WO2016145207A1 - Method of co-processing nanocarbons in carbon black, and products therefrom - Google Patents

Method of co-processing nanocarbons in carbon black, and products therefrom Download PDF

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Publication number
WO2016145207A1
WO2016145207A1 PCT/US2016/021791 US2016021791W WO2016145207A1 WO 2016145207 A1 WO2016145207 A1 WO 2016145207A1 US 2016021791 W US2016021791 W US 2016021791W WO 2016145207 A1 WO2016145207 A1 WO 2016145207A1
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aggregates
carbon black
nanocarbons
nanocarbon
carbon
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PCT/US2016/021791
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English (en)
French (fr)
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Jun Ma
Howard Tennent
Robert Hoch
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Hyperion Catalysis International, Inc.
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Priority to JP2017547432A priority Critical patent/JP6832863B2/ja
Priority to EP16762521.9A priority patent/EP3268131A4/en
Priority to CA2979220A priority patent/CA2979220C/en
Priority to KR1020177027500A priority patent/KR20170127487A/ko
Priority to US15/557,574 priority patent/US10633544B2/en
Priority to CN201680009006.2A priority patent/CN107206389B/zh
Publication of WO2016145207A1 publication Critical patent/WO2016145207A1/en
Priority to US16/757,537 priority patent/US11827794B2/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44Carbon
    • C09C1/48Carbon black
    • C09C1/56Treatment of carbon black ; Purification
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44Carbon
    • C09C1/48Carbon black
    • C09C1/56Treatment of carbon black ; Purification
    • C09C1/60Agglomerating, pelleting, or the like by dry methods
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/168After-treatment
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/194After-treatment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44Carbon
    • C09C1/46Graphite
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/45Aggregated particles or particles with an intergrown morphology

Definitions

  • nanocarbons such as nanotubes, graphene, buckyballs, nanohorns, etc.
  • 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.
  • 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.
  • Figs. 1 A-1 B are scanning electron microscope (SEM) micrographs of carbon nanotubes
  • Figs. 2A-2B are SEM micrographs of carbon black.
  • Figs. 3-16 are SEM micrographs of samples of co-processed nanocarbons and carbon black under different conditions. DETAILED DESCRIPTION
  • 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.
  • 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.
  • 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.
  • 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.
  • nanocarbons and nanographenic carbons implies that at least one dimension of the material is less than 1 00 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.
  • 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, et al. and U.S. Patent No. 5,569,635 to Moy, et al., both of which are hereby incorporated by reference in their entireties.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • nanocarbons have one or more layers of ordered graphitic carbon atoms.
  • nanocarbon is a carbon nanotube.
  • carbon nanotube “fibril,” “nanofibers,” and “nanotube” are used interchangeably to refer to single wall ⁇ i.e., 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 layer of less structured amorphous carbon (note, other forms of nanocarbons can also be functionalized if desired).
  • 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.
  • 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.
  • 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, for example, which is hereby incorporated by reference in its entirety.
  • "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, both of which are hereby incorporated by reference in their entireties.
  • Figs. 1 A and 1 B are SEM micrographs of carbon nanotubes. As illustrated in Figs. 1 A and 1 B, carbon nanotubes (BN type in Fig. 1 A and CC type in Fig. 1 B) 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 substantial energy sources, such as ultrasound. See U.S. Patent No. 5,691 ,054, which is co-owned and incorporated herein by reference.
  • CC Continuity
  • ON agglomerates
  • CY agglomerates
  • their TEMs reveal a preferred orientation of the nanotubes.
  • U.S. Patent No. 5,456,897 hereby incorporated by reference in its entirety, 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.
  • Carbon nanotubes are distinguishable from commercially available so called “continuous carbon fibers” ⁇ i.e., commercially available, larger than nanotube- sized carbon fibers).
  • 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.
  • 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.
  • nanographenic carbon 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.
  • 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.
  • 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 microns, less than 100 nm, less than 50 nm, less than 20 nm, or less than 5 nanometers.
  • 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.
  • 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.
  • carbon black is intended to include a carbon powder with carbon aggregates of various sizes.
  • 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.
  • 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, which is hereby incorporated by reference.
  • Figs. 2A and 2B are SEM micrographs of carbon black from different sources.
  • Fig. 2A is Cabot Sterling 1 120 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 magnification. As shown in Fig. 2A and 2B, the carbon black as supplied are aggregated.
  • Co-processed nanocarbons and carbon black were prepared at varying concentrations, as well as using different methods to facilitate co-processing.
  • nanocarbons and carbon black dispersion of nanocarbon aggregates into carbon black aggregates can be observed.
  • co-processing can result in looser nanocarbon aggregates and individualized nanocarbons, as further discussed 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).
  • 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.
  • 5 wt.% to 50 wt.% nanocarbons can provide individualization of nanocarbons in carbon black.
  • Singh et al. 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 et al. further discuss methods of forming graphene.
  • These loosened aggregates can have a nanocarbon to nanocarbon distance greater than that of the starting material's nanocarbon to nanocarbon distance.
  • carbon nanotube loosened aggregates can be separated by a distance of about 10 nanotubes or about 1 0Onm, as observed in the samples discussed below.
  • 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.
  • 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 coprocessing, 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.
  • the nanocarbon and carbon black may be added to the liquid in any order or the liquid may be added to the
  • the quantity of liquid employed may range from 0.10 lbs. to 100 lbs. of liquid per lb. of mixed solids depending on 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 CO 2 , 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • dispersion methods such as physical mixing can be utilized to disperse nanocarbons in carbon black.
  • mortar and pestle hand or motorized
  • shakers with or without media added
  • tumblers with or without media
  • 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.
  • Sample 2 is formed from 5% graphene in N330 by mixing 0.1 Og 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 10g of PA12 (polyamide 1 2) granules (2-6mm OD) as grinding media and tumbled with a roller (Model: Tru- Square Metal Products) at 120rpm for 4 hrs.
  • PA12 polyamide 1 2
  • Sample 3 is formed by combining of 0.1 Og carbon nanotubes (CC conformation; previously ground in a Fitzpatrick hammer mill, herein after referred to as "ground CC”) and 0.90g Cabot Sterling 1 1 20 carbon black in a stainless steel cylinder.
  • ground CC carbon nanotubes
  • Cabot Sterling 1 1 20 carbon black 0.90g
  • Fig. 3 is a SEM micrograph of sample 3 at 50,000x magnification showing numerous individual nanotubes and loosened aggregates.
  • Sample 4 is formed by co-processing 0.1 Og of as made ground carbon nanotube powder with 0.90g of Cabot Sterling NS 1 120 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.
  • 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.
  • Sample 5 is formed by co-processing 0.1 g of as made CC carbon nanotubes and 0.90g Cabot Sterling 1 120 carbon black under the same conditions (equipment and time) as sample 3.
  • 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.
  • Sample 6 is formed by co-processing 0.1 g as made BN carbon nanotubes and 0.90g Cabot Sterling 1 120 carbon black in a plastic tumbler with irregular spherical (2-6mm OD) PA 12 media therein at 1 20 rpm for 4 hrs.
  • Fig. 6 is a SEM micrograph of sample 6 at 100,000x magnification showing numerous loosened carbon nanotube aggregates.
  • Sample 7 is formed by co-processing 0.1 g of as made ground CC carbon nanotubes and 0.90g Cabot Sterling 1 120 carbon black under the same conditions as sample 6.
  • 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.
  • Sample 8 is formed by co-processing 0.3g of as made CC carbon nanotubes and 0.70g Cabot Sterling 1 120 carbon black by hand grinding using a mortar and a pestle for 30 minutes.
  • 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.
  • Sample 9 is formed by co-processing 0.05g BN carbon nanotubes with
  • Figs. 9 and 10 are SEM micrographs of samples 9 and 1 0,
  • Sample 1 1 is formed by co-processing 0.1 Og 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 1 00,000x
  • Sample 12 is formed by co-processing 2.50g of as-made BN carbon nanotubes with 47.50g of Cabot Sterling 1 120 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).
  • Sample 13 is co-processed by tumbling with a steel pipe equipped with a baffle. A mixture of 2.0g 1 0 wt.% BN in carbon black N330 (Columbian) was charged into the pipe along with 10g 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 1 0) with no agglomerates observed.
  • 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 1 0, and thus are not provided. The carbon black aggregate structure appeared unchanged.
  • 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.
  • Fig. 1 2 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.
  • Sample 1 6 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.
  • 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.
  • Sample 1 7 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.
  • 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.
  • 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 1 0 minutes to 0.31 g/cc. at 20 minutes of processing a sample is withdrawn and prepared for microscopy as previously.
  • Fig. 1 5 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.
  • Sample 19 was co-processed by lightly mixing with a spatula 10 wt.% as made BN nanotubes and 90wt.% 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.
  • 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.
  • Fig. 16 is a SEM micrograph of sample 20 at 100,000x magnification, which shows the presence of individual nanotubes.
  • 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.
  • inert fillers and active agents can also be provided.
  • inert fillers such as glass, pumice, etc.
  • active agents such as vulcanization activators, release agents, antioxidants, inks or other colorants, etc.
  • inert fillers such as glass, pumice, etc.
  • active agents such as vulcanization activators, release agents, antioxidants, inks or other colorants, etc.

