CA2979220C - Method of co-processing nanocarbons in carbon black, and products therefrom - Google Patents

Abstract

Provided herein is a method of forming a composition by co-processing nanocarbon aggregates and carbon black aggregates, which includes providing nanocarbon aggregates, providing carbon black aggregates, and mixing the nanocarbon aggregates and the carbon black aggregates such that the nanocarbon aggregates disperse into looser aggregates of nanocarbons and carbon black, or individualized nanocarbons dispersed among the carbon black aggregates.

Description

METHOD OF CO-PROCESSING NANOCARBONS IN CARBON BLACK, AND
PRODUCTS THEREFROM
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefits of U.S. Provisional Application Nos. 62/133,256 filed on March 13, 2015, and 62/177,212 filed on March 10, 2015.
SUMMARY

[0002] Provided herein is a method of dispersing nanocarbons into carbon black.
In examples discussed below, nanocarbons, such as nanotubes, graphene, buckyballs, nanohorns, etc., and carbon black can be mixed together to facilitate integration of nanocarbons and carbon black. The mixture of nanocarbons and carbon black can assist in dispersion of the nanocarbons into the carbon black, and also assist in dispersion of the mixture of the nanocarbons and carbon black within a medium, such as an elastomer.

[0003] Also provided herein is a method of dispersing nanocarbons and carbon black into a polymer, such as rubber or a thermoplastic. This method can include pre-processing the nanocarbons and carbon black into "loosened" aggregates, and then combining the loosened aggregates with the polymer. By combining the loosened aggregates with the polymers, improved properties of the nanocarbon-carbon black-polymer product can be achieved.
[0003a] Also provided herein is a method of forming a matrix composition by:
providing a matrix; providing a co-processed nanocarbon-carbon black dispersion consisting essentially of: co-processing nanocarbon agglomerates and carbon black agglomerates, comprising: providing nanocarbon agglomerates, wherein nanocarbons in the nanocarbon agglomerates have a diameter of less than 50 nm; providing carbon black agglomerates; and mixing the nanocarbon agglomerates and the carbon black agglomerates such that the nanocarbon agglomerates disperse into: a nanocarbon-carbon black dispersion with looser agglomerates of nanocarbons and carbon black; or a nanocarbon-carbon black dispersion with individualized nanocarbons dispersed among the carbon black agglomerates; and combining the matrix and the co-processed nanocarbons-carbon black dispersion to form the matrix composition.

Date Recue/Date Received 2022-04-06 [0003b] Also provided herein is a method of making a nanocarbon-carbon black dispersion, comprising: providing agglomerated nanocarbons; providing carbon black;
and mixing the agglomerated nanocarbons with carbon black in an essentially dry state and applying sufficient shear force for a sufficient time to render the agglomerate structure of the nanocarbons unobservable by scanning electron microscope (SEM) at a magnification of 100,000x or less.
[0003c] Also provided herein is a method of a dispersion of nanocarbons in carbon black, comprising: nanocarbon aggregates with a maximum cross-section or diameter of less than 50 nm; and carbon black aggregates, wherein the nanocarbon aggregates are dispersed in carbon black aggregates such that individual nanocarbons are observable by SEM.
[0003d] Also provided herein is a method of a composition comprising: a co-processed material consisting essentially of nanofibers with a diameter of less than 50 nm and carbon black; and a polymeric matrix material, wherein the co-processed material is formed by mixing the nanofibers and carbon black to co-process the mixture into individualized nanofibers and/or loosened agglomerates of nanofibers and carbon black, and wherein the co-processed material is incorporated within the polymeric matrix material.
[0003e] Also provided herein is a method of forming a composition by co-processing nanocarbon aggregates and carbon black aggregates, comprising:
providing nanocarbon aggregates with a maximum cross-section or diameter of less than 50nm;
and mixing the nanocarbon aggregates and the carbon black aggregates such that individual carbon nanotubes release from said nanocarbon aggregates, as confirmed by electron microscopy, wherein the co-processing consists essentially of a total of 100 wt.% of nanocarbon aggregates and carbon black aggregates, wherein 50 wt.% or less nanocarbon aggregates and 50 wt.% or more carbon black aggregates.
[0003f] Also provided herein is a method of a dispersion of carbon fibers and carbon black, comprising: carbon fibers aggregates; and carbon black aggregates, wherein the carbon black aggregates disperse carbon fibers in the carbon fiber aggregates, and wherein each carbon fiber and each carbon fibers aggregate in the dispersion consist essentially of carbon nanotubes having a cross-section or a diameter of less than 50 nm.
la Date Recue/Date Received 2022-04-06 [0003g] Also provided herein is a method of a dispersion of carbon fibers and carbon black, comprising: nanocarbon aggregates; and carbon black aggregates, wherein the carbon black aggregates disperse nanocarbon aggregates in the carbon fiber aggregates, wherein the dispersion is free of continuous carbon fibers with a diameter of greater than 50 nm, and wherein the nanocarbon aggregates consist of multiwalled carbon nanotubes with a diameter less than 50 nm in cross-section or diameter.
BRIEF DESCRIPTION OF THE DRAWINGS

[0004] The accompanying drawings, which are incorporated and constitute a part of this specification, illustrate example embodiments of the claimed invention. In the drawings,

[0005] Figs. 1A-1B are scanning electron microscope (SEM) micrographs of carbon nanotubes;

[0006] Figs. 2A-2B are SEM micrographs of carbon black; and

[0007] Figs. 3-16 are SEM micrographs of samples of co-processed nanocarbons and carbon black under different conditions.
lb Date Recue/Date Received 2022-04-06 DETAILED DESCRIPTION

[0008] The following detailed description refers to the accompanying drawings. The same reference numbers in different drawings may identify the same or similar elements. Also, the following detailed description describes embodiments of the invention and is not intended to limit the invention.

