KR20170127487A - A method of co-treating nanocarbon in carbon black, and a product obtained therefrom - Google Patents

Abstract

A method of producing a composition by co-treating a nano carbon aggregate and a carbon black aggregate, comprising the steps of providing a nanocarbon aggregate, providing a carbon black aggregate, and mixing the nanocarbon agglomerate and the carbon black agglomerate, Dispersing the carbon nanotubes into looser aggregates of carbon and carbon black, or allowing the individualized nanocarbon to be dispersed in the carbon black aggregates.

Description

A method of co-treating nanocarbon in carbon black, and a product obtained therefrom

Reference description for related application

This application claims priority to U.S. Provisional Application No. 62 / 133,256, filed March 13, 2015, and 62 / 177,212, filed March 10, 2015, each of which is incorporated herein by reference.

The present invention provides a method of dispersing nano carbon in carbon black. In the examples discussed below, nanocarbon and carbon black such as nanotubes, graphene, buckyball, nanohorn, etc. can be mixed together to promote the integration of nanocarbon and carbon black. A mixture of nanocarbon and carbon black may help disperse the nanocarbon within the carbon black and may also help disperse the mixture of nanocarbon and carbon black in a medium such as an elastomer.

The present invention also provides a method of dispersing nanocarbon and carbon black in polymers such as rubber or thermoplastic materials. The method may include pretreatment of the nanocarbon and carbon black to "loose" agglomerates and then blending the loose aggregates with the polymer. By combining loose aggregates and polymers, improved properties of nanocarbon-carbon black-polymer products can be achieved.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate exemplary aspects of the claimed invention. In the drawings,
Figures 1 a and 1 b are scanning electron microscope (SEM) micrographs of carbon nanotubes;
Figures 2a and 2b are SEM micrographs of carbon black;
Figures 3 to 16 are SEM micrographs of nanocarbon and carbon black samples co-treated under different conditions.

The following detailed description refers to the following figures. Like reference numbers in the different drawings may identify the same or similar elements. In addition, the following detailed description is intended to illustrate aspects of the invention and is not intended to limit the invention.

A. Overview

Without wishing to be bound by any theory, it is believed that the carbon black in the carbon black agglomerate with the main particles of the same size range as the individual nano carbon in the nano carbon agglomerate can be separated by electrostatic or mechanical forces It is thought that it can attach itself to nano carbon. These forces de-agglomerate individual nano-carbons from the initial nanocarbon agglomerates. Once disaggregated, the individual nanocarbon is a particle size that can fit within the space between the individual carbon black particles and the agglomerates so that the carbon black keeps the individual nanocarbon separate from the other individual nanocarbon. In other words, the close contact between the nanocarbon and the carbon black, and the shear force acting in the small region provided by the physical co-processing, are believed to lead to the retention of disintegration and maintenance of the individuality of the individualized nanocarbon .

B. Nano Carbon

The term "nano carbon" is intended to refer to nano-sized carbon, which may include carbon nanotubes, nano-graphene carbon, buckyballs and nanohorns. Carbon nanotubes are a preferred form of nanocarbon.

In general, the use of the prefix "nano ", as used in nanocarbon and nano-graphene carbons, implies that at least one dimension of the material is less than 100 nm, and at least one size dimension is less than 1 micron, less than 0.5 micron, Less than 100 nm, less than 50 nm, less than 20 nm, or less than 5 nanometers. Nanocarbon is generally also desirable in properties such as high surface area and electrical conductivity; For example, refer to the basic properties of carbon nanotubes.

Nanocarbon can exist in various forms and can be prepared through catalytic cracking of various carbon-containing gases on metal surfaces. Examples include those described in U.S. Patent 6,099,965 (Tennent, et al.), And U.S. Patent 5,569,635 (Moy, et al.), Each of which is herein incorporated by reference in their entirety.

According to one embodiment, the nanocarbon can be prepared by catalytic growth from hydrocarbons or other gaseous carbon compounds, such as CO, mediated by supported or free-standing type catalyst particles.

