Shielding formulation using discrete carbon nanotubes having a target oxidation level

Abstract

To provide discrete, individualized carbon nanotubes having targeted or selective oxidation levels and / or content on the interior and exterior of tube walls.SOLUTION: The carbon nanotubes have little or no inner tube surface oxidation, or differing amounts and / or types of oxidation between inner and outer surfaces of the tubes. These new discrete carbon nanotubes are useful in electromagnetic and radio frequency shielding applications, especially where the shielding is essentially constant over a relatively wide range of frequencies. Additives such as plasticizers can be used in synthesis and preparation of an elastomeric, thermoplastic and thermoset composite for improvement of mechanical, electrical and thermal properties.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of U.S. Patent Application No. 13 / 164,456, filed Jun. 20, 2011, and its divisional applications, U.S. Patent Application No. 13 / 140,029, filed Aug. 9, 2011, and its divisional applications, and U.S. Patent Application No. 15 / 482,304, filed Apr. 7, 2017, the disclosures of each of which are hereby incorporated by reference herein. This application claims the benefit of U.S. Provisional Patent Application No. 62 / 571,101, filed Oct. 11, 2017, the disclosure of which is hereby incorporated by reference herein.

[0002] The present invention relates to a novel composition of discrete carbon nanotubes having a target oxidation level and / or content, such as a metal oxide and / or a plasticizer, and to a shielding formulation using the same and a method of formulating the same. The shielding formulation includes applications for electromagnetic and radio frequency shielding.

Background Art

[0003] Carbon nanotubes can be classified by the number of walls in the tube, such as single - wall (single - wall), double - wall (double - wall), and multi - wall (multi - wall). Carbon nanotubes are currently produced as agglomerated nanotube balls, bundles, or forests adhered to a substrate. The use of carbon nanotubes as reinforcing agents in elastic, thermoplastic, and thermosetting polymer composites is an area where carbon nanotubes are predicted to have high utility. However, the use of carbon nanotubes in these applications is generally not possible to reliably produce individualized carbon nanotubes and individualized nanotubes has been inhibited due to the ability to disperse the resulting carbon nanotubes in a polymer matrix Bosnyak et al. have, in various patent applications (e.g., U.S. Patent Application Publication No. 2012-01 83770A1 and U.S. Patent Application Publication No. 2011-0294013A1), by the use of oxidation and shear force in a moderate and substantially simultaneous manner, standardly oxidize both the inner and outer surfaces of the nanotubes at substantially the same oxidation level, producing discrete carbon nanotubes such that individual or discrete tubes are obtained. SUMMARY OF THE INVENTION

[0004] The present invention is different from these prior Bosnyak et al. applications and disclosures. The present invention describes a composition of discrete fragmented carbon nanotubes having a targeted or selective oxidation level and / or content on the outside and / or inside of the tube wall. Such novel carbon nanotubes have little to no oxidation of the inner surface of the tube, i.e., differentiate the amount and / or type of oxidation between the inner and outer surfaces of the tube. These new discrete tubes are useful in a number of applications including plasticizers, and they can be used as additives in the synthesis and formulation of elastic, thermoplastic, and thermosetting composites for the improvement of mechanical, electrical, and thermal properties.

[0005] Other useful applications include electromagnetic interference (EMI) and radio frequency interference (RFI) shielding applications . Currently, the electronics industry has many developments that require devices to operate in the frequency range of 1 GHz to 14 GHz to keep up with the high demand for data transport. Electromagnetic interference (EMI) is ​It is interference from an external source that affects the electrical circuit or vice versa. Electromagnetic shielding is a process that reduces the transmission of electromagnetic radiation that interferes with electronic circuits. The EMI shielding effect (SE) is measured in decibels ( dB) and can be expressed as the attenuation of power. SE = 10 log (Pi / Pt) where Pi is the incident power and Pt is the transmitted power. SE is the sum of three processes: reflection, absorption and multiple reflections of the radiation. The reflection of radiation is due to the interaction of mobile charge carriers (electrons and / or holes) with the electromagnetic field. Absorption requires that the material has electrical or magnetic dipoles that interact with the electromagnetic field. Multiple reflections occur when the radiation crosses two or more reflective interfaces.

[0006] Metals are known for their high EMI shielding effects due to the reflection of radiation, but they are not good materials for applications such as mobile phones due to their weight, heat trapping properties and potential for corrosion. Thin metal coatings also reflect in many cases, but in a state where many circuits are close to each other problems due to crosstalk can occur. What is becoming increasingly preferred is for EMI shielding materials that absorb rather than reflect. Carbon-based polymer composites as enclosures are most promising as lightweight, high-strength composites with some shielding ability that can be enhanced by metal flakes or fibers. However, in these discontinuous phase metal / carbon fiber-based composites, as the frequency increases beyond 2 GHz, the shielding effect rapidly decreases, such that values of ~ -1 0 dB / cm are common, and these composites also have relatively small absorption characteristics. As electronic components become more complex and finer, it becomes increasingly difficult to shield through metal enclosures. / carbon fiber-based composites, as the frequency increases beyond 2 GHz, the shielding effect rapidly decreases, such that values of ~ -1 0 dB / cm are common, and these composites also have relatively small absorption characteristics. As electronic components become more complex and finer, it becomes increasingly difficult to shield through metal enclosures.

[0007] Generally, metals such as iron, chromium, aluminum, uranium, platinum, copper, cobalt, lithium um and nickel are essentially magnetic. Some rare earth metals such as neodymium and samarium can form alloys for very strong permanent magnets. Their metal compounds and alloys are also, in some cases, essentially magnetic together with various metals. For an example of an oxide compound, the formation of magnetite Fe3O4 occurs via Fe 2+ +2Fe 3+ +8OH - →2Fe3 O4+4H2O. Magnetic particles with a diameter exceeding about 1 micrometer, such as iron oxide Fe3O4 magnetite, are used at a high loading, for example, at a loading higher than 70% by weight in a silicone or acrylic medium. These have good absorption characteristics at about 6 GHz and above, reaching -150 dB / cm typically at 25 GHz, but typically have a density higher than 4 g / ml and low strength or tear resistance. Due to their low handleability, plastic sheets are often used on their surfaces to provide handleability without crushing. Therefore, there is a large unmet need for a broader broadband (2 - 50 GHz) high absorption material with good strength or tear resistance that results in improved handleability. Although not limited to this frequency range, further improvement in the absorption characteristics of magnetic particles at frequencies below 6 GHz is expected for particles with a diameter less than a certain diameter where superparamagnetism is observed. Superparamagnetic materials are very small, so they consist of only one magnetic domain. For this reason, they have different magnetic properties from those of micrometer-sized or larger particles consisting of multiple magnetic domains with the same composition.

[0008] ​​​​​​​​​​Compared with particles of a diameter, these multiple domains interfere not only with an external electromagnetic field but also with each other and are thus considered to be more easily affected by absorbing energy from the external electromagnetic field The standard particle size showing superparamagnetism is less than 70 nanometers. However, these nanoscale particles are very difficult to disperse in their elementary particle state and often larger-scale agglomerates lead to a decrease in the strength of the composite. Therefore, although not limited thereto, there is a need for improved dispersion of magnetic elementary particles with a diameter of less than about 70 nanometers in a host liquid matrix at room temperature such as silicone, or although not limited thereto, a solid matrix at room temperature such as a thermoplastic or thermosetting polymer In this regard, there is a need for improved dispersion of magnetic elementary particles with a diameter of less than about 70 nanometers in.

[0009] One embodiment of the present invention is an electromagnetic shielding composition comprising a plurality of discrete carbon nanotubes and at least one magnetic metal and / or an alloy thereof, the discrete carbon nanotubes having an inner surface and an outer surface, each surface having an interior surface oxidized species content and an exterior surface oxidized species content, wherein the interior surface oxidized species content is at least 20% to a maximum of 1 00% different from the exterior surface oxidized species content, preferably the interior surface oxidized species content is less than the exterior surface oxidized species content. The interior surface oxidized species content is up to 3 weight percent based on the weight of the carbon nanotubes,

[0010] preferably from about 0.01 to about 3 weight percent, more preferably from about 0.01 to about 2 weight percent, and most preferably from about 0.01 to about 0. preferably from about 0.01 to about 3 weight percent based on the weight of the carbon nanotubes, more preferably from about 0.01 to about 2 weight percent, and most preferably from about 0.01 to about 0. 1 weight percent, based on the weight of the carbon nanotubes It can be 8 weight percent. A particularly preferred internal surface oxide species content is from 0 to about 0.01 weight percent based on the weight of the carbon nanotubes.

[0011] The external surface oxide species content is from about 1 to about 6 weight percent, preferably from about 1 to about 4 weight percent, more preferably from about 1 to about 2 weight percent based on the weight of the carbon nanotubes. This is measured by comparing the external oxide species content for a given plurality of nanotubes relative to the total weight of the plurality of nanotubes. It is.

[0012] The total of the internal surface oxide species content and the external surface oxide species content can be from about 1 to about 9 weight percent based on the weight of the carbon nanotubes. It is.

[0013] Another embodiment of the invention is an electromagnetic shielding composition comprising a plurality of discrete carbon nanotubes and at least one magnetic metal and / or its alloy, the discrete carbon nanotubes having an internal surface and an external surface, each surface having an internal surface oxide species content and an external surface oxide species content, the internal surface oxide species content being less than about 0.01 to about 0.8 percent based on the weight of the carbon nanotubes, and the external surface oxide species content being more than about 1.2 to about 3 percent based on the weight of the carbon nanotubes.

[0014] The discrete carbon nanotubes of embodiments of any of the above compositions preferably comprise a plurality of open-ended tubes, and more preferably the plurality of discrete carbon nanotubes comprise a plurality of open-ended tubes. The discrete carbon nanotubes of embodiments of any of the above compositions have an inner It is particularly preferred when the difference between the oxidation of the inner surface and the oxidation of the outer surface is at least about 0.2 weight percent. is preferred.

[0015] The compositions described herein can be used as ion transporters. Compounds / drugs / chemicals of various species or classes that exhibit this ion transport effect, including ionic, somewhat non-ionic compounds, hydrophobic or hydrophilic compounds, can be used. / chemical substances can be used. For all of the uses disclosed herein, the magnetic metal and / or its alloy is selected from the group consisting of iron, chromium, aluminum, uranium, platinum, copper, cobalt, lithium, nickel, neodymium, and samarium. The magnetic metal and / or its alloy preferably consists of an oxidized metal and / or an oxidized alloy.

[0016] The novel carbon nanotubes disclosed herein, along with at least one magnetic metal and / or its alloy, are also useful for groundwater remediation. is also useful for groundwater remediation.

[0017] In all of the uses disclosed herein, the magnetic metal and / or its alloy is selected from the group consisting of iron, chromium, aluminum, uranium, platinum, copper, cobalt, lithium, nickel, neodymium, and samarium. The magnetic metal and / or its alloy preferably consists of an oxidized metal and / or an oxidized alloy. ium, aluminum, uranium, platinum, copper, cobalt, lithium, nickel, neodymium, and samarium. The magnetic metal and / or its alloy preferably consists of an oxidized metal and / or an oxidized alloy. from the group consisting of iron, chromium, aluminum, uranium, platinum, copper, cobalt, lithium, nickel, neodymium, and samarium. The magnetic metal and / or its alloy preferably consists of an oxidized metal and / or an oxidized alloy. consists of an oxidized metal and / or an oxidized alloy.

[0018] The composition comprises novel discrete targeted oxidized carbon nanotubes and can also be used as a component in or as a sensor. as a component in or as a sensor.

[0019] The compositions disclosed herein can also be used as components in drug delivery or sustained release formulations or as drug delivery or sustained release formulations. as components in drug delivery or sustained release formulations or as drug delivery or sustained release formulations.

