Any of embodiments 1-5, wherein a portion of the nanostructured carbon comprises single-cell particles. One dispersion.

[0118] Embodiment 7: Any of embodiments 1-6, wherein a portion of the nanostructured carbon comprises multi-cell particles. One dispersion.

[0119] Embodiment 8: The method of any one of embodiments 1 to 7, wherein the matrix phase further comprises a solvent. Dispersion.

[0120] Embodiment 9: Any of Embodiments 1-8, wherein the matrix phase comprises a thermoplastic polymer. One dispersion.

[0121] Embodiment 10: Any of Embodiments 1-9, wherein the matrix phase comprises an epoxy-functional resin. One of the dispersions.

[0122] Embodiment 11: The matrix phase is selected from the following list: amines, phenols, thiols, 11. The composition of claim 1, further comprising one or more curing agents selected from Lewis acids or acid anhydrides. Any one dispersion.

[0123] Embodiment 12: The matrix phase comprises a polyolefin or a modified polyolefin. The dispersion of any one of embodiments 1 to 11.

[0124] Embodiment 13: Embodiments 1-12, wherein the matrix phase comprises urea or modified urea A dispersion of any one of the above.

[0125] Embodiment 14: The portion of the nanostructured carbon has a Raman 2-D / G peak intensity of 0.40 or less. 14. The dispersion of any one of embodiments 1 to 13, wherein the ratio is

[0126] Embodiment 15: The portion of the nanostructured carbon has a Raman 2-D / G peak intensity of 0.20 or less. 15. The dispersion of any one of embodiments 1 to 14, wherein the ratio is

[0127] Embodiment 16: A portion of the nanostructured carbon is synthesized by template-directed chemical vapor deposition. 16. The dispersion of any one of embodiments 1 to 15, wherein

[0128] Embodiment 17: The template-directed chemical vapor deposition is carried out at a temperature of less than 800°C. The dispersion of any one of embodiments 1 to 16.

[0129] Embodiment 18: An embodiment in which a portion of the nanostructured carbon is functionalized with chemical functional groups. A dispersion of any one of forms 1 to 17.

[0130] Embodiment 19: The method of embodiment 18, wherein the chemical functional groups are covalently bonded to the nanostructured carbon. Dispersion.

[0131] Embodiment 20: The dispersion of embodiment 19, wherein the chemical functionality is an oxygen functionality.

[0132] Embodiment 21: The cavity contains at least one component that is chemically different from the matrix. 21. The dispersion of any one of embodiments 1 to 20, which is partially filled.

[0133] Embodiment 22: A liquid matrix phase and nanostructuring dispersed in the liquid matrix phase and carbon, wherein the liquid matrix phase is selected from the group consisting of monomers, resins, prepolymers, and the like. the nanostructure comprising two or more of a polymer, a curing agent, a catalyst, and a solvent; The carbonized material may be: one or more walls with a structure formed by a template; one or more a cellular structure having cavities, each cavity being substantially enclosed by one or more walls; and the ink is partially impregnated with the matrix phase.

[0134] Embodiment 23: An additive for improving the properties of a material, comprising: a liquid matrix phase and the and nanostructured carbon dispersed in a liquid matrix phase, the liquid matrix The phases may be one or more of the following: monomer, resin, prepolymer, polymer, hardener, and catalyst. the nanostructured carbon comprises: a template-formed structure; a cellular structure having one or more walls; and one or more cavities, each cavity The matrix phase is: substantially surrounded by the one or more walls; and partially impregnated with the matrix phase. Additives.

[0135] Embodiment 24: The additive of embodiment 23, wherein the property is a mechanical property or an electrical property.

[0136] Embodiment 25: A solid matrix phase and nanostructuring embedded in the solid matrix phase and carbon, wherein the solid matrix phase is a mixture of monomers, resins, polymers, and the like. the nanoparticles include one or more of a copolymer, a polymer, a curing agent, and a catalyst; Structured carbon is: one or more walls with structures formed by a template; one or more The present invention relates to a cellular structure having a plurality of cavities, each cavity being formed by one or more walls. a nanocomposite that is qualitatively surrounded by a matrix phase; and partially impregnated with the matrix phase.

[0137] Embodiment 26: A majority of the one or more walls have a thickness of 100 nm or less; and the one or more The majority of cavities have diameters of 10 nm or more; linear structures and asymmetric structures smaller than 10:1. aspect ratio; non-linear structures and aspect ratios greater than 10:1; or non-linear structures and and an aspect ratio of less than 10:1; and a majority of the cellular structure is 1 m 26. The nanocomposite of embodiment 25, having a diameter of less than or equal to 1 m.