When produced, the nanocarbon can be in the form of a separated nanocarbon (ie, separate individual nanocarbon), a nanocarbon agglomerate / agglomerate (ie, tightly entangled nanocarbon), or a mixture of both. Agglomerates of nanocarbons can be dense, particulate structures of entangled nanocarbons.

Aggregates can be formed during the production of nanocarbon, wherein the shape of the agglomerates can be influenced by the selected catalyst support. Porous supports with a completely irregular internal texture, such as fumed silica or fumed alumina, can grow nanocarbon in all directions to form aggregates.

As used herein, nanocarbon aggregates consist of a plurality of nanocarbon agglomerates that adhere to each other or form a single agglomerate of multiple agglomerates. Nano carbon agglomerates can maintain their structure within nanocarbon aggregates.

In addition, nanocarbon is physically and chemically distinct from other types of carbon, such as standard graphite and carbon black. Standard graphite is, by definition, flat rather than fibrous. Carbon black is an irregular shaped amorphous structure, and is generally characterized by the presence of sp2 and sp3 bonds. On the other hand, the nanocarbon has one or more regular graphite carbon atomic layers. This difference, among other things, makes graphite and carbon black a poor predictor of nano-carbon-polymer structure properties.

One form of nanocarbon is carbon nanotubes. The term "carbon nanotubes "," fibrils ", "nanofibers ", and" nanotubes "refer to a single wall (i.e. a single graphene layer parallel to the nanotube axis) and / Is meant to be used interchangeably to mean carbon nanotubes in which more than one graphene layer is more or less parallel to the tube axis, which may additionally be functionalized or may have an outer layer of less structured amorphous carbon ( Note that, if necessary, other forms of nanocarbon can be functionalized).

The carbon nanotubes may have a cross-sectional area (e.g., angular fibers) or diameters (e.g., round), for example, in the case of multi-walled carbon nanotubes, less than 100 nm, preferably less than 50 nm, more preferably less than 20 nm ; Or, for example, in the case of single-walled nanotubes, a three-elongated structure of less than 5 nanometers. Other types of carbon nanotubes are also known, such as fulgidal fibrils (e.g., graphene sheets are arranged in a herringbone pattern with respect to the nanotube axes), "bucky tubes ", and the like.

Aggregates of carbon nanotubes may be similar to the forms of birds ("BN"), cotton candy ("CC"), comas ("CY"), open networks ("ON" Carbon nanotubes can also be grown on a flat support, one end of which is attached to the support and parallel to each other to form a "forest" structure.

The individual carbon nanotubes in the aggregate can be elongated in a particular direction (e.g., in "CC", "CY" and "ON" aggregates), or unextracted (ie, . The "BN" structure can be prepared as disclosed in U.S. Patent 5,456,897, which is incorporated herein by reference in its entirety. The "BN" agglomerates are typically packed densely with a density of greater than 0.08 g / cc, such as 0.12 g / cc. Transmission electron microscopy ("TEM") does not reveal the true orientation of carbon nanotubes formed as a "BN" Patents describing the methods and catalysts used to produce the "BN" agglomerates include U.S. Patent Nos. 5,707,916 and 5,500,200, which are incorporated herein by reference in their entirety.

1A 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) exhibit a carbon nanotube aggregate structure. The prepared carbon nanotube aggregates did not successfully decolorize in the dry state. Rather, decontamination in this situation represents the production of a significant number of individualized tubes or nearly complete absence of the manufactured agglomerates. In particular, scavenging in the liquid phase may require the use of considerable energy sources such as ultrasound. See U.S. Patent 5,691,054, co-owned and cited herein.

On the other hand, the "CC", "ON" and "CY" agglomerates have lower densities, generally less than 0.1 g / cc, eg 0.08 g / cc, and their TEMs indicate the preferred orientation of the nanotubes. U.S. Patent No. 5,456,897, the disclosure of which is incorporated herein by reference, describes the production of said oriented agglomerates from a catalyst supported on a flat support. Also, "CY" can generally refer to aggregates in which each carbon nanotube is oriented, and "CC" aggregates are more specific low density forms of "CY" aggregates.