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PCT/US2016/021791 2015-03-10 2016-03-10 Method of co-processing nanocarbons in carbon black, and products therefrom WO2016145207A1 (en)

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JP2017547432A JP6832863B2 (ja) 2015-03-10 2016-03-10 カーボンブラック中でナノカーボンを共処理する方法及びそれから得られる生成物
EP16762521.9A EP3268131A4 (en) 2015-03-10 2016-03-10 Method of co-processing nanocarbons in carbon black, and products therefrom
CA2979220A CA2979220C (en) 2015-03-10 2016-03-10 Method of co-processing nanocarbons in carbon black, and products therefrom
KR1020177027500A KR20170127487A (ko) 2015-03-10 2016-03-10 카본 블랙 중의 나노탄소를 공동처리하는 방법, 및 이로부터 수득되는 생성물
US15/557,574 US10633544B2 (en) 2015-03-13 2016-03-10 Method of co-processing nanocarbons in carbon black, and products therefrom
CN201680009006.2A CN107206389B (zh) 2015-03-10 2016-03-10 共处理碳黑中纳米碳的方法和由其获得的产品
US16/757,537 US11827794B2 (en) 2015-03-13 2020-04-20 Nanocarbons in carbon black, carbon fibers and carbon black, and methods of forming a composition by co-processing nanocarbon aggregates and carbon black aggregates

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CA2979220A1 (en) 2016-09-15
EP3268131A1 (en) 2018-01-17
CA2979220C (en) 2023-03-14
JP6832863B2 (ja) 2021-02-24
CN107206389A (zh) 2017-09-26
EP3268131A4 (en) 2018-12-12
JP2021073165A (ja) 2021-05-13
JP7087128B2 (ja) 2022-06-20
KR20170127487A (ko) 2017-11-21
CN107206389B (zh) 2021-09-17

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