[0020] In certain embodiments, the compositions disclosed herein can be used in payload molecule delivery, drug delivery or sustained release formulations or as components in payload molecule delivery, drug delivery or sustained release formulations. In particular, various drugs including small molecule therapeutics, peptides, nucleic acids or combinations thereof in payload molecule delivery, drug delivery or sustained release formulations or as components in payload molecule delivery, drug delivery or sustained release formulations. In particular, various drugs including small molecule therapeutics, peptides, nucleic acids or combinations thereof can be used. In particular, various drugs including small molecule therapeutics, peptides, nucleic acids or combinations thereof The agent can be incorporated into nanotubes and delivered to specific locations. Discrete carbon nanotubes are non-permeable to cell membranes or are difficult to pass through the cell membrane into the interior of the cell and can be used to assist small molecules / peptides / nucleic acids. When small molecules / peptides / nucleic acids cross the cell membrane it can have a very significant impact. Small molecules are defined here as those having a molecular weight of about 500 daltons or less or less.

[0021] The apoptosis-promoting peptide KLAKLAK is known to be non-permeable to cell membranes By incorporating the peptide into discrete carbon nanotubes, KLAKLAK can cross the cell membrane of LNCaP human prostate cancer cells and trigger apoptosis . The KLAKLAK-discrete carbon nanotube construct can result in apoptosis of up to 100% of target LNCaP human prostate cancer cells. Discrete carbon nanotubes can also be useful for delivering other small molecules / peptides / nucleic acids across the cell membranes of a wide range of other cell tumors . Discrete carbon nanotubes can be arranged to have a high incorporation efficiency thereby enabling the delivery of large amounts of drugs or peptides. In some cases, the movement across the cell membrane can be achieved without the need for targeting or permeating moieties that assist or enable the movement . In other cases, discrete carbon nanotubes can be conjugated with targeting moieties (e.g., peptides, chemical ligands , antibodies) to assist the direction in which the drug or small molecule / peptide / nucleic acid travels towards a specific target . Discrete carbon nanotubes are well tolerated on their own and do not trigger apoptosis independently .

[0022] Peptides, small molecules, nucleic acids, and other agents can attach to the exterior of discrete carbon nanotubes via van der Waals bonds, ionic bonds, or covalent bonds. As described, the level of oxidation can be controlled to promote specific interactions with a given agent or small molecule / peptide / nucleic acid. In some cases, sufficiently small agents or peptides can localize within the interior of discrete carbon nanotubes. The process for filling the interior of discrete carbon nanotubes can occur over a number of temperature ranges, including below room temperature. In some cases, discrete carbon nanotubes need only be fully loaded with both small molecule agents and large molecule agents for as little as 60 minutes. The payload molecule can be selected from the group consisting of drug molecules, radioactive tracer molecules, radiation therapy molecules, diagnostic imaging molecules, fluorescent tracer molecules, protein molecules, and combinations thereof. Exemplary types of payload molecules that can be covalently or non-covalently attached to the discrete functionalized carbon nanotubes disclosed herein include, but are not limited to, proton pump inhibitors, H2 -receptor antagonists, cytoprotective agents, prostaglandin analogs, beta blockers, calcium channel blockers, diuretics, cardiotonic glycosides, antiarrhythmics, antianginals, vasoconstrictors, vasodilators,

[0023] ACE inhibitors, angiotensin receptor blockers, alpha blockers, anticoagulants, antiplatelet agents, fibrinolytic agents, lipid-lowering agents, statins, sleep aids, antipsychotics, antidepressants, monoamine oxidase inhibitors, selective serotonin reuptake inhibitors, antiemetics, anticonvulsants, anxiolytics, barbituric acid, stimulants, amphetamines, benzodiazepines, dopamine antagonists, antihistamines,

[0024] Here, the exemplary types of payload molecules that can be covalently or non-covalently attached to the discrete functionalized carbon nanotubes are not limited to these, but also include proton pump inhibitors, H2 -receptor antagonists, cytoprotective agents, prostaglandin analogs, beta blockers, calcium channel blockers, diuretics, cardiotonic glycosides, antiarrhythmics, antianginals, vasoconstrictors, vasodilators, ACE inhibitors, angiotensin receptor blockers, alpha blockers, anticoagulants, antiplatelet agents, fibrinolytic agents, lipid-lowering agents, statins, sleep aids, antipsychotics, antidepressants, monoamine oxidase inhibitors, selective serotonin reuptake inhibitors, antiemetics, anticonvulsants, anxiolytics, barbituric acid, stimulants, amphetamines, benzodiazepines, dopamine antagonists, antihistamines, platelet drugs, fibrinolytics, lipid-lowering drugs, statins, sleeping pills, antipsychotics, antidepressants, monoamine oxidase inhibitors, selective serotonin reuptake inhibitors, antiemetics, anticonvulsants, anxiolytics, barbituric acid, stimulants, amphetamines, benzodiazepines, dopamine antagonists, antihistamines, Stamina drugs, cholinergic drugs, anticholinergic drugs, emetics, cannabinoids, 5-HT antagonists, NS AID, opioids, bronchodilators, anti-allergy drugs, mucolytics, corticosteroids , beta receptor antagonists, anticholinergic drugs, steroids, androgens, anti-androgens, growth hormones, thyroid hormones, anti-thyroid drugs, vasopressin analogs, antibiotics, antibacterial drugs, anti-tuberculosis drugs, anti-malarial drugs, anti-viral drugs, anti-protozoal drugs, radiation protectors, chemotherapeutic agents, cell growth inhibitors drugs, and cytotoxic agents such as paclitaxel may be included.

[0025] Batteries comprising the compositions disclosed herein are also useful. Such batteries include lithium um, nickel cadmium or lead acid types.

[0026] Formulations comprising the compositions disclosed herein may further comprise epoxy, polyurethane or elastomer s. Such formulations may take a dispersed form. The formulations may also include nano plate structures.

[0027] The composition may further comprise at least one hydrophobic material in contact with at least one internal surface s.

[0028] The present invention relates to a composition comprising a plurality of discrete carbon nanotubes and a plasticizer, the discrete carbon nanotubes having an aspect ratio of 10 to about 500, and the carbon nanotubes being functionalized with oxidized species on their outermost wall surfaces. The discrete carbon nanotubes have an internal surface and an external surface, each surface having an internal surface oxidized species content and an external surface oxidized species content, the internal surface oxidized species content being from about 0.01 to about 0.8 percent by weight of the carbon nanotubes s. is less than, and the external surface oxide species content is from about 1.2 to about 3 percent by weight of the carbon nanotubes. The oxide species consists of carboxylic acid, phenol, or a combination thereof obtained.

[0029] The composition may further comprise a plasticizer selected from the group consisting of dicarboxyl / tricarboxyl esters, trimellitates, adipates , sebacates, maleates, glycols and polyethers, polymeric plasticizers, bio-based plasticizers and mixtures thereof. The composition may further comprise a plasticizer comprising a process oil selected from the group consisting of naphthenic oil, paraffinic oil, paraben oil, aromatic oil, vegetable oil, seed oil and mixtures thereof.

[0030] The composition may further comprise a plasticizer selected from the group of water-immiscible solvents consisting of, but not limited to, xylene, pentane, methyl ethyl ketone, hexa ne, heptane, ethyl acetate, ether, dichloromethane, dichloroethane, cyclo hexane, chloroform, carbon tetrachloride, butyl acetate butanol, benzene or mixtures thereof .

[0031] In yet other embodiments, the composition further comprises an inorganic filler selected from the group consisting of silica, nano-clay, carbon black, gra phen, glass fiber and mixtures thereof .

[0032] In other embodiments, the composition is in the form of free-flowing particles.

[0033] In other embodiments, the composition comprises a plurality of discrete carbon nanotubes and a plasticizer, and the discrete carbon nanotubes are from about 10 weight percent to about 90 weight percent, preferably 10 By weight, from 40% to 40 wt%, most preferably from 10% to 20 wt% %.

[0034] Another embodiment forms a composition comprising discrete carbon nanotubes in a plasticizer, The process comprising: a) selecting a plurality of discrete carbon nanotubes having an average aspect ratio of about 10 to about 500 and a total level of oxidized species content of about 1 to about 15 wt%; b) suspending the discrete carbon nanotubes in an aqueous medium (water) at a nanotube concentration of about 1 wt% to about 10 wt% to form an aqueous medium / nanotube slurry; c Mixing the carbon nanotube / aqueous medium (e.g., water) slurry with at least one plasticizer at a temperature of about 30 °C to about 100 °C for a time sufficient for the carbon nanotubes to migrate from the water to the plasticizer to form a wet nanotube / plasticizer mixture; d) separating water from the wet carbon nanotube / plasticizer mixture to form a dry nanotube / plastic Agent mixture; e) drying at about 40 °C to about 120 °C to remove residual water from the dry Nanotube / plasticizer mixture to form an anhydrous nanotube / plasticizer mixture. And f) removing residual water from the dry nanotube / plasticizer mixture by drying at about 40 °C to about 120 °C to form an anhydrous nanotube / plasticizer mixture. And f) removing residual water from the dry nanotube / plasticizer mixture by drying at about 40 °C to about 120 °C to form an anhydrous nanotube / plasticizer mixture. Agent mixture; e) separating water from the wet carbon nanotube / plasticizer mixture to form a dry nanotube / plastic Agent mixture; e) drying at about 40 °C to about 120 °C to remove residual water from the dry Nanotube / plasticizer mixture to form an anhydrous nanotube / plasticizer mixture.

[0035] Another embodiment is a composition of discrete carbon nanotubes in a plasticizer further mixed with at least one rubber. The rubber may be natural or synthetic rubber, preferably Natural rubber, polyisobutylene, polybutadiene and styrene-butadiene rubber, butyl rubber , polyisoprene, styrene-isoprene rubber, styrene-isoprene rubber, ethylene Propylene diene rubber, silicone, polyurethane, polyester-polyether, water ​Selected from the group consisting of non-hydrogenated and non-hydrogenated nitrile rubbers, halogen-modified elastomers, fluorine elastomers, and combinations thereof. Thereof.

[0036] Other embodiments are compositions of discrete carbon nanotubes in a plasticizer further mixed with at least one thermoplastic polymer or at least one thermoplastic elastomer. Thereof. The thermoplastic can be selected from, but is not limited to, acrylic, polyamide, polyethylene, polystyrene, polycarbonate, methacrylic, phenol, polypropylene, polyolefin plastics and elastomers such as polyolefins, EPDM, and copolymers of ethylene, propylene and functional monomers. and elastomers, etc. Thereof.

[0037] Still other embodiments are compositions of discrete carbon nanotubes in a plasticizer further mixed with at least one thermosetting polymer, preferably epoxy or urethane. Thereof. The thermosetting polymer can be selected from, but is not limited to, epoxy, polyurethane, or unsaturated polyester resin. Thereof.

[0038] For a more complete understanding of the present disclosure and its effects, reference is now made to the following description of specific embodiments of the disclosure. Thereof.

Brief Description of the Drawings

[0039]

Figure 1

Figure 2

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Figures 4-5A

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Figures 6-7

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Figures 10-11

[0040] In the following description, specific examples are provided to provide a thorough understanding of the presently disclosed embodiments. Specific details are set forth, such as quantities, sizes, etc., although the present disclosure does not necessarily require such specific details. It will be apparent to one skilled in the art that the present invention can be implemented without such details. Details are not necessary to obtain a complete understanding of the present disclosure and will be understood by those skilled in the relevant art. Insofar as it is within the scope, details regarding such considerations and the like have been omitted.