Carbon nanotubes are distinguished from so-called "continuous carbon fibers" (i.e., fibers larger than carbon nanotube-sized carbon fibers available in the market) available in the market. For example, the diameter of continuous carbon fibers is always greater than 1.0 micron, typically 5 to 7 microns, and much larger than carbon nanotubes usually less than 1.0 micron. Because of this small size, carbon nanotubes often exhibit increased conductivity over the same amount of carbon fiber provided as an additive to the polymer.

The carbon nanotubes used in the present invention may be used as they are in the form of the aggregate produced, or may be pretreated with a mortar, ball mill, rod mill, hammer mill or the like to reduce the maximum size of the agglomerates. The prepared nanotubes can also be washed with a strong acid such as phosphoric acid or a strong base to dissolve the support and the optional catalyst on which the carbon nanotubes grow.

Another form of nanocarbon is nanographed carbon. The term "nanograping carbon" is intended to mean nano-sized carbon which may include carbon with nanoscale and graphene structures. For example, nanographed carbon may contain nano-scale graphite, but not macroscopic graphite. One type of nano-grained carbon, graphene or graphite nanoparticles can be described as one or more sheets of graphitic carbon. For example, graphene may comprise a single sheet of nanoplatelet, or graphite carbon, with several carbon sheets. Graphene can be of the same dimension as the carbon nanotubes described above, with dimensions in one direction less than 1 micron, less than 0.5 microns, less than 0.2 microns, less than 100 nanometers, less than 50 nanometers, less than 20 nanometers, or less than 5 nanometers have.

Another form of nanocarbon is buckyball. Buckyballs, also known as buckminsterfullerenes, are carbon arranged in a spherical structure resembling a ball. The buckyball consists of 60 carbon atoms and is about 1-2 nm in size.

Another form of nanocarbon is nanohorn. Nanohorns are horn-shaped agglomerates of a graphene sheet stack. Carbon nanotubes are included in the class of nanohorns because they are made of at least one graphene sheet in both single wall and multiple wall. In addition, the nanophone is a structure with dimensions in one direction less than 1 micron, less than 0.5 micron, less than 0.2 micron, less than 100 nm, less than 50 nm, less than 20 nm, or less than 5 nanometers.

C. carbon black

The term "carbon black" is meant to include carbon agglomerates of various sizes and carbon powder. In general, carbon black agglomerates can be difficult to disperse due to strong attraction between adjacent particles. Due to the difficulty of dispersing the carbon black particles from the carbon black agglomerates, the carbon black particles are subjected to a treatment similar to the nanocarbon, such as shear mixing in the medium, dry shear and wet shear, I did it together.

Carbon black was named according to the ASTM standard used by all manufacturers. In addition, carbon black may be characterized by its porosity. Carbon black porosity is described in Porosity in Carbons, Patrick, J.W. ed., Halsted Press 1995].

A discussion of the dispersion of carbon black agglomerates can be found, for example, in the literature. For example, Pomchaitawarda et al., "Investigation of the Dispersions of Carbon Black Agglomerates of Various Sizes in Simple Shear Flows ", Chem. Eng. Sci. 58 (2003), pp. 1859-1865.

2A and 2B are SEM micrographs of carbon blacks of different feedstock. 2A is a Cabot Sterling 1120 carbon black (100,000x magnification) supplied by Cabot Corporation (MA, Boston). 2B is a Continental Carbon N330 (200,000x magnification) supplied by Continental Carbon Company of TX, Houston. As shown in Figs. 2A and 2B, the supplied carbon black is agglomerated.

D. Co-treated nano carbon and carbon black

Co-treated nanocarbon and carbon black were prepared at various concentrations as well as using other methods to promote co-treatment. By co-treating the nano carbon and the carbon black, it is possible to observe the dispersion of the nano carbon aggregates into the carbon black aggregate. Specifically, the cavitation treatment can result in looser nanocarbon agglomerates and individualized nanocarbon as described in more detail below.