[0009] A. Overview

[0010] While not wishing to be bound by any theory, it is believed that carbon black within carbon black agglomerates, which has primary particles in the same size range as individual nanocarbons in nanocarbon agglomerates, is able to affix itself via electrostatic or mechanical forces (because of its irregular structure) to the individual nanocarbons. These forces cause the individual nanocarbons to de-agglomerate from their original nanocarbon aggregates. Once de-agglomerated, the individualized nanocarbons are of a particular size that is able to fit within an interstitial space between the individual carbon black particles and agglomerates, such that the carbon black keeps individual nanocarbons apart from other individual nanocarbons. In other words, it is believed that the close contact between the nanocarbons and carbon black, as well as the shear forces acting within a small area provided by physical co-processing, causes the de-agglomeration and maintenance of individuality of the individualized nanocarbons.

[0011] B. Nanocarbons

[0012] The term "nanocarbons" is intended to refer to nano-sized carbons, which can include carbon nanotubes, nanographenic carbons, buckyballs and nanohorns. Carbon nanotubes are a preferred form of nanocarbon.

[0013] In general, the use of prefix "nano," as used in nanocarbons and nanographenic carbons, implies that at least one dimension of the material is less than 100 nm, and can include material on the size scale of at least one dimension being less than 1 micron, less than 0.5 microns, less than 0.2 microns, less than 100 nm, less than 50 nm, less than 20 nm, or less than 5 nanometers. Nanocarbons generally also have desirable properties, such as, high surface area and electrical conductivity; see, for example, basic properties of carbon nanotubes.

[0014] Nanocarbons can exist in a variety of forms and can be prepared through the catalytic decomposition of various carbon-containing gases at metal surfaces. These include those described in U.S. Patent No. 6,099,965 to Tennent, etal. and U.S. Patent No. 5,569,635 to Moy, et al..

[0015] In an embodiment, nanocarbons can be made by catalytic growth from hydrocarbons or other gaseous carbon compounds, such as CO, mediated by supported or free floating catalyst particles.

[0016] As produced, nanocarbons may be in the form of discrete nanocarbons (i.e., separated individual nanocarbons), aggregates/agglomerates of nanocarbons (i.e., dense, entangled nanocarbons), or a mixture of both. Aggregates of nanocarbons may be dense particulate structures of entangled nanocarbons.

[0017] Aggregates can be formed during the production of nanocarbons, where the morphology of the aggregate can be influenced by the choice of catalyst support. Porous supports with completely random internal texture, e.g., fumed silica or fumed alumina, can grow nanocarbons in all directions leading to the formation of aggregates.

[0018] As used herein, nanocarbon agglomerates are composed of multiple nanocarbon aggregates, which adhere to one another or otherwise form a unitary agglomeration of numerous aggregates. Nanocarbon aggregates can retain their structure in nanocarbon agglomerates.

[0019] Nanocarbons also differ physically and chemically from other forms of carbon such as standard graphite and carbon black. Standard graphite is, by definition, flat shaped rather than fibrous. Carbon black is an amorphous structure of irregular shape, generally characterized by the presence of both sp2 and sp3 bonding. On the other hand, nanocarbons have one or more layers of ordered graphitic carbon atoms. These differences, among others, make graphite and carbon black poor predictors of nanocarbon-polymer structure properties.

[0020] One form of nanocarbon is a carbon nanotube. The terms "carbon nanotube," "fibril," "nanofibers," and "nanotube" are used interchangeably to refer to single wall (Le., only a single graphene layer parallel to the nanotube axis) and/or multi-wall (i.e., more than one graphene layer more or less parallel to the nanotube axis) carbon nanotubes, which may additionally be functionalized or have an outer Date Recue/Date Received 2022-04-06 layer of less structured amorphous carbon (note, other forms of nanocarbons can also be functionalized if desired).

[0021] Carbon nanotubes have an elongated structure with a cross-section (e.g., angular fibers having edges) or a diameter (e.g., rounded) of, for example for multi-wall carbon nanotubes, less than 100 nm, preferably less than 50 nm, more preferably less than 20 nm; or, for example for single wall nanotubes, less than 5 nanometers. Other types of carbon nanotubes are also known, such as fishbone fibrils (e.g., wherein the graphene sheets are disposed in a herringbone pattern with respect to the nanotube axis), "buckytubes," etc.

[0022] Aggregates of carbon nanotubes may resemble the morphology of bird nest ("BN"), cotton candy ("CC"), combed yarn ("CY"), open net ("ON"), or other conformations. Carbon nanotubes may also be grown on a flat support, attached by one end to the support and parallel to each other, forming a "forest"
structure.