[0041] Most of the terms used herein will be recognizable to those skilled in the art, but are not explicitly defined. If not defined, terms shall have the meaning currently accepted by those skilled in the art. It should be understood that the construction of terms should be interpreted in a meaningful or substantial manner. If meaningless, the definition should be taken from Webster's Dictionary, Third Edition, 2009. The definitions and / or interpretations may be incorporated into other patent applications, patents, publications, whether related or not. should not be incorporated from the information provided.

[0042] The functionalized carbon nanotubes of the present disclosure generally refer to the carbon nanotubes described above. Such modifications may occur at the nanotube ends, sidewalls, or Chemical modifications include, but are not limited to, covalent bonds, ionic bonds, Chemisorption, intercalation, surfactant interactions, polymer wrapping, cutting, dissolution In some embodiments, the carbon nanotubes may be prepared by: It can be functionalized during and after exfoliation.

[0043] In various embodiments, the aspect ratio is from about 10 to about 500, preferably from about 40 to about 200, with an overall (total) oxidation level of about 1 weight percent to about 15 weight percent, preferably More preferably, about 1 weight percent to about 10 weight percent, more preferably about 1 weight percent from about 1 weight percent to about 5 weight percent, more preferably from about 1 weight percent to about 3 weight percent A plurality of carbon nanotubes, including single-walled, double-walled, or multi-walled carbon nanotubes. The oxidation level is determined by the weight of the oxidized species covalently attached to the carbon nanotubes. The percent weight of oxidized species in carbon nanotubes is defined as the amount of The temperature-specific gravity measurement method for this purpose uses approximately 7 to 15 mg of dried oxidized carbon nanotubes. This involves heating from 100°C to 700°C at 5°C / min in a dry nitrogen atmosphere. The percent weight loss from 00 to 600 °C was taken as the percent weight loss of the oxidized species. Oxidizing species are also observed, especially in the wavelength range 1730–1680 cm -1 In the Fourier transform This can be quantified using FTIR (transformation infrared spectroscopy).

[0044] Carbon nanotubes are oxidized with carboxylic acid or derivative carbonyl-containing species. It can have essentially discrete individual nanotubes that are entangled as a whole. Generally, the amount of discrete carbon nanotubes after the oxidation and shearing processes are were mostly (i.e., multiple), and the remainder of the tube was partially entangled in some way. As it stands, 70, 80, 90 or even 99 percent of the discrete carbon nanotubes The complete conversion of nanotubes into discrete singulated tubes (i.e., 10 0 percent) is most preferred. The derived carbonyl species are phenols, ketones, quaternary These may include amines, amides, esters, acylhalogens, monovalent metal salts, etc. It can vary between the inner and outer surfaces of the tube.

[0045] For example, an acid may be used to oxidize the outer surface of the tube, followed by water washing and induced shear. This allows the tube to be severed and separated, if desired. The formation of discrete tubes without (i.e., zero) tube wall oxidation was achieved with different oxidants. or further oxidized at different concentrations with the same oxidizing agent used on the outer wall of the tube. may result in different amounts—and / or different types—of internal and surface oxidation.

[0046] Finished carbon nanotubes using metal catalysts such as iron, aluminum, or cobalt. B can hold 5 weight percent or more of a large amount of catalyst bonded or trapped within the carbon nanotube. These residual metals are harmful in such applications as electronic devices due to increased corrosion, or can inhibit vulcanization when curing an elastomer composite. Furthermore, these divalent or polyvalent metal ions can bind to carboxylic acid groups in the carbon nanotube and inhibit the dispersion of the carbon nanotube in subsequent dispersion processes. In other embodiments, the oxidized carbon nanotube has a residual metal concentration of less than about 10,000 parts per million (ppm) per million, preferably less than about 5,000 parts per million per million. Metals can be conveniently measured using energy-dispersive X-ray spectroscopy or thermogravimetry.

[0047] Compositions of discrete carbon nanotubes in plasticizers can be used as additives to various compounds and composites that improve mechanical properties, temperature, and electrical conductivity. One example is as an additive in rubber compounds used to make rubber parts in applications in the oil field such as sealants, anti-extrusion devices, and drill motors having improved wear resistance, tear strength, and thermal conductivity. Another example is as an additive in rubber compounds used to make tires, sealants, and vibration dampers. By selecting the appropriate plasticizer, the additive has utility in the synthesis and formulation of thermoplastics, thermosets, and composites.

[0048] The produced carbon nanotubes are in the form of bundles or entangled agglomerates, CNa no Technology, Nanocyl, Arkema, and Kumho Pet ​​​​​​​​​​​​​​​Discrete carbon nanotubes can be made from different sources such as rochemicals. An acidic solution, preferably at a concentration higher than about 60 wt%, more preferably a nitric acid solution with a nitric acid concentration of 65% or more can be used to prepare carbon nanotubes. U.S. Patent Application Publication 2012-0183770A1 and U.S. Patent Application Publication 2011-0294013A1, the disclosures of which are incorporated herein by reference, such as a mixed acid system (e.g., nitric acid and sulfuric acid) can be used to produce discrete oxidized carbon nanotubes from the completed bundles or entangled carbon nanotubes. (For example, nitric acid and sulfuric acid) can be used to produce discrete oxidized carbon nanotubes from the completed bundles or entangled carbon nanotubes. A mixture of 0.5 wt% to 5 wt%, preferably 3 wt% of carbon nanotubes is prepared with C

[0049] Schematic process for generating discrete carbon nanotubes with targeted oxidation process Nano grade Flotube9000 carbon nanotubes and 65% nitric acid. While stirring, the mixture of acid and carbon nanotubes is heated at 70 - 90 °C for 2 - 4 hours. Then, the formed oxidized carbon nanotubes are isolated from the acid mixture. Although not limited thereto, several methods including centrifugation, filtration, pressing, decantation, and other solid-liquid separation techniques can be used to isolate the oxidized carbon nanotubes. And the residual acid is removed by washing the oxidized carbon nanotubes with water, preferably an aqueous medium such as deionized water, to a pH of 3 - 4. And the carbon nanotubes are suspended in water at a concentration of 0.5 wt% to 4 wt%, preferably 1.5 wt%. The solution is capable of generating an energy density of 10 ~10 Joules / m 6 ~10 8 ~10 3 Joules / m 3 and a treatment capable of generating an energy density of Concentrated and destructively powerful forces generated by shearing (turbulence) and / or cavitation in a machine are subjected to. Devices that meet this specification include, but are not limited to, ultrasonic processors, cavitators, mechanical homogenizers, pressure homogenizers, and microfluidizers ( Table 1). One such homogenizer is shown in U.S. Patent No. 756,953, the disclosure of which is hereby incorporated by reference. After the shearing process, the oxidized carbon nanotubes become discrete and fragmented carbon nanotubes. Typically, based on a given starting amount of the untreated, entangled carbon nanotubes and the finished carbon nanotubes, a minority of the tubes, usually a very small minority of the tubes, remain entangled or are not completely fragmented, and preferably at least about 60%, more preferably at least about 75%, most preferably at least about 95% and up to 100% of a plurality of discrete oxidized carbon nanotubes are produced from this processing process or are produced from this processing process. Another exemplary process for producing discrete carbon nanotubes is as follows is as follows. A mixture of 0.5 wt% to 5 wt%, preferably 3 wt% of carbon nanotubes is prepared with C Nano Flotube 9000 grade carbon nanotubes and 3 parts by weight of sulfuric acid (97% sulfuric acid and 3% water) and 1 part by weight of nitric acid (65 - 70% nitric acid). The mixture is maintained at room temperature while stirring for 3 - 4 hours. And the formed

[0050] oxidized carbon nanotubes are isolated from the acid mixture. Several methods including, but not limited to, centrifugation, filtration, pressing, decantation, and other solid - liquid separation techniques can be used to isolate the oxidized carbon nanotubes. And the oxidized carbon nanotubes formed are isolated from the acid mixture. Several methods including, but not limited to, centrifugation, filtration, pressing, decantation, and other solid - liquid separation techniques can be used to isolate the oxidized carbon nanotubes. And the oxidized carbon nanotubes​​ Washing the nanotubes with water, preferably an aqueous medium such as deionized water, until the pH reaches 3 to 4 removes the acid. Then, the oxidized carbon nanotubes are suspended in water at a concentration of 0.5 wt% to 4 wt%, preferably 1.5 wt%. The solution is subjected to shear (turbulent flow) and / or 6 ~10 8 J / m 3 of energy density generating ability by a processing device and is subjected to intensively destructive forces generated by cavitation. Devices that meet this specification include, but are not limited to, ultrasonic processors, cavitators, mechanical homogenizers, pressure homogenizers, and microfluidizers (Table 1). After the shear and / or cavitation treatment, the oxidized carbon nanotubes become discrete oxidized carbon nanotubes. Usually, based on a given starting amount of the untreated entangled carbon nanotubes and the finished carbon nanotubes, a small number of tubes, usually a very small number of tubes, remain entangled or are not completely fragmented, preferably at least about 60%, more preferably at least about 75%, most preferably at least about 95% and up to 100% of a plurality of discrete oxidized carbon nanotubes are produced from this process. : Entangled oxidized carbon nanotubes as MWCNT-3 hours (oMWCNT-3) 100 milliliters of nitric acid over 64% is heated to 85 °C. To the acid, 3 grams of untreated multi-walled carbon nanotubes (C9000, CNano Technology) are added. The untreated tubes have the form of a woolly entangled ball. The solution is 3 and / or, preferably at least about 60%, more preferably at least about 75%, most preferably at least about 95% and up to 100% of a plurality of discrete oxidized carbon nanotubes are produced from this process. at least about 75%, most preferably at least about 95% and up to 100% of a plurality of discrete oxidized carbon nanotubes are produced from this process.

[0051] Example 1 : Entangled oxidized carbon nanotubes as MWCNT-3 hours (oMWCNT-3) oxidized carbon nanotubes 100 milliliters of nitric acid over 64% is heated to 85 °C. To the acid, 3 grams of untreated multi-walled carbon nanotubes (C9000, CNano Technology) are added. The untreated tubes have the form of a woolly entangled ball. The solution is 3 While maintaining the temperature at 85 °C, a mixture of an acid and carbon nanotubes is mixed and designated as "oMWC NT-3". At the end of the reaction period, oMWCNT-3 is filtered to remove the acid and washed with reverse osmosis (RO) water to a pH of 3 - 4. After the acid treatment, the carbon nanotubes remain in a tangled ball. The tubes are dried at 60 °C until they reach a constant weight.

[0052] Example 2 : Oxidized carbon nanotubes in a tangled state as MWCNT-6 hours (oMWCNT-6) 100 milliliters of nitric acid with a concentration of over 64% is heated to 85 °C. To this acid, 3 grams of untreated multi-walled carbon nanotubes (C9000, CNano Technology) are added. The untreated tubes have the form of a tangled ball of wool. While maintaining the solution at 85 °C for 6 hours, a mixture of the acid and carbon nanotubes is mixed and designated as "oMWC NT-6". At the end of the reaction period, oMWCNT-6 is filtered to remove the acid and washed with reverse osmosis (RO) water to a pH of 3 - 4. After the acid treatment, the carbon nanotubes remain in a tangled ball. The tubes are dried at 60 °C until they reach a constant weight.