According to aspects provided below, the composition of the mixture of nanocarbon and carbon black may vary from 0.001 wt% to 99.999 wt% nanocarbon (99.999 wt% to 0.001 wt% carbon black). For example, 2 wt% to 50 wt% nanocarbon can provide dispersion of nanocarbon in the carbon black, for example, 50 wt% or less of nanocarbon agglomerates, 50 wt% or more of carbon black agglomerates, 30 wt% or less of nanocarbon agglomerates, % Carbon black agglomerates, or 10 wt% or less of nano carbon agglomerates and 90 wt% or more of carbon black agglomerates. As another example, 5 to 50 wt% nanocarbon may provide for individualization of nanocarbon in the carbon black.

In U.S. Patent No. 8,771,630, which is incorporated herein by reference, Wu et al. Describe a method of making graphene and graphene. In this patent, graphene dispersion is generally discussed as graphene.

InTech (2012), incorporated herein by reference), which is incorporated herein by reference in its entirety, by Singh et al. [Polymer-Graphene Nanocomposites: Preparation, Characterization, Properties, and Applications, Nanocomposites - New Trends and Developments, Ebrahimi, F. Singe et al. Further discuss carbon isotopes such as graphite, diamond, fullerene, and carbon nanotubes. Singh et al. "The assembly of single-layer graphenes is difficult at room temperature, because high-surface-area graphene sheets form irreversible aggregates and restacks, resulting in pp lamination and Van der Waals interactions (Li, et al., "Processable aqueous dispersions of graphene ", " Processes < RTI ID = 0.0 > , " Hydrosine-reduction of graphite- and graphene oxide ", Carbon 49 (2011) 3019-3023 (1999), " Nanosheets ", Nature Nanotechnology, 3 (2) See also reference).

As discussed below, by co-treating the nanocarbon in the carbon black, the aggregate can collapse and individual nanocarbon can be observed in the SEM.

Although not intending to be bound by theory, the co-treatment of nanocarbon and carbon black may first cause nanocarbon agglomerates to loosen. The loosening of nanocarbon agglomerates can be seen as a "cloud" like large and loose aggregates observed in SEM. Such loose aggregates may have a spacing of nanocarbon to nanocarbon greater than the nanocarbon to nanocarbon spacing of the starting material. For example, in agglomerates in which carbon nanotubes are loosened, carbon nanotubes may be separated by about 10 nanotubes or at intervals of about 100 nm, as observed in the samples discussed below.

For example, in a carbon nanotube aggregate, cavitated carbon nanotube-carbon black such as "clouds " is a carbon that is initially produced by separation of carbon nanotubes and other carbon nanotubes in carbon nanotube- Can be distinguished from nanotube aggregates.

The co-treatment of nanocarbon and carbon black can be carried out in a dry or wet state. Dry-state cavitation may be desirable because this process requires fewer steps due to the addition and removal of liquids. On the other hand, the wet state cavity treatment may be desirable if the nanocarbon, carbon black or both are provided in a wetted form. For example, if the carbon nanotubes and the carbon black are provided in a wetted form, the co-treatment in the wet state may require fewer steps, which may be desirable.

In wet pretreatment, 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. Depending on the type of pretreatment apparatus used, the amount of liquid used may vary from 1 lb. Per liter liquid 0.10 lbs. To 100 lbs. Lt; / RTI > Although any liquid may be used, water is the preferred liquid. As well as organic liquids, supercritical media, such as supercritical CO ₂ , may also be used. After the pretreatment, the added liquid can most easily be removed from the treated solid, such as by decanting. The final liquid removal is preferably accomplished by volatilization of the residual liquid from the solid.

The dry co-treatment may be carried out using any type of apparatus used to finely blend anhydrous powders or a combination of such devices, such as ball mills, tumbling and agitating roll mills, mortar bowls, Banbury mixers, 2 rolls and 3 roll mills, Waring blender and similar stirring devices (both in the presence and absence of additional media).