[0138] Embodiment 27: The structure of the one or more walls is formed by the template. Any of embodiments 25-26, wherein the structure is physically or chemically modified to be different from the original structure. or one nanocomposite.

[0139] Embodiment 28: The physical alteration disrupts or deforms the structural portion of the one or more walls. The nanocomposite of embodiment 27.

[0140] Embodiment 29: The deformation of the structure substantially collapses the one or more cavities. 29. The nanocomposite of embodiment 28.

[0141] Embodiment 30: The method of any of embodiments 25-29, wherein a portion of the nanostructured carbon comprises single-cell particles. Either one nanocomposite.

[0142] Embodiment 31: The method of any of embodiments 25-30, wherein a portion of the nanostructured carbon comprises multicellular particles. Either one nanocomposite.

[0143] Embodiment 32: Any of Embodiments 25-31, wherein the polymer comprises a thermoplastic polymer. One nanocomposite.

[0144] Embodiment 33: Any of Embodiments 25-32, wherein the polymer comprises a thermosetting polymer. One nanocomposite.

[0145] Embodiment 34: The nanocomposite of embodiment 33, wherein the thermosetting polymer is partially cured. tt.

[0146] Embodiment 35: Any of Embodiments 33-34, wherein the thermosetting polymer comprises an epoxy. One nanocomposite.

[0147] Embodiment 36: An embodiment wherein the epoxy comprises a diglycidyl ether of bisphenol A. Nanocomposite of state 35.

[0148] Embodiment 37: A material having a higher ultimate tensile strength, a higher tensile elasticity than that of the material containing the matrix phase. High elongation at break, high GIC critical strain energy release rate, high maximum bending strength, high bending At least one of high flexural modulus, high ultimate compressive strength, high compressive modulus, high hardness or high impact strength 37. The nanocomposite of any one of embodiments 25 to 36, showing at least one.

[0149] Embodiment 38: An experimental method for producing a composite material comprising a matrix phase, the composite exhibiting a KIC fracture toughness higher than that of a material comprising the matrix phase. The nanocomposite of any one of embodiments 25 to 37.

[0150] Embodiment 39: An embodiment that exhibits higher electrical conductivity than that of the material comprising the matrix phase. Nanocomposite of any one of states 25 to 38.

[0151] Embodiment 40: An embodiment in which a portion of the nanostructured carbon is functionalized with a chemical functional group. Nanocomposite of any one of states 25 to 39.

[0152] Embodiment 41: The method of embodiment 40, wherein the chemical functional groups are covalently attached to the nanostructured carbon. Nanocomposites.

[0153] Embodiment 42: Any one of embodiments 40-41, wherein the chemical functional group is an oxygen functional group. Nanocomposite.

[0154] Embodiment 43: The cavity contains at least one component that is chemically different from the matrix. 43. The nanocomposite of any one of embodiments 25 to 42, which is partially filled.

[0155] Embodiment 44: The nanocomposite of any one of embodiments 25 to 43, further comprising a fiber reinforcing phase. Composite.

[0156] Embodiment 45: The method of any of embodiments 25-44, wherein the fiber reinforcement phase comprises chopped fibers. Either one nanocomposite.

[0157] Embodiment 46: A solid matrix phase and nanostructuring dispersed in the solid matrix phase and carbon, wherein the solid matrix phase is selected from the group consisting of monomers, resins, prepolymers, and the like. the nanostructure comprises one or more of a polymer, a polymer, a curing agent, and a catalyst; The structured carbon is: one or more walls with a structure formed by a template; one or more a cellular structure having cavities, each cavity being substantially a membrane or coating that is substantially surrounded by a matrix phase; and that is partially impregnated with the matrix phase.

[0158] Embodiment 47: A solid matrix phase and nanostructuring dispersed in the solid matrix phase A molded casting comprising carbon, wherein the solid matrix phase is a monomer, a resin, a prepolymer, or the like. the nanostructured carbon comprises one or more of a polymer, a curing agent, and a catalyst; The element is: one or more walls with a structure formed by a template; one or more cavities The cavity has a cellular structure with a cavity, each cavity being substantially surrounded by the one or more walls. and a molded casting in which a portion of the matrix phase is impregnated.

[0159] The words "less than," "greater than," "up to," " References to "at least," "less than," "more than" or other similar terms mean that the term is It is intended to apply to each value or parameter in a series of values ​​or parameters, e.g. , the statement that the weight percent of oxygen may be less than 1%, 0.5%, or 0.1% The weight percent of oxygen may be less than 1%, less than 0.5%, or less than 0.1%. is intended to mean that

[0160] This application discloses several numerical ranges in the text and figures. Even if strict range limitations are not literally set forth in the document, the present disclosure is not intended to limit the scope of the invention to the disclosed numerical values. The disclosed numerical ranges are intended to be illustrative and not restrictive, as the entire range may be practiced. Supports ranges or values ​​within the range.