[0023] Individual carbon nanotubes in aggregates may be oriented in a particular direction (e.g., as in "CC," "CY," and "ON" aggregates) or may be non-oriented (i.e., randomly oriented in different directions, for example, as in "BN"
aggregates). "BN" structures may be prepared as disclosed in U.S. Patent No.
5,456,897. "BN" agglomerates are tightly packed with typical densities of greater than 0.08 g/cc, for example, 0.12 g/cc. Transmission electron microscopy ("TEM") reveals no true orientation for carbon nanotubes formed as "BN" agglomerates.
Patents describing processes and catalysts used to produce "BN" agglomerates include U.S. Patent Nos. 5,707,916 and 5,500,200.

[0024] Figs. lA and 1B are SEM micrographs of carbon nanotubes. As illustrated in Figs. 1A and 1B, carbon nanotubes (BN type in Fig. 1A and CC
type in Fig. 1B) show carbon nanotube agglomerate structures. As made carbon nanotube agglomerates have not been successfully de-agglomerated in a dry state.
Rather, de-agglomeration in this context indicates either the creation of substantial numbers of individualized tubes or the essentially complete absence of the as-made agglomerates. Even de-agglomeration in a liquid phase can require the use of Date Recue/Date Received 2022-04-06 substantial energy sources, such as ultrasound. See U.S. Patent No. 5,691,054.

[0025] On the other hand, "CC," "ON," and "CY" agglomerates have lower density, typically less than 0.1 g/cc, for example, 0.08 g/cc and their TEMs reveal a preferred orientation of the nanotubes. U.S. Patent No. 5,456,897 describes the production of these oriented agglomerates from catalyst supported on planar supports. "CY" may also refer generically to aggregates in which the individual carbon nanotubes are oriented, with "CC" aggregates being a more specific, low density form of "CY" aggregates.

[0026] Carbon nanotubes are distinguishable from commercially available so called "continuous carbon fibers" (i.e., commercially available, larger than nanotube-sized carbon fibers). For instance, the diameter of continuous carbon fibers, which is always greater than 1.0 micron and typically 5 to 7 microns, is also far larger than that of carbon nanotubes, which is usually less than 1.0 micron. Due to their smaller size, carbon nanotubes often have increased conductivity than carbon fibers for the same amount provided as additive to polymers.

[0027] Carbon nanotubes, as used herein, may be used in their as-made agglomerated form, or they may be pre-treated by, for example, mortar and pestle, ball mill, rod mill, hammer mill, etc. to reduce the maximum size of the agglomerates.
Additionally, the as-made nanotubes maybe washed in a strong acid or strong base to dissolve any catalyst and support from which the carbon nanotubes are grown, such as, for example, phosphoric acid.

[0028] Another form of nanocarbon is nanographenic carbon. The term "nanographenic carbons" is intended to refer to nano-sized carbons, which can include carbons having nanoscale and graphenic structure. For example, nanographenic carbons can include graphite of a nanoscopic scale, but would not include graphite of macroscopic scale. One type of nanographenic carbon, graphene, or graphite nanoparticles, can be described as one or more sheets of graphitic carbon. For example, graphene can include a single sheet of graphitic carbon, or nanoplatelets with a few sheets of carbon. Graphene can be on the same order of size as carbon nanotubes, as mentioned above, with a structure having a dimension in one direction of less than 1 micron, less than 0.5 microns, less than 0.2 Date Recue/Date Received 2022-04-06 microns, less than 100 nm, less than 50 nm, less than 20 nm, or less than 5 nanometers.

[0029] Another form of nanocarbon is a buckyball. Buckyballs, also known as buckminsterfullerenes, are carbons arranged in a spherical structure resembling a ball. Buckyballs are made of 60 carbon atoms and have a dimension on the order of 1 to 2 nm.

[0030] Another form of nanocarbon is a nanohorn. Nanohorns are horn-shaped aggregates of stacks of graphene sheets. Carbon nanotubes, both single and multi-wall are included within the category of nanohorns, as they are made of one or more graphene sheets. Nanohorns also have a structure having a dimension in one direction of less than 1 micron, less than 0.5 microns, less than 0.2 microns, less than 100 nm, less than 50 nm, less than 20 nm, or less than 5 nanometers.

[0031] C. Carbon black

[0032] The term "carbon black" is intended to include a carbon powder with carbon aggregates of various sizes. In general, carbon black aggregates can be difficult to disperse due to its strong attractions between adjacent particles. Due to the difficulty in dispersing carbon black particles from carbon black aggregates, carbon black particles have been subjected to similar treatment to nanocarbons for dispersion, such as shear mixing within a medium, dry shearing, and wet shearing, as mentioned above concerning nanocarbons.

[0033] Carbon blacks are named according to an ASTM standard used by all manufacturers. Carbon blacks can also be characterized by their porosity.
Carbon black porosity is discussed in Porosity in Carbons, Patrick, J.W. ed., Halsted Press 1995.