The wet co-treatment may utilize any kind of apparatus used in the dry pretreatment, as well as any type of stirred vessel with a jet mill, such as a microfluidizer, and any kind of impeller.

Depending on the intended use of the nano carbon-carbon black mixture, the individualization step may occur during the co-treatment step just described, or may take place in the subsequent compounding step in the presence of a polymer or other material. Such compounding steps may be carried out in any known type of apparatus used to formulate additives in the polymer, such as extruders such as twin-screw extruders and single screw extruders, Banbury mixers, Brabender mixers, 2 rolls and 3 roll mills ≪ / RTI >

Also, in the aspects provided below, a dispersion method such as physical mixing can be used to disperse the nanocarbon in the carbon black. For example, a mortar (manual or motorized), a shaker (with or without a medium), and a tumbler (with or without a medium) are discussed in the following aspects, although other mechanical means may also be used.

The following table summarizes some examples of the co-treatment of nanocarbon and carbon black. As shown in the table below, the nano carbon source and form, the carbon black and form, the ratio of nano carbon to carbon black, the type of device, the mixing parameters such as time, It can have an impact.

Sample drawing Furtherance Device time One No city 10% graphene in N330 Mash and bowl (M & P) 30 min. 2 No city 5% graphene in N330 A steel tumbler having a polyamide (PA) 12 medium 4 hrs at 120 rpm. 3 3 10% finishing CC + 1120 Shaker 4 hrs. 4 4 10% finishing CC + 1120 Manual M & P 1 hr. 5 5 10% CC + 1120 Shaker 1 hr. 6 6 10% BN + 1120 Plastic tumbler with PA 12 4 hrs. 7 7 10% finishing CC + 1120 " " 8 8a, 8b 30% finishing CC + 1120 Manual M & P 30 min. 9 9 5% BN + 1120 Plastic tumbler with PA 12 " 10 10 2% BN + 1120 " " 11 11 5% CC + N330 " " 12 No city 5% BN + 1120 Ceramic "rod mill" 2 hrs at 60 rpm 13 No city 10% BN + N330 Steel tumbler with PA 12 4 hrs at 120 rpm. 14 No city 10% BN + N330 Teflon tumbler with steel media 2 hrs at 120 rpm. 15 12 5% CC + N330 " " 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 No city 10% BN + N330 Brabender Mixer 1 hr. 20 16 10% BN + N330 3 wet on roll mill 5 times

Sample 1 was prepared from 10% graphene in N330 by mixing 0.30 g of supplied xGnP 占 graphene nano platelet (Grade M, XG Sciences, Inc.) with 2.70 g of carbon black N330 (Columbian Chemicals, Co.). The mixture was ground in a mortar for 30 minutes with a ball (Model: Retsch, Brinkmann, Type: RMO).

Sample 2 was prepared from 5% graphene in N330 by mixing 0.10 g of the supplied xGnP 占 graphene nano plastic (Grade M, XG Sciences, Inc.) with 1.90 g of carbon black N330 (Columbian Chemicals, Co.). This mixture was loaded on a tumbler made of steel pipe with a baffle fitted with PA12 (polyamide 12) particles (2 to 6 mm OD) as a grinding medium and was pulverized using a roller (Model: Tru-Square Metal Products) at 120 rpm Tumbled for 4 hours.

The SEM examination of Samples 1 and 2 shows that the graphene nanosopane is well dispersed in the carbon black. Individual nanosplatons can be observed in Samples 1 and 2, respectively, by SEM.

Sample 3 was prepared by combining 0.90 g of Cabot Sterling 1120 carbon black and 0.10 g of carbon nanotubes (CC form; previously called Fitzpatrick hammer mill, hereinafter referred to as "crushed CC ") in a stainless steel cylinder. The cylinder was shaken for 4 hours at a high frequency of the Retsch Brinkmann shaker set to 60.