[0053] Example 3 : Discrete carbon nanotubes - oxidized outermost wall (out-dMWCNT) 922 kilograms of 64% nitric acid is heated to 83 °C in a container. To this acid, 20 kilograms of untreated multi-walled carbon nanotubes (C9000, CNano Technol ogy) are added. The mixture is mixed and maintained at 83 °C for 3 hours. After 3 hours, the acid is removed by filtration, and the carbon nanotubes are washed with RO water to a pH of 3 - 4. ​​​​​​​​​​​​ This is the case. After the acid treatment, the carbon nanotubes remain as entangled balls with a few open ends. This is the case. While the outside of the tube is oxidized to form various oxidized species, the inside of the nanotube is hardly exposed to the acid and thus hardly oxidized. And the oxidized carbon nanotubes are suspended in RO water at a concentration of 1.5 wt%. The solution of RO water and the oxidized entangled nanotubes is subjected to intense 6 ~10 8 Joules / m 3 energy density generating capable treatment equipment and is subjected to destructive forces generated by shear (turbulent flow) and / or cavitation. The resulting sample has an oxidized outer wall and is designated as "out-dMWCNT" with "d" representing discrete. Equipment that meets this shear includes, but is not limited to, ultrasonic processors, cavitators, mechanical homogenizers, pressure homogenizers, and microfluidizers (Table 1). The shear and / or cavitation treatment usually causes tube breakage and opening at the ends by mechanical means that result in breakage particularly at defects in the CNT structure which is usually a 6-membered ring of carbon, thereby disaggregating the oxidized carbon nanotubes. The defects occur at locations in the tube that are not 6-membered rings of carbon. When this is done in water, oxidation does not occur on the inner surface of the discrete carbon nanotubes. This is the case. To oxidize the inside of the discrete carbon nanotubes, 3 grams of out-dMWCNT is added to 64% nitric acid heated to 85 °C. The solution is mixed and maintained at a constant temperature for 3 hours. When this is done in water, oxidation does not occur on the inner surface of the discrete carbon nanotubes.

[0054] Example 4 : Discrete carbon nanotubes - oxidized outer and inner walls (out / in-dMWCNT ) To oxidize the inside of the discrete carbon nanotubes, 3 grams of out-dMWCNT is added to 64% nitric acid heated to 85 °C. The solution is mixed and maintained at a constant temperature for 3 hours. It was held. During this time, nitric acid oxidizes the inner surface of the carbon nanotubes. At the end of 3 hours Upon completion, the tubes are filtered to remove the acid and then washed with RO water to pH 3 - 4 . This sample is designated as "out / in - dMWCNT" with "d" representing oxidation and dispersion on both the outer and inner walls .

[0055] The oxidation of the carbon nanotube samples is measured using thermogravimetric analysis. In this example, a TA Instruments Q50 Thermogravimetr ic Analyzer (TGA) is used. The dried carbon nanotube s ample is pulverized using a vibrating ball mill. 7 - 15 mg of the pulverized carbon nanotubes is added into the tar platinum pan of the TGA. The measurement protocol is as follows . In a nitrogen environment, the temperature is raised from room temperature to 100 °C at a rate of 10 °C / min to enable the removal of residual water, and held at this temperature for 45 minutes. Next, it is heated to 700 °C at a rate of 5 °C / min. During this process, the change in weight percentage is recorded as a function of temperature and time . All values are normalized for any changes related to residual water removal during the 100 °C isotherm. The weight percentage of oxygen in the carbon nanotubes (%Ox) is determined by subtracting the change in weight percentage at 600 °C from the change in weight percentage at 200 °C.

[0056] The comparison table (Table 2 below) shows the levels of oxidation of different batches of carbon nanotubes oxidized only externally (Batch 1, Batch 2, and Batch 3) or both externally and internally (Batch 4). Batch 1 (oMWCNT - 3 prepared in Example 1 above is a batch of entangled carbon nanotubes that are oxidized externally only when the batch remains in an entangled form (Table 2, first column). Batch 2 (oMWCNT-6 fabricated in Example 2 above) is also a batch of entangled carbon nanotubes that are oxidized externally only when the batch remains in an entangled form (Table 2, second column). The average oxidation rate of Batch 1 (2.04% Ox) and that of Batch 2 (2.06% Ox) are substantially the same. The difference between Batch 1 (3-hour exposure to acid) and Batch 2 (6-hour exposure to acid) is that in Batch 2, the carbon nanotubes were exposed to acid for twice the time. This indicates that further exposure to acid does not increase the amount of oxidation on the surface of the carbon nanotubes. Batch 2 (oMWCNT-6 fabricated in Example 2 above) is also a batch of entangled carbon nanotubes that are oxidized externally only when the batch remains in an entangled form (Table 2, second column). Batch 2 (oMWCNT-6 fabricated in Example 2 above) is also a batch of entangled carbon nanotubes that are oxidized externally only when the batch remains in an entangled form (Table 2, second column). Batch 2 (oMWCNT-6 fabricated in Example 2 above) is also a batch of entangled carbon nanotubes that are oxidized externally only when the batch remains in an entangled form (Table 2, second column). The average oxidation rate of Batch 1 (2.04% Ox) and that of Batch 2 (2.06% Ox) are substantially the same. The average oxidation rate of Batch 1 (2.04% Ox) and that of Batch 2 (2.06% Ox) are substantially the same. The difference between Batch 1 (3-hour exposure to acid) and Batch 2 (6-hour exposure to acid) is that in Batch 2, the carbon nanotubes were exposed to acid for twice the time. The difference between Batch 1 (3-hour exposure to acid) and Batch 2 (6-hour exposure to acid) is that in Batch 2, the carbon nanotubes were exposed to acid for twice the time. This indicates that further exposure to acid does not increase the amount of oxidation on the surface of the carbon nanotubes.

[0057] Batch 3 (Out-dMWCNT fabricated in Example 3 above) is a batch of entangled carbon nanotubes that were oxidized externally only when the batch remained in an entangled form (Table 2, third column). And Batch 3 was made into discrete batches of carbon nanotubes without further oxidation. Batch 3 serves as a control sample for the effect of oxidation on converting entangled carbon nanotubes into discrete nanotubes. Batch 3 shows substantially the same average oxidation level (1.99% Ox) as Batch 1 and Batch 2. Therefore, Batch 3 indicates that by dissociating the carbon nanotubes and dispersing them in water, the ends of the tubes are opened without internal oxidation. Batch 3 (Out-dMWCNT fabricated in Example 3 above) is a batch of entangled carbon nanotubes that were oxidized externally only when the batch remained in an entangled form (Table 2, third column). Batch 3 (Out-dMWCNT fabricated in Example 3 above) is a batch of entangled carbon nanotubes that were oxidized externally only when the batch remained in an entangled form (Table 2, third column). And Batch 3 was made into discrete batches of carbon nanotubes without further oxidation. Batch 3 serves as a control sample for the effect of oxidation on converting entangled carbon nanotubes into discrete nanotubes. Batch 3 shows substantially the same average oxidation level (1.99% Ox) as Batch 1 and Batch 2. Batch 3 shows substantially the same average oxidation level (1.99% Ox) as Batch 1 and Batch 2. Therefore, Batch 3 indicates that by dissociating the carbon nanotubes and dispersing them in water, the ends of the tubes are opened without internal oxidation.

[0058] Finally, Batch 4 (Out / In-dMW fabricated in Example 4 here) The CNTs were oxidized externally when the batches were in a tangled form and then were oxidized again after the batches were made into discrete batches of carbon nanotubes in the tangled state of carbon nanotubes (Table 2, 4th column). Since the discrete carbon nanotubes are open-ended, in Batch 4, the acid enters the inside of the tube and oxidizes the inner surface. Batch 4 shows a significantly elevated average oxidation level (2.39% Ox) compared to Batch 1, Batch 2, and Batch 3. The significant increase in the average oxidation level in Batch 4 represents further oxidation on those inner surfaces of the carbon nanotubes. Thus, the average oxidation level (2.39% Ox) for Batch 4 is approximately 20% higher than the average oxidation level (1.99% Ox ) of Batch 3. In Table 2 below, the average values of oxidation are shown for replicates of four batches of tubes. The oxidation rates are within the standard deviation for Batch 1, Batch 2, and Batch 3.

[0059]

Table 1

[0060]

Table 2

[0061] An exemplary process for forming a composition comprising discrete carbon nanotubes in a plasticizer is , first, an average aspect ratio of about 10 to about 500 and an oxidized species content of about 1 to about 15 wt. %. The objective of the present invention is to select a plurality of discrete carbon nanotubes having different levels. The carbon nanotubes are dissolved in a solution of about 1% by weight to about 10% by weight to form a nanotube-water slurry. The nanotubes are suspended in water at a concentration of 100% by volume using a shear. At least one plasticizer and temperatures between about 30°C and about 100°C are required to dissolve carbon nanotubes in water. Mix for a sufficient time for the water to migrate into the plasticizer and form a nanotube / plasticizer mixture. The mixture may contain from 70% to about 99.9% water. Most of the water is filtered, decanted, or The filtered material is separated from the mixture by filtration, or other means of mechanical separation. The material may contain about 50% to about 10% water, and the filtered material may be heated to about 40°C to about 1 Dry at a temperature of 20°C to less than 3% water by weight, most preferably less than 0.5% water by weight, In some applications, an anhydrous nanotube / plasticizer mixture is formed with 0% water by weight.

[0062] Example 5 Concentration of discrete carbon nanotubes in water with only the outer wall oxidized as in Example 3 The product is diluted to 2% by weight in deionized water. The slurry is stirred by an overhead agitator. The mixture is heated to 40°C while stirring at 400 rpm. Each gram of discrete carbon nanotubes 4 grams of TOTM (trioctyl trimer) from Sigma Aldrich The mixture is stirred at 750 rpm for 4 hours. During this time, the grease and grease are removed from the mixture, leaving the purified water at the bottom. The bonnanotubes float. When this occurs, water is separated from the TOTM / carbon nan otube mixture by filtration. The TOTM and discrete carbon nanotubes are dried at 70 °C in a forced air convection oven until the residual water is removed. A free-flowing powder is obtained. The concentration of the discrete carbon nanotubes is measured by temperature specific gravity measuring means and found to be 2 0% discrete carbon nanotubes and 80% TOTM.

[0063] Example 6 The discrete carbon nanotube and plasticizer composition of Example 5 containing 20% discrete carbon nanotubes and 80% TOTM (trioctyl trimellitate) is added to the nitrogen rubber formulation at concentrations of 2 parts per hundred resin (phr) and 3 parts per hundred resin (phr) (Table 3). The oil-fat concentration of the compound is adjusted to compensate for the additional oil-fat from the composition of the present invention. Then, the compound is cured to form plaques for testing. A forced tear test is performed using an Instron tensiometer. The forced tear sample is punched using a die to form a 1.5 inch × 1 inch × 1 inch rectangle with a 1 / 2 inch long center notch in the specimen and sliced perpendicular to the longitudinal dimension. The specimen is supported at an equal distance from the notch and pulled by Instron. The shear tensile force and stress are recorded and the area under the stress-tensile force curve from zero tensile force to final failure is measured. This area is the total tear energy. The results in Table 4 show an increase in tear strength imparted by the discrete carbon nanotubes.