[0034] Discussion of dispersion of carbon black agglomerates can be found, for example, in the literature. See Pomchaitawarda etal., "Investigation of the dispersion of carbon black agglomerates of various sizes in simple-shear flows,"
Chem. Eng. Sci. 58 (2003), pp. 1859¨ 1865.

[0035] Figs. 2A and 2B are SEM micrographs of carbon black from different sources. Fig. 2A is Cabot Sterling 1120 carbon black as supplied from Cabot Corporation, Boston, MA at 100,000x magnification. Fig. 2B is Continental Carbon N330 as supplied from Continental Carbon Company, Houston, TX at 200,000x Date Recue/Date Received 2022-04-06 magnification. As shown in Fig. 2A and 2B, the carbon black as supplied are aggregated.

[0036] D. Co-processed Nanocarbons and Carbon Black

[0037] Co-processed nanocarbons and carbon black were prepared at varying concentrations, as well as using different methods to facilitate co-processing. By co-processing nanocarbons and carbon black, dispersion of nanocarbon aggregates into carbon black aggregates can be observed. Specifically, co-processing can result in looser nanocarbon aggregates and individualized nanocarbons, as further discussed below.

[0038] In embodiments provided below, compositions of the mixtures of nanocarbons and carbon black can vary from 0.001 wt.% to 99.999 wt.%
nanocarbons (with 99.999 wt.% to 0.001 wt.% carbon black). For example, 2 wt.%

to 50 wt.% nanocarbons can provide dispersion of nanocarbons in carbon black, such as 50 wt.% or less nanocarbon aggregates and 50 wt.% or more carbon black aggregates, 30 wt.% or less nanocarbon aggregates and 70 wt.% or more carbon black aggregates, or 10 wt.% or less nanocarbon aggregates and 90 wt.% or more carbon black aggregates. As another example, 5 wt.% to 50 wt.% nanocarbons can provide individualization of nanocarbons in carbon black.

[0039] In U.S. Patent No. 8,771,630 Wu et al. describe graphene and a method for the preparation of graphene. In this patent, graphene dispersion is discussed, as is graphene generally.

[0040] In a paper by Singh, etal., "Polymer-Graphene Nanocomposites:
Preparation, Characterization, Properties, and Applications," Nanocomposites -New Trends and Developments, Ebrahimi, F. (Ed.), InTech (2012) Singh etal. further discuss carbon allotropes, such as graphite, diamond, fullerene, and carbon nanotube. Singh et al. discuss that "the fabrication of single-layer graphene is difficult at ambient temperature ... [because] graphene sheets with a high surface area tend to form irreversible agglomerates and restacks to form graphite through p-p stacking and Vander Waals interactions." See, p. 38 middle of the first full paragraph. Singh etal. further discuss methods of forming graphene. See also Li, et al., "Processable aqueous dispersions of Date Recue/Date Received 2022-04-06 graphene nanosheets," Nature Nanotechnology, 3(2), (2008) 101-105; and Park etal., "Hydrazine-reduction of graphite- and graphene oxide," Carbon 49 (2011) 3019-3023.

[0041] As discussed below, by co-processing nanocarbons in carbon black, aggregates can be disrupted, and individual nanocarbons can be observed in a SEM.

[0042] While not wishing to be bound by theory, it is believed that co-processing of nanocarbons and carbon blacks can lead initially to loosening of the nanocarbon aggregates. The loosening of the nanocarbon aggregates can appear to be "cloud"-like large, loosened aggregates that can be observable in a SEM.

Further processing can convert these loosened aggregates into individual nanocarbons, which can also be observed in a SEM. These loosened aggregates can have a nanocarbon to nanocarbon distance greater than that of the starting material's nanocarbon to nanocarbon distance. For example, in carbon nanotube loosened aggregates, carbon nanotubes can be separated by a distance of about nanotubes or about 100nm, as observed in the samples discussed below.

[0043] For example, in carbon nanotube aggregates, these "cloud"-like co-processed carbon nanotube-carbon black may be differentiated from the starting as-made carbon nanotube aggregates by the separation of the carbon nanotubes from other carbon nanotubes within a carbon nanotube-carbon black aggregate.

[0044] Co-processing of nanocarbons and carbon black may be carried out in a dry state or a wet state. Dry state co-processing may be preferred as the process may require fewer steps due to the addition and removal of liquid. Wet state co-processing, on the other hand, may be preferred if the nanocarbons, carbon black, or both are provided in wetted form. For example, if carbon nanotubes and carbon black are provided in wetted form, co-processing in a wet state may require fewer steps, and may be preferable.

[0045] In the case of wet pre-processing, the nanocarbon and carbon black may be added to the liquid in any order or the liquid may be added to the nanocarbon and carbon black again in any order. The quantity of liquid employed may range from 0.10 lbs. to 100 lbs. of liquid per lb. of mixed solids depending on Date Recue/Date Received 2022-04-06 the type of pre-processing equipment to be used. Any liquid may be used, but water is a preferred liquid. Organic liquids as well as supercritical media, such as supercritical 002, may also be used. After pre-processing most of the added liquid may be readily removed, such as via decanting, from the processed solids.
Final liquid removal is preferably by volatilizing residual liquid from the solids.