Figure 3 is a SEM micrograph of sample 3 at 50,000x magnification showing numerous individual nanotubes and loosened aggregates. The aggregate structure of carbon black appears to be essentially unchanged.

Sample 4 was prepared by co-treating 0.10 g of ground carbon nanotube powder and 0.90 g of Cabot Sterling NS 1120 carbon black as prepared in a mortar bowl at room temperature for 1 hour. Samples were prepared for SEM according to the procedure used in Sample 3.

4 is an SEM micrograph of Sample 4 in which the cavity treated carbon nanotube powder and carbon black were photographed at 100,000x magnification. As shown in FIG. 4, since a carbon nanotube is dispersed in carbon black, a number of individual carbon nanotubes can be observed.

Sample 5 was prepared by co-treating 0.90 g Cabot Sterling 1120 carbon black and 0.1 g prepared CC carbon nanotubes under the same conditions (apparatus and time) as Sample 3.

Figure 5 is a SEM micrograph taken at 100,000x magnification of Sample 5 showing loose agglomerates that appear to have a "cloud" structure with a width of about 200 nm and a length of at least 0.5 microns.

Sample 6 was prepared by co-treating 0.1 g of BN carbon nanotubes as prepared and 0.90 g of Cabot Sterling 1120 carbon black in a plastic tumbler containing irregular spherical (2 to 6 mm OD) PA 12 medium at 120 rpm for 4 hours.

Figure 6 is a SEM micrograph of a 100,000x magnification sample 6 showing a number of loosened carbon nanotube aggregates.

Sample 7 was prepared by co-treating 0.1 g of polished CC carbon nanotubes and 0.90 g of Cabot Sterling 1120 carbon block as prepared in the same manner as in Example 6.

Figure 7 is a SEM micrograph of a sample 7 at 50,000x magnification showing the presence of loosened aggregates having a "cloudy" structure with a length of at least 1 micron.

Sample 8 was prepared by co-treating 0.3 g of CC carbon nanotubes as prepared and 0.70 g of Cabot Sterling 1120 carbon black by manual grinding using a mortar and pestle for 30 minutes.

8A and 8B are SEM micrographs of Sample 8 at different magnifications. As shown in FIG. 8A, a plurality of loosened aggregates are present at 50,000x magnification. As shown in FIG. 8B, a plurality of individual nanotubes are observed at a magnification of 100,000x. As before, the structure of the carbon black agglomerate appears unchanged.

Sample 9 was prepared by co-treating 0.95 g Cabot Sterling 1120 carbon black with 0.05 g BN carbon nanotubes and Sample 10 using 0.02 g BN carbon nanotubes and 0.98 g Cabot Sterling 1120 carbon black in a plastic tumbler containing PA 12 medium Followed by co-treating at 120 rpm for 4 hours.

Figures 9 and 10 are SEM micrographs of Samples 9 and 10, respectively, illustrating individual nanotubes and loosened aggregates at 100,000x magnification.

Sample 11 was prepared by co-treating 0.10 g CC carbon nanotubes and 1.90 g Continental N330 carbon black by manual grinding using a mortar and pestle for 30 minutes. Also, individual nanotubes are observed at 100,000x magnification as shown in Fig.

Sample 12 was prepared by co-treating 2.50 g of prepared BN carbon nanotubes and 47.50 g of Cabot Sterling 1120 carbon black. The mixture was loaded into a ceramic bottle and tumbled for 2 hours at 60 rpm using a ceramic bar (the volume of a small marshmallow rod is about 1/2 of the bottle volume). Shortened nanotubes are observed (not shown).

Sample 13 is tumbled and co-treated with steel pipe with baffle. A mixture of 2.0 g of 10 wt% BN in carbon black N330 (Columbian) was injected into the pipe with 10 g of PA12 particles. The tumbler was rotated at 120 rpm for 4 hours. A SEM image of Sample 13 (not shown) showed a set of individual nanotubes similar to Samples 9 and 10 (Figures 9 and 10) where no aggregates were observed.