[0064]

Table 3

[0065]

Table 4

[0066] Example 7 Example 5 discrete carbon nanotube and plasticizer composition containing 20% discrete carbon nanotubes and 80% TOTM (trioctyl trimellitate) is added to the nitrogen rubber formulation at a concentration of 3 parts per hundred resin (phr) (Table 5). The oil concentration of the compound is adjusted so that all formulations have the same oil concentration to compensate for additional oil from the compositions of the present invention. The comparative compound is prepared with unmodified carbon nanotubes (Flotube C9000, CNano) (Table 5). The carbon black content is adjusted so that the measured hardness is the same for 3 samples. The Shore A hardness of the 3 phr CNT of the present invention relative to the control is 67, and for the 3 phr "As is" carbon nanotubes (C9000) it is 68. The forced tear strength is measured as described in Example 6. The discrete carbon nanotube and oil composition (dCNT) of the present invention has a higher total tear energy than the entangled carbon nanotubes (C9000) and the control. The tear energy of the entangled carbon nanotubes C9000 is worse than that of the control (Table 6). The carbon black content is adjusted so that the measured hardness is the same for 3 samples. For the 3 phr CNT of the present invention the Shore A hardness relative to the control is 67, and for the 3 phr "As is" carbon nanotubes (C9000) it is 68. The forced tear strength is measured as described in Example 6. The discrete carbon nanotube and oil composition (dCNT) of the present invention has a higher total tear energy than the entangled carbon nanotubes (C9000) and the control. The tear energy of the entangled carbon nanotubes C9000 is worse than that of the control (Table 6). than the entangled carbon nanotubes (C9000) and the control. The discrete carbon nanotube and oil composition (dCNT) of the present invention has a higher total tear energy than the entangled carbon nanotubes (C9000) and the control. The tear energy of the entangled carbon nanotubes C9000 is worse than that of the control (Table 6). than the entangled carbon nanotubes (C9000) and the control. The tear energy of the entangled carbon nanotubes C9000 is worse than that of the control (Table 6). than the entangled carbon nanotubes (C9000) and the control. The tear energy of the entangled carbon nanotubes C9000 is worse than that of the control (Table 6).

[0067]

Table 5

[0068]

Table 6

[0069] It is known to those skilled in the art that the addition of fillers to rubber compounds increases the viscosity of the compounds. Contrary to expectations, the addition of discrete carbon nanotubes and oil and fat mixtures from Example 7 decreased the viscosity without increasing it, while the entangled carbon nanotubes (C9000) of Example 7 increased the viscosity. The viscosity was measured at 125 °C using a Mooney Rheometer. The initial viscosity measured represents the processability of the compound. The compound containing the discrete carbon nanotubes of the present invention was found to be equal to the control, while the compound containing the entangled carbon nanotubes (C9000) was found to be higher than the control (Table 7).

[0070]

Table 7

[0071] The disclosed embodiments may also relate to compositions useful for treating and / or modifying contaminated soil, groundwater and / or wastewater by treating, removing, denaturing, sequestering, target labeling and / or cleaving at least a portion of any dry cleaning compound and related compounds such as perchloroethylene (PCE), trichloroethylene (TCE), 1,2-dichloroethylene (DCE), vinyl chloride and / or ethane. The embodiments may also relate to compounds useful for treating, removing, denaturing, sequestering, target labeling and / or cleaving at least a portion of oils and fats, harmful or unwanted chemicals and other contaminants. The disclosed embodiments may comprise a plurality of discrete carbon nanotubes, the discrete carbon nanotubes comprising an inner surface and an outer surface ​​​​​​​​​​​​​ Each surface may comprise an internal surface oxidation species content and / or an external surface oxidation species content. Embodiments may also comprise at least one degradable or chemically active molecule attached to either the internal surface or the external surface of a plurality of discrete carbon nanotubes. Such embodiments may be used to deliver known degradable and / or chemically active molecules to the location of any contaminated soil, groundwater, and / or wastewater.

[0072] Materials used Ferrous chloride tetrahydrate FeCl2·4H2O, Sigma Aldrich, for analysis Ferric chloride FeCl3, Sigma Aldrich, for analysis Sodium hydroxide (NaOH, 10% by mass solution) Ammonium hydroxide (NH4OH, 30% by mass solution) For the dry carbon nanotubes of the present invention, the weight percentage of oxidation species is measured by performing TGA in nitrogen at a heating rate of 10 °C / min and measuring the weight loss between 200 °C and 600 °C to be 1.8%. The carbon nanotubes of the present invention in the form of a wet cake (93.7% by weight of water) Polyvinylpyrrolidone (PVP, average molecular weight 4000 0 Daltons) from Sigma Aldrich Polyvinylpyrrolidone (high molecular weight PVP, average molecular weight 360000 Daltons) from Sigma Aldrich An aqueous dispersion solution with a ratio of 0.2 PVP:1 MR (3% by weight of the carbon nanotubes of the present invention, total solids content 3.6% by weight, see the procedure in the following paragraph) Poly(bisphenol A carbonate) from Teijin Limited, melt flow rate 15 Dimethyl silicone 500 cps, Gelesat Deionized water

[0073] ​​​​​ The solution was stirred with an IKA mixer by the control of Eurostar60 and the aggressive rotor design. The pH and temperature were monitored with an Oakton pH5+ handheld meter. The dry samples were ground into fine powder for microscopy, and a Wig-L-Bug consisting of stainless steel balls and a stainless steel vial was used to improve their dispersibility. The Wig-L-Bug quickly moves the vial so that the balls inside the vial powder the material. To further improve the dispersion when necessary, two types of ultrasonic processors were used: a Crest Ultrasonic Heated Cleaner for small-scale sonication on the millimeter scale and a Sonics Vibra-Cell 505 for larger-scale sonication.

[0074] HAAKE PolyLab OS was employed together with a roller rotor for high-viscosity material synthesis. To produce the sheets, the material was compressed using thermocompression at a set temperature according to the melting point of the material for 5 minutes under a platen pressure of 25000 psi.

[0075] A JEOL JSM-7100F was used for scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and energy-dispersive X-ray spectroscopy (EDX). To prepare these sheets for microscopy, thin sections were cut using a LEICA EM UC7 microtome with glass and diamond knives. A Torbal ATS 60 moisture analyzer (muffle furnace) was used to measure the solid content of the aqueous mixture. MinFlex measures X-ray diffraction (XRD), and thermogravimetric analysis (TGA) measures the ultraviolet (UV) spectrum measured by an Agilent 8453 diode array UV / VIS spectrophotometer, model number G1103A, in the range of 200 to 100 nanometers for a 1 centimeter path length quartz cuvette. The weight fraction of magnetic materials and carbon nanotubes is conveniently measured from the temperature specific gravity measurement analysis of the sample (about 10 - 20 mg). The sample is held at 100 °C for 45 minutes and then analyzed in air at 100 °C to 800 °C at a heating rate of 10 °C / min. During the heating period, up to Fe3O4 undergoes a weight loss of about 10.5%, while the carbon nanotubes of the present invention lose about 99% of their weight. UV and XRD spectra are used to characterize the magnetic particle composition, and SEM or STEM gives the particle size. The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C. - Synthesis of Magnetite Nanometer - Sized Particles

[0076] The weight fraction of magnetic materials and carbon nanotubes is conveniently measured from the temperature specific gravity measurement analysis of the sample (about 10 - 20 mg). The sample is held at 100 °C for 45 minutes and then analyzed in air at 100 °C to 800 °C at a heating rate of 10 °C / min. During the heating period, up to Fe3O4 undergoes a weight loss of about 10.5%, while the carbon nanotubes of the present invention lose about 99% of their weight. UV and XRD spectra are used to characterize the magnetic particle composition, and SEM or STEM gives the particle size. The weight fraction of magnetic materials and carbon nanotubes is conveniently measured from the temperature specific gravity measurement analysis of the sample (about 10 - 20 mg). The sample is held at 100 °C for 45 minutes and then analyzed in air at 100 °C to 800 °C at a heating rate of 10 °C / min. During the heating period, up to Fe3O4 undergoes a weight loss of about 10.5%, while the carbon nanotubes of the present invention lose about 99% of their weight. UV and XRD spectra are used to characterize the magnetic particle composition, and SEM or STEM gives the particle size. The weight fraction of magnetic materials and carbon nanotubes is conveniently measured from the temperature specific gravity measurement analysis of the sample (about 10 - 20 mg). The sample is held at 100 °C for 45 minutes and then analyzed in air at 100 °C to 800 °C at a heating rate of 10 °C / min. During the heating period, up to Fe3O4 undergoes a weight loss of about 10.5%, while the carbon nanotubes of the present invention lose about 99% of their weight. UV and XRD spectra are used to characterize the magnetic particle composition, and SEM or STEM gives the particle size. The weight fraction of magnetic materials and carbon nanotubes is conveniently measured from the temperature specific gravity measurement analysis of the sample (about 10 - 20 mg). The sample is held at 100 °C for 45 minutes and then analyzed in air at 100 °C to 800 °C at a heating rate of 10 °C / min. During the heating period, up to Fe3O4 undergoes a weight loss of about 10.5%, while the carbon nanotubes of the present invention lose about 99% of their weight. UV and XRD spectra are used to characterize the magnetic particle composition, and SEM or STEM gives the particle size. The weight fraction of magnetic materials and carbon nanotubes is conveniently measured from the temperature specific gravity measurement analysis of the sample (about 10 - 20 mg). The sample is held at 100 °C for 45 minutes and then analyzed in air at 100 °C to 800 °C at a heating rate of 10 °C / min. During the heating period, up to Fe3O4 undergoes a weight loss of about 10.5%, while the carbon nanotubes of the present invention lose about 99% of their weight. UV and XRD spectra are used to characterize the magnetic particle composition, and SEM or STEM gives the particle size. The weight fraction of magnetic materials and carbon nanotubes is conveniently measured from the temperature specific gravity measurement analysis of the sample (about 10 - 20 mg). The sample is held at 100 °C for 45 minutes and then analyzed in air at 100 °C to 800 °C at a heating rate of 10 °C / min. During the heating period, up to Fe3O4 undergoes a weight loss of about 10.5%, while the carbon nanotubes of the present invention lose about 99% of their weight. UV and XRD spectra are used to characterize the magnetic particle composition, and SEM or STEM gives the particle size.

[0077] The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C. The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C. The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C. The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C. The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C. The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C. The EMI test is performed in the frequency range of 1.6 to 12 GHz using an Agilent EX6 analog signal generator, an Anritsu MS2691A spectrum analyzer coaxial with a waveguide adapter, and an HP11692D 2 - 18 GHz directional coupler with a 50 ohm termination. The waveguide adapters used are for the frequency ranges of 1.6 to 2.6, 2.7 to 4, 4.1 to 6, 6.1 to 8, and 8.1 to 12 GHz. The measurements are made at 0.1 GHz intervals. First, a blank spectrum is obtained, and then a specimen with a thickness of 1 - 2 mm is placed between two waveguide adapters. All measurements are at 25 °C.

[0078] Example 1 (EMI) - Synthesis of Magnetite Nanometer - Sized Particles First, 0.79 g of FeCl2·4H2O is dissolved in 200 g of deionized water at room temperature. Using an overhead mixer equipped with an aggressive 6 cm diameter rotor, After vigorous stirring at 400 rpm for 1 minute, 1.29 g of FeCl3 was added and the sample The resulting yellow solution has an iron concentration of 0.06M and and a pH between 1.9 and 2.0. 12.5 g of 10% sodium hydroxide quickly In other words, it took less than about 2 seconds for the solution to be added, and the solution turned black. It is used as a base, but other bases such as ammonium hydroxide can be used to reduce the pH to about 9-11. The base may be employed in an amount sufficient to provide a sufficient amount of base to the sample. After vigorously stirring the sample for another minute, the solution was stirred for 1 minute to ensure complete chemical conversion to Fe3O4. Gentle stirring is continued for 1 hour. The final pH is about 9.

[0079] The Fe3O4 nanoparticles were allowed to settle to the bottom of the beaker, and the supernatant was decanted and sieved. The pH of the water on top of the sample is then adjusted to 6.5-7.0. The sample is then heated at 95°C for at least 12 hours. The yield recorded was 1.25g for the conversion of iron chloride to magnetite. The SEM shows that the particle size is approximately 20-30 nanometers in diameter. was measured.

[0080] Figure 1 shows the UV spectrum of dirty water on top of Fe3O4 particles during the cleaning process.