[0161] The above description is presented to enable any person skilled in the art to make or use the disclosure. Various modifications to the present embodiment will be readily apparent to those skilled in the art and may be implemented in accordance with the principles set forth herein. The general principles may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Accordingly, the present disclosure is not intended to be limited to the illustrated embodiments. rather, it is intended to accord the widest scope consistent with the principles and features disclosed herein. Finally, the entire disclosures of the patents and publications referred to in this application are hereby incorporated by reference. It will be incorporated into the specification.

[0162] References TIFF2025183292000009.tif190158TIFF2025183292000010.tif179162

Claims

1. a liquid matrix phase; nanostructured carbon dispersed in said liquid matrix phase; A dispersion comprising: The liquid matrix phase may comprise a monomer, a resin, a prepolymer, a polymer, a hardener, and catalysts; The nanostructured carbon comprises: one or more walls having features formed by the template; One or more cavities wherein each cavity comprises: being substantially surrounded by said one or more walls; Impregnated with a portion of the matrix phase Dispersion.

2. a majority of said one or more walls having a thickness of 100 nm or less; said one or more cavities Most of the: a diameter of 10 nm or greater; Linear structure and aspect ratio less than 10:1; non-linear structure and an aspect ratio greater than 10:1; or Non-linear structure and aspect ratio less than 10:1 One of the having a majority of the cellular structures having a diameter of 1 mm or less; The dispersion of claim 1 .

3. The structure of the one or more walls is formed by the template.

10. The dispersion of claim 1, which is differently physically or chemically modified.

4. The physical alteration disrupts or deforms the structural portion of the one or more walls. The dispersion of claim 3 .

5. 5. The method of claim 4, wherein deformation of the structure substantially collapses the one or more cavities. The dispersion according to claim 1.

6. The dispersion of claim 1 , wherein a portion of the nanostructured carbon comprises single-cell particles.

7. The dispersion of claim 1 , wherein a portion of the nanostructured carbon comprises multi-cell particles.

8. The dispersion of claim 1 , wherein the matrix phase further comprises a solvent.

9. The dispersion of claim 1 , wherein the matrix phase comprises a thermoplastic polymer.

10. The dispersion of claim 1 , wherein the matrix phase comprises an epoxy-functional resin.

11. The matrix phase may be selected from the following list: amines, phenols, thiols, Lewis acids or 10. The dispersion of claim 1, wherein the at least one curing agent is selected from an acid anhydride.

12. 2. The method of claim 1, wherein the matrix phase comprises a polyolefin or a modified polyolefin. The dispersion is as described above.

13. The dispersion of claim 1 , wherein the matrix phase comprises urea or modified urea.

14. a portion of said nanostructured carbon exhibiting a Raman 2-D / G peak intensity ratio of 0.40 or less; 2. The dispersion of claim 1.

15. a portion of said nanostructured carbon exhibiting a Raman 2-D / G peak intensity ratio of 0.20 or less; 2. The dispersion of claim 1.

16. a portion of said nanostructured carbon is synthesized by template-directed chemical vapor deposition; 2. The dispersion of claim 1.

17. 10. The method of claim 1, wherein the template-directed chemical vapor deposition is performed at a temperature below 800°C.

7. The dispersion according to claim 6.

18. 10. The composition of claim 1, wherein a portion of the nanostructured carbon is functionalized with a chemical functional group. Scattered body.

19. 20. The dispersion of claim 18, wherein the chemical functional groups are covalently bonded to the nanostructured carbon. 。

20. 20. The dispersion of claim 19, wherein the chemical functionality is an oxygen functionality.

21. The cavity is at least partially filled with a component that is chemically different from the matrix. The dispersion of claim 1 which is filled.

22. a liquid matrix phase; nanostructured carbon dispersed in said liquid matrix phase; An ink comprising: The liquid matrix phase may comprise a monomer, a resin, a prepolymer, a polymer, a hardener, a catalyst, or the like. and a solvent; The nanostructured carbon comprises: one or more walls having features formed by the template; One or more cavities wherein each cavity comprises: being substantially surrounded by said one or more walls; Impregnated with a portion of the matrix phase ink.