Sample 14 was co-treated by injecting 2.0 g of 10 wt% BN in carbon black N330 into a Teflon bottle with stainless steel balls (1/8 "OD) and tumbling for 2 h at 120 rpm. At 100,000x magnification, And absence of agglomerates were not observed and shown similar to Figures 9 and 10. The carbon black agglomerate structure appeared to be unchanged.

Sample 15 was prepared by mixing 0.05 g CC carbon nanotubes and 0.95 g carbon black N330 (Columbian) together in a mortar and co-treating for 30 minutes.

12 is a SEM micrograph of a sample 15 at 198,000x magnification showing both the loosened aggregate structure close to 1 micron in length and the presence of individual nanotubes. The carbon black aggregate structure appears to be unchanged.

Sample 16 was prepared by co-milling 0.3 g of BN carbon nanotubes and 0.7 g of carbon black N330 together in a mortar for 30 minutes.

13 is an SEM micrograph of Sample 16 taken at 200,000x magnification. Most individualized nanotubes and aggregates are not observed at all. The carbon black aggregate structure appears to be unchanged.

Sample 17 was prepared by adding 5 grams of BN powder as prepared and 45 grams of N330 carbon black to a Waring blender (model: Blender 7012G, Waring Commercial product, Torrington, Conn.) And treating at the lowest speed for 10 minutes. The density was measured to be 0.39 g / cc.

Figure 14 is a SEM micrograph of sample 17 at 100,000x magnification showing individualized carbon nanotubes in a carbon black aggregate structure that appears unchanged.

Sample 18 was co-treated (as performed in Sample 17) by treating 5 g of BN powder as previously prepared and 45 g of N330 carbon black together in a Waring blender for 10 minutes at low speed. The resulting mixture was then transferred to a motorized pestle bowl and treated again for 10, 20 and 30 minutes to obtain the final co-treated material. The tap density dropped to 0.31 g / cc after 10 minutes and samples at 20 minutes treatment were withdrawn and prepared as described above for microscopic examination.

Figure 15 is a SEM micrograph taken at 200,000x magnification of sample 18 after 20 minutes of further treatment showing the presence of individual nanotubes within the carbon black aggregate structure that appears unchanged.

Sample 19 was prepared by lightly mixing 10 wt% of BN nanotubes and 90 wt% of N330 carbon black as prepared, followed by co-treatment. 19 g of the mixture was transferred to a biaxial mixing head of a Brabender mixer (model: Plasti-Corder DR-2052-K13 (CWBrabender Instruments, Inc., So Hackensack, NJ) designed similar to the operation of a Banbury mixer. This mixture was treated at 100 rpm for 1 hour. The tap density belongs to 0.28 g / cc. Both individualized nanotubes and loosened aggregates are observed. Sample 19 appears to be similar to Sample 18 (Figure 14), but does not provide SEM micrographs of Sample 19.

Sample 20 was prepared by mixing 5.0 g of the 10 wt% BN / N330 mixture prepared in Sample 19 with 7 g of deionized water to form a wet paste material. The wet paste material was passed through a three roll mill (model: Keith 27502, Keith Machinery Corp., Lindenhurst, NY) five times, resulting in a thin film, which was dried in a 100 ° C vacuum oven.

16 is an SEM micrograph of sample 20 taken at 100,000x magnification showing the presence of individual nanotubes.

As disclosed herein, co-treated nanocarbon and carbon black can provide loosened aggregates and / or individualized nanocarbon, such as individualized carbon nanotubes. Such loosened aggregates and / or individualized nanocarbon can be used to improve the dispersion of nanocarbon and / or carbon black in a matrix such as a polymer or other material. Suitable matrix materials include polymers, both organic and inorganic, metals, ceramics, and other non-polymer matrices such as asphalt, cement or glass. Examples of the polymer include thermosetting materials such as vulcanizable rubber, polyurethane, epoxy resin, polyimide and the like or thermoplastic materials such as polyolefin, acrylic, nylon, polycarbonate and the like. The combination of co-treated nanocarbon and carbon black with the polymer can provide improved properties of the polymer, such as improved modulus and elongation.