[0081] Example 2 (EMI) Same as Example 1 (EMI), but the amount of base added is such that the final pH is about 11. It is as follows. The particles have a diameter of about 10 to 20 nanometers, and the yield was about 30% by weight. .

[0082] Example 3 (EMI) It is the same as Example 2 (EMI), but the temperature is maintained at 50 °C. The average particle size is about 40 to 50 nanometers, and the yield was about 30% by weight.

[0083] Example 4 (EMI) It is the same as Example 2 (EMI), but the base is added gradually over 30 minutes. The average particle size is about 40 to 50 nanometers. The yield is about 30% by weight.

[0084] Examples 1 to 4 (EMI) are those that give the maximum yield (higher than 90% by weight) of magnetite at a temperature of 25 °C, rapid addition of the base, and a final pH of about 9, indicating that SEM gives an average particle size of about 20 to 3 0 nanometers. The UV and XRD spectra of the particles are consistent with the magnetite structure. 0 nanometers. The UV and XRD spectra of the particles are consistent with the magnetite structure. The UV and XRD spectra of the particles are consistent with the magnetite structure.

[0085] Examples of binding magnetic particles to the carbon nanotubes of the present invention, and examples of the suitable oxidation level in discrete carbon nanotubes with respect to the degree of adhesion of magnetic particles Examples of the suitable oxidation level in discrete carbon nanotubes with respect to the degree of adhesion of magnetic particles

[0086] Examples 5-8 (EMI) -Examine the influence of the weight ratio of -MR to magnetic particles For Examples 5, 6 and 8 (EMI), a certain amount of 7. 9 g of FeCl2·4H2O and 12.9 g of FeCl3 are employed in 2 liters of deionized water, which would amount to 9.3 g of Fe3O4 (magnetite) assuming 1 00% conversion of iron chloride. The procedure is first to dissolve 7.9 g of FeCl2·4H2O in 2000 g of water at room temperature. This is vigorously stirred for 1 minute After stirring, 12.9 g of Fe3O4 is added and the sample is stirred for an additional 1 minute. The resulting solution has an iron concentration of 0.06 M and a pH between 1.9 and 2.0. 125 g of 10 wt% NaOH solution is added to increase the pH from 1.97 to 9.16. The sample is vigorously stirred for more than 1 minute to thoroughly mix the NaOH with the sample. After that, the sample is gently stirred for 1 hour to complete the chemical conversion to Fe3O4. After 1 hour of stirring, the pH becomes 8.8 and the sample is washed as described in Example 1 (EMI). Example 7 (EMI) has the same procedure, but the amounts of materials are scaled down to 1 / 10.

[0087] Example 5 (EMI) The weight ratio of carbon nanotubes to magnetite is 65:35.

[0088] 344.8 g of wet cake (carbon nanotubes with 93.7% water and 1.8 wt% oxidized species measured by TGA) and 1677 g of water are stirred at 400 rpm for 10 minutes in a 3-liter stainless steel beaker at 25°C. While stirring vigorously for an additional 1 minute, 12.9 g of FeCl3 follows 7.9 g of FeCl2·4H2O. The pH at this instant is approximately 1.8. 126 grams of 10% sodium hydroxide solution is added within about 1 minute while stirring the sample vigorously, and then the stirring is continued gently for about 1 hour. The materials are washed and dried as in Example 1 (EMI). TGA analysis showed a dry weight ratio of carbon nanotubes to magnetite of 65:35.

[0089] Example 6 (EMI)- The weight ratio of carbon nanotubes to magnetite is 47:53 . Same as Example 5 (EMI), but 147.6 g of wet cake and 1862 g of deionized water are used.

[0090] Example 7 (EMI) - The weight ratio of carbon nanotubes to magnetite is 25:75 . Same as Example 5 (EMI), but 1 / 10 the amount of iron chloride, 4.90 g of wet cake and 195.4 g of deionized water are used.

[0091] Example 8 (EMI) - The weight ratio of carbon nanotubes to magnetite is 10:90 . Same as Example 5 (EMI), but 16.3 g of wet cake and 1985 g of deionized water are used.

[0092] Example 9 (EMI) - Use of the carbon nanotubes and surfactant of the present invention 6.0 grams of PVP with an average molecular weight of 40,000 daltons is added to deionized water and stirred vigorously until the PVP is completely dissolved. While stirring vigorously for 3 minutes, 47 6.2 grams of 6.3% wet cake is added, and then the solution is sonicated until the solution shows good dispersion in an optical microscopy examination. During sonication, the solution does not exceed 40 °C.

[0093] 33.3 g of 0.2PVP:1MR solution is added to 167.87 g of deionized water and stirred vigorously for 1 0 minutes. 0.15 g of PVP is added and stirred for an additional 5 minutes. Next 0.86 g of FeCl2·4H2O is added, stirred for 1 minute, and the addition of 1.40 g of Fe Cl3 follows, and stirring continues for an additional 1 minute. Subsequently, the sample is sonicated while being stirred It is processed. After sonication of about 40 kJ, the sample temperature reaches 56 °C. The sample is cooled to 31 °C over about 1 hour. The pH is 1.7. 12.9 g of NaOH is quickly added while stirring and the pH rises to 9.4. Gentle stirring is continued for 1 hour and the washing procedure outlined for Example 1 (EMI) follows. The Fe3O4 particle size is about 20 nanometers in diameter. The yield is 98%.

[0094] Comparing Examples 5 - 8 (EMI) by electron microscopy results, surprisingly, it was found that when the weight fraction of magnetic particles exceeded that of the carbon nanotubes used in Examples 5 - 8 (EMI), clusters of magnetic particles appeared. The number of particles attached per carbon nanotube is about 5 - 8 in Examples 5 - 8 (EMI). Generally speaking, long straight carbon nanotubes have fewer particles than bent or coiled ones do. This demonstrates that there is a specific relationship between the amount of oxidized species on the outermost surface of the carbon nanotube and the number of nanoparticles that can adhere to the outermost surface of the carbon nanotubes of the present invention. Without being bound by theory, it is expected that bends or twists along the length of the tube are caused by wall defects and that the defects allow for more facile chemical reactions

[0095] A comparison of Example 9 (EMI) having the carbon nanotubes of the present invention homogeneously dispersed in an iron chloride mixture using polyvinylpyrrolidone before the addition of base with Example 6 (EMI) shows that, as shown in Figure 2, by An increase from about 5 to about 10 was revealed. This is a surprising result because the porosity of the small amount of coagulant of the carbon nanotubes with a dispersed wet cake is very high, which does not limit the movement of iron chloride or the base. nanotubes with a dispersed wet cake is very high, which does not limit the movement of iron chloride or the base. limit the movement of iron chloride or the base, which is a surprising result.

[0096] Examples regarding EMI shielding Figure 3 shows the EMI shielding effect of four compositions of polycarbonate compositions with and without MR, indicating that the EMI shielding effect is affected by dispersion. Figure 3 shows the EMI shielding effect of four compositions of polycarbonate compositions with and without MR, indicating that the EMI shielding effect is affected by dispersion.

[0097] Figure 4 shows the attenuation of NBR compounds with 5, 10, and 15% MR.

[0098] Figures 5A - C show the power transmittance, reflectance, and absorbance in NBR compositions with 5, 10, and 15% MR. As can be understood, the higher the frequency, the higher the absorbance of MR. The frequency at which the high absorbance occurs decreases with increasing MR. The frequency of the peak of the reflected power is at about 5 - 6 GHz, independent of the MR content. Figures 5A - C show the power transmittance, reflectance, and absorbance in NBR compositions with 5, 10, and 15% MR. As can be understood, the higher the frequency, the higher the absorbance of MR. The frequency at which the high absorbance occurs decreases with increasing MR. The frequency of the peak of the reflected power is at about 5 - 6 GHz, independent of the MR content. Figures 5A - C show the power transmittance, reflectance, and absorbance in NBR compositions with 5, 10, and 15% MR. As can be understood, the higher the frequency, the higher the absorbance of MR. The frequency at which the high absorbance occurs decreases with increasing MR. The frequency of the peak of the reflected power is at about 5 - 6 GHz, independent of the MR content. Figures 5A - C show the power transmittance, reflectance, and absorbance in NBR compositions with 5, 10, and 15% MR. As can be understood, the higher the frequency, the higher the absorbance of MR. The frequency at which the high absorbance occurs decreases with increasing MR. The frequency of the peak of the reflected power is at about 5 - 6 GHz, independent of the MR content.

[0099] Figures 6 - 11 show the TGA of Fe3O4 nanoparticles and / or MR compositions.

[0100] Addition of payload molecules The water solubility of drug substances is an important parameter in the pre - formulation study of drug products. Some drugs are slightly water - soluble, which brings challenges for formulation and dosing. Organic solvents or oils and additional surfactants that generate dispersion can be used. If the payload molecule is easily dissolved or dispersed in an aqueous medium, the filter cake does not need to be dried. If the payload molecule is not easily dissolved or dispersed in an aqueous medium, the filter cake is first vacuumed. The water solubility of drug substances is an important parameter in the pre - formulation study of drug products. Some drugs are slightly water - soluble, which brings challenges for formulation and dosing. Organic solvents or oils and additional surfactants that generate dispersion can be used. If the payload molecule is easily dissolved or dispersed in an aqueous medium, the filter cake does not need to be dried. If the payload molecule is not easily dissolved or dispersed in an aqueous medium, the filter cake is first vacuumed. The water solubility of drug substances is an important parameter in the pre - formulation study of drug products. Some drugs are slightly water - soluble, which brings challenges for formulation and dosing. Organic solvents or oils and additional surfactants that generate dispersion can be used. If the payload molecule is easily dissolved or dispersed in an aqueous medium, the filter cake does not need to be dried. If the payload molecule is not easily dissolved or dispersed in an aqueous medium, the filter cake is first vacuumed. The water solubility of drug substances is an important parameter in the pre - formulation study of drug products. Some drugs are slightly water - soluble, which brings challenges for formulation and dosing. Organic solvents or oils and additional surfactants that generate dispersion can be used. If the payload molecule is easily dissolved or dispersed in an aqueous medium, the filter cake does not need to be dried. If the payload molecule is not easily dissolved or dispersed in an aqueous medium, the filter cake is first vacuumed. The water solubility of drug substances is an important parameter in the pre - formulation study of drug products. Some drugs are slightly water - soluble, which brings challenges for formulation and dosing. Organic solvents or oils and additional surfactants that generate dispersion can be used. If the payload molecule is easily dissolved or dispersed in an aqueous medium, the filter cake does not need to be dried. If the payload molecule is not easily dissolved or dispersed in an aqueous medium, the filter cake is first vacuumed. The desired concentration of the Peyro in the liquid medium is then dried at 80°C until a constant weight is obtained. The ion-doped molecules are added to the discrete carbon nanotubes and allowed to grow uniformly within the tube cavity for several hours. The mixture is then filtered to form a cake less than about 1 mm thick. The large amount of payload solution not present in the tubing is removed by high flow rate filtration. The rate of filtration is determined by the short time it takes for the payload molecules to diffuse out of the tube cavity. The filter cake is then selected to be only tolerant to the payload drug. The present invention relates to the preparation of such aqueous solutions of biopolymers, amino acids, proteins or peptides. If it is desired to attach larger molecules, they undergo additional processing.