[0046] Dry co-processing can be carried out in any type of equipment or combination of such equipment used for intimately mixing dry powders, such as ball mills, both tumbling and stirred, rod mills, mortar and pestles, Banbury mixers, two and three roll mills, Waring blenders and similar stirred equipment, both with and without the presence of added media.

[0047] Wet co-processing can employ any of the types of equipment used for dry pre-processing as well as jet mills, including microfluidizers, and agitated vessels of any sort with any type of impeller.

[0048] Depending on the intended use of the nanocarbon-carbon black mixture the individualization step may take place in the co-processing step just described or it may occur in a subsequent compounding step in the presence of polymer or other material. This compounding step may be carried out in any of the known types of equipment used for compounding additives into polymers including extruders, such as twin screw extruders and single screw extruders, Banbury mixers, Brabender mixers, two and three roll mills, etc.

[0049] Also in embodiments provided below, dispersion methods, such as physical mixing can be utilized to disperse nanocarbons in carbon black. For example, mortar and pestle (hand or motorized), shakers (with or without media added), and tumblers (with or without media) are discussed below in the embodiments, but other mechanical means can be also be used.

[0050] Table summarizes some examples of co-processing nanocarbons and carbon blacks. As shown in the Table below, the nanocarbon source and morphology, the carbon black and morphology, the ratio of nanocarbon to carbon black, the type of equipment, the mixing parameters, such as time, intensity, etc., can affect the resulting co-processed nanocarbon-carbon black products.

[0051] Table Sample Figure Composition Device Time 1 Not shown 10% graphene in Motorized mortar and pestle 30 min.
N330 (M&P) 2 Not shown 5% graphene in Steel tumbler with 4 hrs. at N330 Polyamide (PA) 12 media 120 rpm 3 3 10% Ground CC Shaker 4 hrs.
+ 1120 4 4 10% Ground CC Hand M&P 1 hr.
+ 1120 5 10% CC + 1120 Shaker 1 hr.
6 6 10% BN + 1120 Plastic tumbler with PA 12 4 hrs.
7 7 10% Ground CC "
+ 1120 8 8A, 8B 30% Ground CC Hand M&P 30 min.
+ 1120 9 9 5% BN + 1120 Plastic tumbler with PA 12 "
10 2% BN + 1120 "
Li 11 11 5% CC + N330 "
12 Not shown 5% BN + 1120 Ceramic "rod mill" 2 hrs. at 60 rpm 13 Not shown 10% BN + N330 Steel tumbler with PA 12 4 hrs. at 120 rpm 14 Not shown 10% BN + N330 Teflon tumbler with steel 2 hrs. at media 120 rpm 12 5% CC + N330 "
Li 16 13 30% BN + N330 "
17 14 10% BN + N330 Waring blender 10 min.
18 15 10% BN + N330 Sample 17, motorized M&P 10 min.
19 Not shown 10% BN + N330 Brabender mixer 1 hr.
16 10% BN + N330 Wet in 3 roll mill 5 passes

[0052] Sample 1 is formed from 10% graphene in N330 with 0.30g of as-received xGnP graphene nanoplatelets (Grade M, XG Sciences, Inc.) is mixed with 2.70g of carbon black N330 (Columbian Chemicals Co.). The mixture is ground with a motorized mortar and pestle (Model: Retsch, Brinkmann, Type: RMO) for 30 min.

[0053] Sample 2 is formed from 5% graphene in N330 by mixing 0.10g of as-received xGnP graphene nanoplatelets (Grade M, XG Sciences, Inc.) with 1.90g of carbon black N330 (Columbian Chemicals Co.). The mixture is loaded to a tumbler made from steel pipe equipped with a baffle along with lOg of PA12 (polyamide 12) granules (2-6mm OD) as grinding media and tumbled with a roller (Model: Tru-Square Metal Products) at 120rpm for 4 hrs.

[0054] Examination of the samples 1 and 2 in a SEM reveals that the graphene nanoplatelets are well dispersed in carbon black. Individual nanoplatelets can be observed in each of samples 1 and 2 within the SEM.

[0055] Sample 3 is formed by combining of 0.10g carbon nanotubes (CC
conformation; previously ground in a Fitzpatrick hammer mill, herein after referred to as "ground CC") and 0.90g Cabot Sterling 11 20 carbon black in a stainless steel cylinder. The cylinder was shaken at high frequency with a Retsch Brinkmann Shaker at the setting of 60 for 4 hrs.

[0056] Fig. 3 is a SEM micrograph of sample 3 at 50,000x magnification showing numerous individual nanotubes and loosened aggregates. The agglomerate structure of the carbon black appears to be essentially unchanged.

[0057] Sample 4 is formed by co-processing 0.10g of as made ground carbon nanotube powder with 0.90g of Cabot Sterling NS 1120 carbon black by hand grinding with mortar and pestle at room temperature for 1 hr. Samples were prepared for the SEM by the procedure used in sample 3.

[0058] Fig. 4 is a SEM micrograph of sample 4 at 100,000x magnification of the co-processed carbon nanotube powder and carbon black. As shown in Fig. 4, numerous individualized carbon nanotubes are observable because the carbon nanotubes are dispersed in the carbon black.