Those skilled in the art will appreciate that the presence of individualized nanotubes and the absence of large dense aggregates results in composites having improved properties such as tensile modulus, toughness, hardness, durometer, resistance to explosive release, endurance, relaxation time, etc. without sacrificing fracture elongation It can be predicted.

In addition to the nanocarbon and carbon black co-treated in the matrix, additional additives such as inert fillers and activators may also be provided. For example, inert fillers such as glass, pumice and / or activators such as vulcanization activators, release agents, antioxidants, inks or other coloring agents may be added before the nanocarbon-carbon black loosened aggregates are added to the matrix Lt; RTI ID = 0.0 > carbon < / RTI > carbon and carbon black in the matrix.

Although the present invention has been described in detail with reference to preferred embodiments thereof, it will be apparent to those skilled in the art that equivalents may be used and variations and modifications may be made without departing from the scope of the following claims.

Claims (13)

Providing a nanocarbon agglomerate;
Providing a carbon black aggregate; And
Mixing nanocarbon agglomerates and carbon black agglomerates to disperse the nanocarbon agglomerates into looser aggregates of nanocarbon and carbon black; Or allowing the individualized nanocarbon to be dispersed in the carbon black aggregate,
Wherein the nanocarbon agglomerates and the carbon black agglomerates are co-treated to produce a composition. The composition of claim 1, wherein the composition comprises
50 wt% or less of nano carbon aggregates and 50 wt% or more of carbon black aggregates;
30 wt% or less of nano carbon aggregates and 70 wt% or more of carbon black agglomerates; or
10 wt% or less of nano-carbon aggregates and 90 wt% or more of carbon black aggregates. The method of claim 1, wherein providing nanocarbon agglomerates comprises providing multiwalled carbon nanotube agglomerates. Providing aggregated nanocarbon;
Providing carbon black;
Comprising mixing the agglomerated nanocarbon and carbon black in essentially dry state and applying sufficient shear force to the nanocarbon agglomerate structure for a time sufficient to observe the agglomerate structure of the nanocarbon with a scanning electron microscope (SEM) - a process for producing a carbon black dispersion. 5. The method of claim 4, wherein providing nanocarbon agglomerates comprises providing multiwalled carbon nanotube agglomerates. Nanocarbon aggregates; And
Carbon black agglomerates; Wherein the nanocarbon aggregates are dispersed in the carbon black aggregates to such an extent that the individual nanocarbon can be observed by SEM,
Dispersion of nanocarbon in carbon black. 7. The dispersion of claim 6, wherein the nanocarbon agglomerates comprise multi-walled carbon nanotube agglomerates. A co-processed material containing nanocarbon and carbon black; And
Matrix material, wherein the co-treated material is formed by mixing nanocarbon and carbon black and co-treating the mixture with individualized nanocarbon and / or nanocarbon and loosened aggregates of carbon black, wherein the co- Wherein the composition is incorporated into the matrix material. 9. The composition of claim 8, wherein the nanocarbon comprises carbon nanotubes. 9. The composition of claim 8, wherein the composition comprises
50 wt% or less of nano carbon and 50 wt% or more of carbon black;
30 wt% or less of nano-carbon and 70 wt% or more of carbon black; or
10 wt% or less of nano-carbon, and 90 wt% or more of carbon black. 9. 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 thermoplastic material. 9. The method of claim 8, wherein the co-treated material contains loosened aggregates of nanocarbon and carbon black and the loosened aggregates are sufficient to form loosened aggregates of nanocarbon and carbon black with nanocarbon agglomerates and carbon black agglomerates. By force or energy; And / or wherein the co-treated material contains individualized nanocarbon in the carbon black aggregate and the individualized nanocarbon in the carbon black aggregate has sufficient strength to form nanocarbon agglomerates and carbon black agglomerates into individualized nanocarbon within the carbon black Or energy.

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