[0101] Example 8 A calibration curve was measured for the UV absorbance of niacin as a function of its concentration in water. A solution was prepared by dissolving 0.0578 grams of the discrete functionalized carbon nanotube of the present invention in 25 ml of water. Prepared by mixing 0.0134 grams of niacin with 1000mg of niacin. (0.231 grams of niacin per gram of carbon nanotubes). The tubes precipitated. An aliquot of the fluid in the tube was removed every hour. The UV-vis absorbance was measured and the resulting amount of niacin in solution was recorded. The amount of niacin in the aqueous solution stabilized after 6 hours. The final sample was taken 20 minutes after mixing. The difference between the amount of niacin remaining in the solution and the initial amount was determined by the amount of the discrete functionalized carbohydrate. The amount of niacin associated with the nanotubes was measured as 0.0746 grams of niacin. It turns out that 100 ketones can be associated with each gram of carbon nanotube. The total amount of niacin absorbed by the tube was 0.0043 grams. The carbon nanotube has a length of 1000 nm, an outer diameter of 12 nm, and an inner diameter of 5 nm. , the available volume in the tube is 0.0 per gram of carbon nanotube. 93cm 3 The density of niacin is 1.473 g / cm 3 Therefore, it is suitable for tubes. The maximum amount of niacin that can be combined is 0.137 grams. The measured absorption rate of the amount of niacin / g of CNT can be confined inside the tube.

[0102] Example 9 Poly(vinyl alcohol) PVOH is very large (30 kDa to 70 kDa) and PVOH cannot be absorbed into the interior of the carbon nanotubes. It binds to and wraps around carbon nanotubes, making it useful as a surfactant for carbon nanotubes. In this experiment, PVOH was dissolved in 25 ml of water at 0.0535 g of carbon nanotubes. tubes and 0.0139g of niacin (0. 26 grams of niacin) was added to the mixture. This was kept overnight. Using V-vis technology, the amount of niacin bound to carbon nanotubes was measured in Example 1. 0.0746 grams in 1, 0.05 per gram of carbon nanotubes The total amount of niacin absorbed was determined to be 0.003 It was grams.

[0103] The calculation was performed with a carbon nanotube length of 1000 nm, an outer diameter of 12 nm, and an inner diameter of 5 nm. The density of PVOH was 1.1 g / cm3 and considering that the ratio of PVOH to carbon nanotubes was 0.23 with respect to 1, the average layer thickness of PVOH on the carbon nanotubes is 0.6 nm. Therefore, there is sufficient PVOH to encapsulate the carbon nanotubes and replace niacin on the surface of the tubes, and 0.0561 grams of niacin per gram of carbon nanotubes is present inside the carbon nanotubes. Considering that the ratio of PVOH to carbon nanotubes was 0.23 with respect to 1, the average layer thickness of PVOH on the carbon nanotubes is 0.6 nm. Therefore, there is sufficient PVOH to encapsulate the carbon nanotubes and replace niacin on the surface of the tubes, and 0.0561 grams of niacin per gram of carbon nanotubes is present inside the carbon nanotubes. and considering that the ratio of PVOH to carbon nanotubes was 0.23 with respect to 1, the average layer thickness of PVOH on the carbon nanotubes is 0.6 nm. Therefore, there is sufficient PVOH to encapsulate the carbon nanotubes and replace niacin on the surface of the tubes, and 0.0561 grams of niacin per gram of carbon nanotubes is present inside the carbon nanotubes. and considering that the ratio of PVOH to carbon nanotubes was 0.23 with respect to 1, the average layer thickness of PVOH on the carbon nanotubes is 0.6 nm. Therefore, there is sufficient PVOH to encapsulate the carbon nanotubes and replace niacin on the surface of the tubes, and 0.0561 grams of niacin per gram of carbon nanotubes is present inside the carbon nanotubes. and considering that the ratio of PVOH to carbon nanotubes was 0.23 with respect to 1, the average layer thickness of PVOH on the carbon nanotubes is 0.6 nm. Therefore, there is sufficient PVOH to encapsulate the carbon nanotubes and replace niacin on the surface of the tubes, and 0.0561 grams of niacin per gram of carbon nanotubes is present inside the carbon nanotubes. and considering that the ratio of PVOH to carbon nanotubes was 0.23 with respect to 1, the average layer thickness of PVOH on the carbon nanotubes is 0.6 nm. Therefore, there is sufficient PVOH to encapsulate the carbon nanotubes and replace niacin on the surface of the tubes, and 0.0561 grams of niacin per gram of carbon nanotubes is present inside the carbon nanotubes.

[0104] In other embodiments, discrete functionalized carbon nanotubes can be dispersed in a polymer matrix, such as polyethylene oxide, in a melt or in a solution and added payload molecules. In other embodiments, discrete functionalized carbon nanotubes can be dispersed in a polymer matrix, such as polyethylene oxide, in a melt or in a solution and added payload molecules. In other embodiments, discrete functionalized carbon nanotubes can be dispersed in a polymer matrix, such as polyethylene oxide, in a melt or in a solution and added payload molecules. [Table 8] Condition 1 is an example of a narrow distribution with a short average length. Condition 2 is an example of a wide distribution with a short average length. Condition 3 is an example of a long average length and a wide dispersion. Condition 1 is an example of a narrow distribution with a short average length. Condition 2 is an example of a wide distribution with a short average length. Condition 3 is an example of a long average length and a wide dispersion.

[0105] To measure the tube length, a sample of the tubes is diluted in isopropyl alcohol and sonicated for 30 minutes. Then it is deposited on a silica wafer and imaged by SEM at 15 kV and 20,000 times magnification. These images are taken at different positions. Using JEOL software (included in the SEM), at least two lines are drawn across each image, and the length of the tubes intersecting this line is measured. To measure the tube length, a sample of the tubes is diluted in isopropyl alcohol and sonicated for 30 minutes. Then it is deposited on a silica wafer and imaged by SEM at 15 kV and 20,000 times magnification. These images are taken at different positions. Using JEOL software (included in the SEM), at least two lines are drawn across each image, and the length of the tubes intersecting this line is measured. To measure the tube length, a sample of the tubes is diluted in isopropyl alcohol and sonicated for 30 minutes. Then it is deposited on a silica wafer and imaged by SEM at 15 kV and 20,000 times magnification. These images are taken at different positions. Using JEOL software (included in the SEM), at least two lines are drawn across each image, and the length of the tubes intersecting this line is measured. To measure the tube length, a sample of the tubes is diluted in isopropyl alcohol and sonicated for 30 minutes. Then it is deposited on a silica wafer and imaged by SEM at 15 kV and 20,000 times magnification. These images are taken at different positions. Using JEOL software (included in the SEM), at least two lines are drawn across each image, and the length of the tubes intersecting this line is measured. To measure the tube length, a sample of the tubes is diluted in isopropyl alcohol and sonicated for 30 minutes. Then it is deposited on a silica wafer and imaged by SEM at 15 kV and 20,000 times magnification. These images are taken at different positions. Using JEOL software (included in the SEM), at least two lines are drawn across each image, and the length of the tubes intersecting this line is measured.

[0106] Skewness is a measure of the asymmetry of a probability distribution. A positive value means that the right tail of the distribution histogram is longer than the left, and vice versa. A positive skewness indicates more long tubes. Skewness is a measure of the asymmetry of a probability distribution. A positive value means that the right tail of the distribution histogram is longer than the left, and vice versa. A positive skewness indicates more long tubes. The skewness is preferable. A value of zero means a relatively uniform distribution on both sides of the mean value. The kurtosis is a measure of the sharpness of the distribution curve and is generally relative to a normal distribution. Neither skewness nor kurtosis has a unit.

[0107] The following table shows representative values of discrete carbon nanotubes. Table 9: Diameter (independent of the above conditions) (L / D) Average diameter value (nm*) 12.5 Median diameter (nm) 11.5 Kurtosis 3.6 Skewness 1.8 Calculated aspect ratio 34 39 58 (L / D) *nm = nanometer

[0108] A small sample of the filter cake is dried in vacuo at 100 °C for 4 hours, and thermogravimetric analysis is performed in nitrogen from 100 °C to 600 °C at a heating rate of 10 °C / min. The amount of the oxidized species of the fiber is obtained as the weight loss between 200 °C and 600 °C. The dispersion of individual tubes (discrete) is also measured by UV spectroscopic analysis. Water is added to the wet cake to give a suspension of 0.5 wt% carbon nanotubes, and then sodium dodecylbenzenesulfonate is added at a concentration 1.5 times the mass of the oxidized carbon nanotubes. The solution is sonicated for 30 minutes using a sonication bath and then diluted to a concentration of 2.5×10 g / ml of carbon nanotubes. The carbon nanotubes will give a UV absorbance of at least 1.2 absorption units at 500 nm. The improvement in the flow processability of the composition is measured using a rheometer, for example, the fluid resistance to flow against flow... -5 g / ml The carbon nanotubes will give a UV absorbance of at least 1.2 absorption units at 500 nm.

[0109] The improvement in the flow processability of the composition is measured using a rheometer, for example, the fluid resistance to flow ​Measure the resistance and measure its viscous behavior using correctly defined geometric concentric cylinders. This is possible. As the outer cylinder rotates relative to the inner cylinder, the composition flows while its resistance to deformation creates a shear stress on the inner wall of the cup and is measured in units of Pa.

[0110] Embodiments The embodiments disclosed in the present application include the following.

[0111] 1. A composition comprising a plurality of discrete carbon nanotubes, wherein the discrete carbon nanotubes comprise an inner surface and an outer surface, each surface having an inner surface oxide species content and an outer surface oxide species content, and the inner surface oxide species content is at least 20% to a maximum of 100% different from the outer surface oxide species content.

[0112] 2. The composition of embodiment 1, wherein the inner surface oxide species content is less than the outer surface oxide species content. .

[0113] 3. The inner surface oxide species content is up to 3 weight percent based on the weight of the carbon nanotubes, preferably about 0.01 to about 3 weight percent based on the weight of the carbon nanotubes, more preferably about 0.01 to about 2 weight percent, and most preferably about 0.01 to about 0. 8 weight percent. The composition of embodiment 1. 8 weight percent. The composition of embodiment 1.

[0114] 4. The outer surface oxide species content is about 1 to about 6 weight percent based on the weight of the carbon nanotubes, preferably about 1 to about 4 weight percent, more preferably about 1 to about 2 weight percent . The composition of embodiment 1.

[0115] 5. The sum of the inner surface oxide species content and the outer surface oxide species content is based on the carbon nanotubes The composition of Embodiment 1, which is about 1 to about 9 weight percent based on the weight of B.

[0116] 6. A composition comprising a plurality of discrete carbon nanotubes, wherein the discrete carbon nanotubes have an inner surface and an outer surface, each surface having an inner surface oxide species content and an outer surface oxide species content, wherein the inner surface oxide species content comprises from about 0.01 to less than about 0.8 percent based on the weight of the carbon nanotubes, and the outer surface oxide species content comprises more than about 1.2 to about 3 percent based on the weight of the carbon nanotubes. wherein the inner surface oxide species content comprises from about 0.01 to less than about 0.8 percent based on the weight of the carbon nanotubes, and the outer surface oxide species content comprises more than about 1.2 to about 3 percent based on the weight of the carbon nanotubes. wherein the inner surface oxide species content comprises from about 0.01 to less than about 0.8 percent based on the weight of the carbon nanotubes, and the outer surface oxide species content comprises more than about 1.2 to about 3 percent based on the weight of the carbon nanotubes.

[0117] 7. The composition of Embodiment 6, wherein the discrete carbon nanotubes comprise a plurality of open-ended tubes. The composition of Embodiment 6, wherein the discrete carbon nanotubes comprise a plurality of open-ended tubes.

[0118] 8. The composition of Embodiment 6, wherein the plurality of discrete carbon nanotubes comprise a plurality of open-ended tubes. The composition of Embodiment 6, wherein the plurality of discrete carbon nanotubes comprise a plurality of open-ended tubes.

[0119] 9. The composition of Embodiment 1, wherein the discrete carbon nanotubes comprise a plurality of open-ended tubes. The composition of Embodiment 1, wherein the discrete carbon nanotubes comprise a plurality of open-ended tubes. [[ID=3!]]