[0059] Sample 5 is formed by co-processing 0.1g of as made CC carbon nanotubes and 0.90g Cabot Sterling 1120 carbon black under the same conditions (equipment and time) as sample 3.

[0060] Fig. 5 is a SEM micrograph of sample 5 at 100,000x magnification showing a loosened aggregate that appears to be a "cloud"-like structure over a half a micron long, and about 200nm wide.

[0061] Sample 6 is formed by co-processing 0.1g as made BN carbon nanotubes and 0.90g Cabot Sterling 1120 carbon black in a plastic tumbler with irregular spherical (2-6mm OD) PA 12 media therein at 120 rpm for 4 hrs.

[0062] Fig. 6 is a SEM micrograph of sample 6 at 100,000x magnification showing numerous loosened carbon nanotube aggregates.

[0063] Sample 7 is formed by co-processing 0.1g of as made ground CC
carbon nanotubes and 0.90g Cabot Sterling 1120 carbon black under the same conditions as sample 6.

[0064] Fig. 7 is a SEM micrograph of sample 7 at 50,000x magnification showing the presence of loosened aggregates with "cloud"-like structures over a micron in length.

[0065] Sample 8 is formed by co-processing 0.3g of as made CC carbon nanotubes and 0.70g Cabot Sterling 1120 carbon black by hand grinding using a mortar and a pestle for 30 minutes.

[0066] Figs. 8A-8B are SEM micrographs of sample 8 at different magnifications. As shown in Fig. 8A, numerous loosened aggregates are present at 50,000x magnification. As shown in Fig. 8B, numerous individual nanotubes are shown at 100,000x magnification. As before the structure of the carbon black aggregate seems unchanged.

[0067] Sample 9 is formed by co-processing 0.05g BN carbon nanotubes with 0.95g Cabot Sterling 1120 carbon black, and sample 10 is formed by co-processing 0.02g BN carbon nanotubes with 0.98g Cabot Sterling 1120 carbon black using a plastic tumbler with PA12 media therein at 120 rpm for 4 hrs.

[0068] Figs. 9 and 10 are SEM micrographs of samples 9 and 10, respectively, illustrate individual nanotubes and loosened aggregates at 100,000x magnification.

[0069] Sample 11 is formed by co-processing 0.10g CC carbon nanotubes and 1.90g Continental N330 carbon black by hand grinding using a mortar and pestle for 30 min. Again, individual nanotubes are observed at 100,000x magnification, as shown in Fig. 11.

[0070] Sample 12 is formed by co-processing 2.50g of as-made BN carbon nanotubes with 47.50g of Cabot Sterling 1120 carbon black. The mixture is loaded in a ceramic jar together with ceramic rods for tumbling at 60 rpm for 2 hrs (the volume of the small marshmallow-like rods is about half of the jar volume).
Shortened nanotubes are observed (not shown).

[0071] Sample 13 is co-processed by tumbling with a steel pipe equipped with a baffle. A mixture of 2.0g 10 wt.% BN in carbon black N330 (Columbian) was charged into the pipe along with lOg of PA12 granules. The tumbler was rolled at 120 rpm for 4 hours. The SEM image of sample 13, which is not provided, displayed a similar set of individual nanotubes as those of Samples 9 and 10 (Figs. 9 and 10) with no agglomerates observed.

[0072] Sample 14 is co-processed by loading 2.0g of 10 wt.% BN in carbon black N330 was charged to a Teflon bottle along with stainless steel balls (1/8' OD) (the volume of the steel ball is about 50% of the bottle volume) and tumbled at 120 rpm for 2 hrs. At 100,000x magnification, the presence of individual tubes and no agglomerates was observed similar to Figs. 9 and 10, and thus are not provided.
The carbon black aggregate structure appeared unchanged.

[0073] Sample 15 is co-processed from 0.05g CC carbon nanotubes and 0.95g of carbon black N330 (Columbian) by mixing together in a mortar and pestle for 30 minutes.

[0074] Fig. 12 is a SEM micrograph of sample 15 at 198,000x magnification shows the presence of both individual nanotubes and loosened aggregate structures approaching a micron in length. The carbon black aggregate structure appears unchanged.

[0075] Sample 16 is co-processed from 0.3g of BN carbon nanotubes and 0.7g of carbon black N330 by hand grinding the combination in a mortar and pestle for 30 minutes.

[0076] Fig. 13 is a SEM micrograph of sample 16 at 200,000x magnification.
Individualized nanotubes are prominent and no aggregates are seen. Carbon black aggregate structure appears unchanged.

[0077] Sample 17 is co-processed by adding 5g of as made BN powder and 45g of N330 carbon black to a Waring Blender (Model: Blender 7012G, made by Waring Commercial, Torrington, CT) and processing at the lowest speed for 10 minutes. Density was measured as 0.39 g/cc.

[0078] Fig. 14 is a SEM micrograph of sample 17 at 100,000x magnification and shows individualized carbon nanotubes in a carbon black aggregate structure, which appears unchanged.