23. 1. An additive for improving the properties of a material, comprising: a liquid matrix phase; nanostructured carbon dispersed in said liquid matrix phase; It contains The liquid matrix phase may comprise a monomer, a resin, a prepolymer, a polymer, a hardener, and catalysts; The nanostructured carbon comprises: one or more walls having features formed by the template; One or more cavities wherein each cavity comprises: being substantially surrounded by said one or more walls; Impregnated with a portion of the matrix phase Additives.

24. 24. The additive of claim 23, wherein the property is a mechanical property or an electrical property.

25. a solid matrix phase; nanostructured carbon embedded in said solid matrix phase; A nanocomposite comprising: The solid matrix phase may comprise a monomer, a resin, a prepolymer, a polymer, a hardener, and catalysts; The nanostructured carbon comprises: one or more walls having features formed by the template; One or more cavities wherein each cavity comprises: being substantially surrounded by said one or more walls; Impregnated with a portion of the matrix phase Nanocomposites.

26. a majority of said one or more walls having a thickness of 100 nm or less; said one or more cavities Most of the: a diameter of 10 nm or greater; Linear structure and aspect ratio less than 10:1; non-linear structure and an aspect ratio greater than 10:1; or Non-linear structure and aspect ratio less than 10:1 One of the having a majority of the cellular structures having a diameter of 1 mm or less; 26. The nanocomposite of claim 25.

27. The structure of the one or more walls is formed by the template.

26. The nanocomposite of claim 25, which is differently physically or chemically modified. to.

28. The physical alteration disrupts or deforms the structural portion of the one or more walls.

28. The nanocomposite of claim 27.

29. 3. The method of claim 2, wherein the deformation of the structure substantially collapses the one or more cavities.

9. The nanocomposite according to claim 8.

30. 26. The nanocomposite of claim 25, wherein a portion of the nanostructured carbon comprises single-cell particles. 。

31. 26. The nanocomposite of claim 25, wherein a portion of the nanostructured carbon comprises multi-cell particles. 。

32. 26. The nanocomposite of claim 25, wherein the polymer comprises a thermoplastic polymer.

33. 26. The nanocomposite of claim 25, wherein the polymer comprises a thermosetting polymer.

34. 34. The nanocomposite of claim 33, wherein the thermosetting polymer is partially cured.

35. 35. The nanocomposite of claim 34, wherein the thermosetting polymer comprises an epoxy.

36. 36. The epoxy of claim 35, wherein the epoxy comprises a diglycidyl ether of bisphenol A. Nanocomposites.

37. Higher ultimate tensile strength, higher tensile modulus, and higher fracture toughness than materials containing the matrix phase High ultimate bending strength, high bending modulus, high elongation at break, high GIC critical strain energy release rate At least one of high ultimate compressive strength, high compressive modulus, high hardness, or high impact strength.

26. The nanocomposite of claim 25, wherein:

38. 26. The method of claim 25, wherein the material exhibits a KIC fracture toughness higher than that of a material containing the matrix phase. Nanocomposite.

39. 26. The method of claim 25, which exhibits an electrical conductivity higher than that of a material comprising the matrix phase. Nanocomposites.

40. 26. The method of claim 25, wherein a portion of the nanostructured carbon is functionalized with a chemical functional group. Nanocomposites.

41. 41. The nanostructured carbon of claim 40, wherein the chemical functional groups are covalently bonded to the nanostructured carbon. Composite.

42. 42. The nanocomposite of claim 41, wherein the chemical functional groups are oxygen functional groups.

43. The cavity is at least partially filled with a component that is chemically different from the matrix.

26. The nanocomposite of claim 25, wherein the nanocomposite is filled.

44. 26. The nanocomposite of claim 25, further comprising a fiber reinforcing phase.

45. 45. The nanocomposite of claim 44, wherein the fiber reinforcement phase comprises chopped fibers. 。

46. a solid matrix phase; nanostructured carbon dispersed in said solid matrix phase; A membrane or coating comprising: The solid matrix phase may comprise a monomer, a resin, a prepolymer, a polymer, a hardener, and catalysts; The nanostructured carbon comprises: one or more walls having features formed by the template; One or more cavities wherein each cavity comprises: being substantially surrounded by said one or more walls; Impregnated with a portion of the matrix phase Membrane or covering.

47. a solid matrix phase; nanostructured carbon dispersed in said solid matrix phase; A molded casting comprising: The solid matrix phase may be one or more of a monomer, a resin, a prepolymer, a polymer, Contains a curing agent and a catalyst; The nanostructured carbon comprises: one or more walls having features formed by the template; One or more cavities wherein each cavity comprises: being substantially surrounded by said one or more walls; Impregnated with a portion of the matrix phase Molded castings.

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