[0120] 10. Use of the composition of Embodiment 1 as an ion conductor.

[0121] 11. Use of the composition of Embodiment 1 as a targeting, sequestering and labeling agent in groundwater remediation. .

[0122] The composition of Embodiment 1 or Embodiment 6.

[0123] 13. A drug delivery or sustained release formulation comprising the composition of Embodiment 1 or Embodiment 6.

[0124] 14. A battery comprising the composition of Embodiment 1 or Embodiment 6.

[0125] Embodiment 1 or Embodiment 6 composition comprising a preparation.

[0126] 16. Further comprising at least one hydrophobic material in contact with at least one inner surface The composition of Embodiment 1 or Embodiment 6.

[0127] 17. The difference between the oxidation of the inner surface and the oxidation of the outer surface is at least about 0.2 weight percent of the composition of Embodiment 1 or Embodiment 6.

[0128] 18. The discrete carbon nanotubes have an aspect ratio of about 10 to about 500, and the carbon nanotubes have an oxidation level of about 1 to 3 weight percent of the carbon nanotubes of the composition of Embodiment 1 or Embodiment 6 and at least one plasticizer.

[0129] 19. The composition comprises from about 10 weight percent to about 90 weight percent, preferably from about 1 0 weight percent to about 40 weight percent of discrete carbon nanotubes, of the composition of Embodiment 18.

[0130] 20. The oxidizing species are selected from the group consisting of carboxylic acids, phenols, aldehydes, ketones, ether linkages, and combinations thereof, of the composition of Embodiment 18.

[0131] 21. The total oxidizing species content of the inner surface and the outer surface constitutes about 1 weight% to 15 weight% of the carbon nanotubes of the composition of Embodiment 18.

[0132] 22. The plasticizer is a dicarboxyl / tricarboxyl ester, trimellitate, a Dipeates, sebacates, maleic esters, glycols and polyethers, polymeric plasticizers, bio-based plasticizers, and mixtures thereof, the composition of embodiment 18 selected from the group consisting of 。 。

[0133] 23. The plasticizer is a process oil selected from the group consisting of naphthenic oil, paraffin oil, paraben oil, aromatic oil, vegetable oil, seed oil and mixtures thereof, the composition of embodiment 18. 。

[0134] 24. Except that the carbon nanotubes are in a tangled state after production without being dispersed, the composition of embodiment 23 having a viscosity substantially the same as or less than that of the same composition having the same elements in the same ratio. 。 。

[0135] 25. The plasticizer is a water-immiscible solvent selected from the group consisting of xylene, pentane, methyl ethyl ketone, hexane, heptane, ethyl acetate, ether, dichloromethane, dichloroethane, cyclohexane, chloro form, carbon tetrachloride, butyl acetate butanol, benzene, and mixtures thereof, the composition of embodiment 18. 。

[0136] 26. The composition of embodiment 18 further comprising an inorganic filler selected from the group consisting of silica, nano-clay, carbon black, graphene, glass fiber, and mixtures thereof 。 。

[0137] 27. The composition of embodiment 18 in the form of free-flowing particles.

[0138] 28. A process for making the composition of embodiment 18, comprising: a) a plurality of discrete carbons having an average aspect ratio of about 10 to about 500 and a total oxidation species content level of about 1 to about 15 wt% Step of selecting carbon nanotubes, and b) suspending the discrete carbon nanotubes in an aqueous medium at a nanotube concentration of about 1 wt% ~ about 10 wt% to form an aqueous medium / carbon nanotube slurry - forming step; c) at least one plasticizer and a temperature of about 30 °C to about 100 °C, mixing the carbon nanotube / aqueous medium slurry for a time sufficient for the carbon nanotubes to move from the aqueous medium to the plasticizer to form a wet carbon nanotube / plasticizer mixture; e) separating the aqueous medium from the wet carbon nanotube / plasticizer mixture to form a dry carbon nanotube / plasticizer mixture; f) drying at about 40 °C to about 120 °C to remove the remaining aqueous medium from the dry carbon nanotube / plasticizer mixture to form an anhydrous carbon nanotube / plasticizer mixture, comprising the steps of process.

[0139]

[0140] 29. The composition of embodiment 18, wherein the composition is further mixed with at least one rubber

[0140] 30. The rubber is a natural or synthetic rubber selected from the group consisting of natural rubber, polyisobutylene, polybutadiene and styrene-butadiene rubber, butyl rubber, polyisoprene, styrene-isoprene rubber, styrene-isoprene rubber, ethylene, propylene diene rubber, silicone, polyurethane, polyester - polyether, hydrogenated and non-hydrogenated nitrile rubber, halogen-modified elastomer, fluorine elastomer, and combinations thereof, the composition of embodiment 29

[0141] 31. The composition further comprises at least one thermoplastic polymer and at least one thermoplastic elastomer The composition of embodiment 18 further comprising a lastmer, or a combination thereof.

[0142] 32. The composition of embodiment 18 further comprising at least one thermosetting polymer, preferably epoxy or poly urethane.

[0143] 33. A composition useful for treating contaminated groundwater using a dry cleaning compound comprising a plurality of discrete carbon nanotubes, wherein the discrete carbon nanotubes have an internal surface and an external surface, each surface having an internal surface oxide species content and an external surface oxide species content, the internal surface and the external surface, and at least one decomposing molecule attached to the internal surface or the external surface of the plurality of discrete carbon nanotubes. The following are also included as other embodiments disclosed in the present application. [1] An electromagnetic shielding composition comprising a plurality of discrete carbon nanotubes and at least one magnetic metal and / or an alloy thereof, wherein the discrete carbon nanotubes have an inner surface and an outer surface, the inner surface has an inner surface oxidation species content, the outer surface has an outer surface oxidation species content, and the inner surface oxidation species content is at least 20% and at most 100% different from the outer surface oxidation species content, the electromagnetic shielding composition. [2] The electromagnetic shielding composition according to [1] above, wherein the inner surface oxidation species content includes from about 0.01 to less than about 0.8 percent based on the weight of the carbon nanotubes, and the outer surface oxidation species content includes more than about 1.2 to about 3 percent based on the weight of the carbon nanotubes. [3] The electromagnetic shielding composition according to [1] above, wherein the magnetic metal and / or an alloy thereof is selected from the group consisting of iron, chromium, aluminum, uranium, platinum, copper, cobalt, lithium, nickel, neodymium, and samarium. [4] The electromagnetic shielding composition according to [1] above, wherein the magnetic metal and / or an alloy thereof consists of metal oxides and / or alloy oxides. [5] The composition according to [1] above, wherein the discrete carbon nanotubes comprise a plurality of open-ended tubes. [6] The composition according to [1] above, wherein the plurality of discrete carbon nanotubes comprise a plurality of open-ended tubes. [7] The composition according to [1] above, wherein the inner surface oxidation species content is less than the outer surface oxidation species content. [8] The composition according to [1] above, wherein the inner surface oxidation species content is up to 3 weight percent based on the weight of the carbon nanotubes. [9] The composition according to [1] above, wherein the content of the oxidation species on the external surface is about 1 to about 6 weight percent based on the weight of the carbon nanotubes.

[10] The composition according to [1] above, wherein the total of the content of the oxidation species on the internal surface and the content of the oxidation species on the external surface is about 1 to about 9 weight percent based on the weight of the carbon nanotubes.

[11] The composition according to [1] above, wherein the difference between the internal surface oxidation and the external surface oxidation is at least about 0.2 weight percent.

[12] The composition according to [1] above, wherein the oxidation species is selected from the group consisting of carboxylic acids, phenols, aldehydes, ketones, ether linkages, and combinations thereof.

[13] The composition according to [1] above, wherein the total content of the oxidation species on the internal surface and the external surface consists of about 1 weight% to 15 weight% of the carbon nanotubes.

[14] The composition according to [1] above, which is in the form of free-flowing particles.

[15] The composition according to [1] above, wherein the composition is further mixed with at least one rubber.

[16] The composition according to [1] or [2] above, wherein the composition further comprises at least one thermoplastic polymer, at least one thermoplastic elastomer, or a combination thereof.

[17] The composition according to [1] above, wherein the composition further comprises at least one thermosetting polymer selected from the group consisting of epoxies, polyurethanes, and combinations thereof.

[18] A composition useful for treating contaminated groundwater, comprising a plurality of discrete carbon nanotubes and at least one magnetic metal and / or an alloy thereof, wherein the discrete carbon nanotubes have an internal surface and an external surface, the internal surface having an internal surface oxidation species content and the external surface having an external surface oxidation species content, the internal surface and the external surface, and at least one degrading molecule attached to the internal surface or the external surface of at least a portion of the plurality of discrete carbon nanotubes The composition comprising.

[19] The composition according to [1] above, wherein the at least one magnetic metal and / or an alloy thereof is bonded or attached to the plurality of discrete carbon nanotubes.

[20] The composition according to [1] above, wherein the plurality of discrete carbon nanotubes consists of multi-walled carbon nanotubes.

Claims

1. Comprising a plurality of discrete carbon nanotubes and at least one magnetic metal and / or its alloy, wherein the discrete carbon nanotubes have an inner surface and an outer surface, the inner surface has an inner surface oxidation species content, and the outer surface has an outer surface oxidation species content, and an electromagnetic shielding composition in which the total oxidation species content of the inner surface oxidation species content and the outer surface oxidation species content is 1 wt% to 15 wt% of the discrete carbon nanotubes.

2. The electromagnetic shielding composition according to Claim 1, wherein the at least one magnetic metal and / or its alloy has a particle size of less than 70 nm.

3. The electromagnetic shielding composition according to Claim 1, wherein the discrete carbon nanotubes include multi-walled carbon nanotubes.

4. The electromagnetic shielding composition according to Claim 1, wherein the discrete carbon nanotubes include single-walled carbon nanotubes.

5. The electromagnetic shielding composition according to Claim 1, wherein the discrete carbon nanotubes include double-walled carbon nanotubes.

6. The electromagnetic shielding composition according to Claim 1, wherein the total oxidation species content of the inner surface oxidation species content and the outer surface oxidation species content is 1 wt% to 10 wt% of the discrete carbon nanotubes.

7. The electromagnetic shielding composition according to Claim 1, wherein the magnetic metal and / or its alloy is selected from the group consisting of iron, chromium, aluminum, uranium, platinum, copper, cobalt, lithium, nickel, neodymium, and samarium.

8. The electromagnetic shielding composition according to Claim 1, wherein the magnetic metal and / or its alloy includes a metal compound, an alloy, or an oxide thereof.

9. The electromagnetic shielding composition according to Claim 1, wherein the discrete carbon nanotubes have open-ended tubes.

10. The electromagnetic shielding composition according to Claim 1, wherein the oxidation species on the inner surface and the outer surface are selected from the group consisting of carboxylic acids, phenols, aldehydes, ketones, ether compounds, and combinations thereof.

11. The electromagnetic shielding composition according to Claim 1, further mixed with at least one rubber.

12. The electromagnetic shielding composition according to Claim 1, further comprising a thermoplastic polymer, a thermoplastic elastomer, or a combination thereof.

13. The electromagnetic shielding composition according to Claim 1, further comprising a thermosetting polymer.

14. The electromagnetic shielding composition according to claim 13, further comprising at least one thermosetting polymer selected from the group consisting of epoxy, polyurethane, and combinations thereof. **Claim 15** The electromagnetic shielding composition according to claim 12, wherein the thermoplastic polymer is selected from acrylic, polyamide, polyethylene, polystyrene, polycarbonate, methacrylic, phenol, polypropylene, polyolefin plastomer, polyolefin elastomer, EPDM, and copolymers of ethylene, propylene, and functional monomers.

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