[0079] Sample 18 was co-processed by first processing 5g of as made BN
powder and 45 g of N330 carbon black together in a Waring blender for 10 minutes at low speed (as was done in sample 17). The resulting mixture was then transferred to a motorized mortar and pestle and further processed for 10, 20 and 30 minutes to finalize the co-processed material. Tap density falls in 10 minutes to 0.31 g/cc. at 20 minutes of processing a sample is withdrawn and prepared for microscopy as previously.

[0080] Fig. 15 is a SEM micrograph of sample 18 after 20 minutes of further processing at 200,000x magnification showing the presence of individual nanotubes in a carbon black aggregate structure, which appears unchanged.

[0081] Sample 19 was co-processed by lightly mixing with a spatula 10 wt.%
as made BN nanotubes and 90wt. /0 N330 carbon black. 19 g of the mixture is transferred to the twin screw mixing head of a Brabender mixer (Model: Plasti-Corder DR-2052-K13, manufactured by C.W. Brabender Instruments, Inc., So. Hackensack, NJ) designed to simulate the action of a Banbury-type mixer. The mixture is processed at 100 rpm for one hour. Tap density falls to 0.28 g/cc. Both individualized nanotubes and loosened aggregates are observed. As sample 19 appeared similar to sample 18 (Fig. 14), sample 19's SEM micrograph is not provided.

[0082] Sample 20 is prepared by mixing 5.0g of the 10 wt.% BN/N330 mix prepared in sample 19 above with 7g of deionized water to form a wet paste material. The wet paste material is passed five times through a three roll mill (Model:

Keith 27502, manufactured by Keith Machinery Corp., Lindenhurst, NY), which results in a thin film, which in turn is dried at 100 C in vacuum oven.

[0083] Fiq. 16 is a SEM micrograph of sample 20 at 100,000x magnification, which shows the presence of individual nanotubes.

[0084] As shown herein, co-processed nanocarbons and carbon black can provide loosened aggregates and/or individualized nanocarbons, such as individualized carbon nanotubes. These loosened aggregates and/or individualized nanocarbons can be used to provide improved dispersion of nanocarbons and/or carbon black in a matrix, such as polymers or other materials. Suitable matrix materials include polymers, both organic and inorganic, metals, ceramics, and other non-polymer matrices, such as asphalt, cement, or glass. Example polymers include thermosets, such as vulcanizeable rubber, polyurethanes, epoxy resins, polyimides, etc., or thermoplastics, such as polyolefins, acrylics, nylons, polycarbonates, etc.
Combining polymers with the co-processed nanocarbons and carbon black can provide improved properties in polymers, such as improved modulus, elongation, etc.

[0085] One of ordinary skill in the art would expect the presence of individualized nanotubes and the absence of large tight aggregates to lead to composites with improved properties, such as tensile modulus, toughness, hardness, durometer, resistance to explosive delamination, tear resistance, relaxation time, etc., without sacrifice of elongation to break.

[0086] In addition to the co-processed nanocarbons and carbon black in a matrix, additional additives, such as inert fillers and active agents, can also be provided. For example, inert fillers, such as glass, pumice, etc., and/or active agents, such as vulcanization activators, release agents, antioxidants, inks or other colorants, etc., can be added to the co-processed nanocarbons and carbon black in a matrix before, during, or after the nanocarbon-carbon black loosened aggregates are added to the matrix.

[0087] While the invention has been described in detail with reference to preferred embodiments thereof, it will be apparent to those skilled in the art that variations and modifications can be made, and equivalents employed without departing from the scope of the appended claims.

Claims (23)

CLAIMS:

1. A method of forming a matrix composition by:
providing a matrix;
providing a co-processed nanocarbon-carbon black dispersion consisting essentially of:
co-processing nanocarbon agglomerates and carbon black agglomerates, comprising:
providing nanocarbon agglomerates, wherein nanocarbons in the nanocarbon agglomerates have a diameter of less than 50 nm;
providing carbon black agglomerates; and mixing the nanocarbon agglomerates and the carbon black agglomerates such that the nanocarbon agglomerates disperse into: a nanocarbon-carbon black dispersion with looser agglomerates of nanocarbons and carbon black; or a nanocarbon-carbon black dispersion with individualized nanocarbons dispersed among the carbon black agglomerates; and combining the matrix and the co-processed nanocarbons-carbon black dispersion to form the matrix composition.

2. The method of claim 1, wherein the providing the co-processed nanocarbon-carbon black dispersion consists essentially of providing:
50 wt.% or less nanocarbon agglomerates and 50 wt.% or more carbon black agglomerates; 30 wt.% or less nanocarbon agglomerates and 70 wt.% or more carbon black agglomerates; or 10 wt.% or less nanocarbon agglomerates and 90 wt.% or more carbon black agglomerates, wherein the composition consists essentially of the matrix, nanocarbons with a diameter of 50 nm or less, and carbon black.

3. The method of claim 1, wherein the providing the nanocarbon agglomerates comprises providing multiwall carbon nanotube agglomerates, wherein the nanocarbons-carbon black dispersion has an aggregate size of less than 1pm.

4. A method of making a nanocarbon-carbon black dispersion, comprising:
providing agglomerated nanocarbons;

Date Recue/Date Received 2022-04-06 providing carbon black; and mixing the agglomerated nanocarbons with carbon black in an essentially dry state and applying sufficient shear force for a sufficient time to render the agglomerate structure of the nanocarbons unobservable by scanning electron microscope (SEM) at a magnification of 100,000x or less.

5. The method of claim 4, wherein the providing the agglomerated nanocarbons comprises providing multiwall carbon nanotube agglomerates.

6. A dispersion of nanocarbons in carbon black, comprising:
nanocarbon aggregates with a maximum cross-section or diameter of less than 50 nm; and carbon black aggregates, wherein the nanocarbon aggregates are dispersed in carbon black aggregates such that individual nanocarbons are observable by SEM.

7. The dispersion of claim 6, wherein the nanocarbon aggregates comprises multiwalled carbon nanotube aggregates.

8. A composition comprising:
a co-processed material consisting essentially of nanofibers with a diameter of less than 50 nm and carbon black; and a polymeric matrix material, wherein the co-processed material is formed by mixing the nanofibers and carbon black to co-process the mixture into individualized nanofibers and/or loosened agglomerates of nanofibers and carbon black, and wherein the co-processed material is incorporated within the polymeric matrix material.

9. The composition of claim 8, wherein the nanofibers comprise carbon nanotubes, and the co-processed material has agglomerates that are less than 1 pm.

10. The composition of claim 8, wherein the composition comprises:
the polymeric matrix material, and the co-processed material incorporated within the polymeric matrix material, wherein the co-processed material consists essentially of:
50 wt.% or less nanofibers with a diameter of 50 nm or less and 50 wt.%
or more carbon black; 30 wt.% or less nanofibers with a diameter of 50 nm or less and Date Recue/Date Received 2022-04-06 70 wt.% or more carbon black; or 10 wt.% or less nanofibers with a diameter of 50 nm or less and 90 wt.% or more carbon black.

11. The composition of claim 8, wherein the matrix material comprises an organic polymer, metal, ceramic, cement, or asphalt.

12. The composition of claim 11, wherein the matrix material is an organic polymer, and the organic polymer comprises a rubber or a thermoplastic.

13. The composition of claim 8, wherein the co-processed material comprises loosened agglomerates of nanofibers and carbon black, and wherein the loosened agglomerates are formed by mixing nanofiber agglomerates with carbon black agglomerates with sufficient force or energy to form the loosened agglomerates of nanofibers and carbon black; and/or wherein the co-processed material comprises individualized nanofibers within a carbon black aggregate, and wherein the individualized nanofibers within the carbon black aggregate are formed by mixing nanofiber agglomerates with carbon black agglomerates with sufficient force or energy to form the individualized nanofibers within the carbon black.

14. A method of forming a composition by co-processing nanocarbon aggregates and carbon black aggregates, comprising:
providing nanocarbon aggregates with a maximum cross-section or diameter of less than 50nm; and mixing the nanocarbon aggregates and the carbon black aggregates such that individual carbon nanotubes release from said nanocarbon aggregates, as confirmed by electron microscopy, wherein the co-processing consists essentially of a total of 100 wt.% of nanocarbon aggregates and carbon black aggregates, wherein 50 wt.%
or less nanocarbon aggregates and 50 wt.% or more carbon black aggregates.

15. The method of claim 14, wherein the co-processing comprises:
co-processing a total of 100 wt.% of nanocarbon aggregates and carbon black aggregates, wherein 30 wt.% or less nanocarbon aggregates and 70 wt.% or more carbon black aggregates.

16. The method of claim 14, wherein the co-processing comprises:

Date Recue/Date Received 2022-04-06 co-processing a total of 100 wt.% of nanocarbon aggregates and carbon black aggregates, wherein 10 wt.% or less nanocarbon aggregates and 90 wt.% or more carbon black aggregates.

17. The method of claim 14, wherein the nanocarbon aggregates comprise multiwalled carbon nanotubes.

18. A dispersion of carbon fibers and carbon black, comprising:
carbon fibers aggregates; and carbon black aggregates, wherein the carbon black aggregates disperse carbon fibers in the carbon fiber aggregates, and wherein each carbon fiber and each carbon fibers aggregate in the dispersion consist essentially of carbon nanotubes having a cross-section or a diameter of less than 50 nm.

19. The dispersion of claim 18, wherein the carbon nanotubes comprise multiwalled carbon nanotubes.

20. A dispersion of carbon fibers and carbon black, comprising:
nanocarbon aggregates; and carbon black aggregates, wherein the carbon black aggregates disperse nanocarbon aggregates in the carbon fiber aggregates, wherein the dispersion is free of continuous carbon fibers with a diameter of greater than 50 nm, and wherein the nanocarbon aggregates consist of multiwalled carbon nanotubes with a diameter less than 50 nm in cross-section or. diameter.

21. The dispersion of claim 20, wherein the nanocarbon aggregates consist of multiwalled carbon nanotubes.

22. The dispersion of claim 20, wherein the nanocarbon aggregates consist of multiwalled carbon nanotubes with a diameter less than 1 micron in cross-section or diameter.

23. The dispersion of claim 20, wherein the nanocarbon aggregates consist of multiwalled carbon nanotubes with at least one dimension being less than 0.5 microns.

Date Recue/Date Received 2022-04-06