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WO2007001412A2 - Compositions et procedes pour les utilisations et la production a grande echelle de nano-oignons de carbone - Google Patents

Compositions et procedes pour les utilisations et la production a grande echelle de nano-oignons de carbone Download PDF

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Publication number
WO2007001412A2
WO2007001412A2 PCT/US2005/036348 US2005036348W WO2007001412A2 WO 2007001412 A2 WO2007001412 A2 WO 2007001412A2 US 2005036348 W US2005036348 W US 2005036348W WO 2007001412 A2 WO2007001412 A2 WO 2007001412A2
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Prior art keywords
onions
carbon nano
carbon
solvent
sample
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PCT/US2005/036348
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WO2007001412A3 (fr
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James M. Howe
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University Of Virginia Patent Foundation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls

Definitions

  • the invention relates to a new method for obtaining and for purifying carbon nanoparticles.
  • the invention further relates to an abundant source, method of producing, and uses of carbon nano-onions.
  • the soot found in used diesel lubricating oil consists of spherical carbon nano- onions; typically 20 to 40 nanometers in diameter (see Figure 1). They form in the oil during thousands of combustion cycles. Soot will enter the lubrication oil at the rate of approximately 0.005 ounces for every gallon of fuel burned. A truck will burn 1,786 gallons of fuel every 12,500 miles, assuming 7 miles per gallon. During this 12,500 mile oil change interval, more than half a pound (8.75 oz. or 248 grams) of carbon nano- onions will form in the crankcase oil.
  • carbon nano-onions are structurally, chemically, and physically different than exhaust soot.
  • the carbon nano-onions found in used diesel lube oil contain approximately 94% carbon, with the balance being oxygen, phosphorous, calcium, and sulfur.
  • the chemical makeup of used lube oil soot is unique and it resembles that of diamond-like carbons, with a mixture of sp, sp2, and sp3 bonding, and with oxygen and sulfur replacing hydrogen.
  • the hardness of used diesel engine oil carbon nano-onions is similar to that of various diamond-like carbons. Carbon nano-onions accumulate in diesel engine oil over time. The longer the oil is used, the large the quantity of carbon nano-onions.
  • carbon nano-onions are very hard and tend to aggregate or agglomerate, they become abrasive and cause unwanted diesel engine wear. Carbon nano-onions are also expelled into the atmosphere through diesel engine exhaust. Typical used diesel engine oil contains 75 grams or more of carbon nano-onions per gallon, all of which have roughly the same size and properties.
  • the central shells ranged from about 0.1 nm diameter to much larger, some containing one- and two-layered giant Fullerenes equivalent to about C 3700 and larger. Subsequently, strikingly spherical onion structures with up to about 70 shells were produced by intense electron-beam irradiation of carbon soot collected from an arc- discharge apparatus.
  • Nanostructures formed on the cathode during arc- discharge carbon vaporization include tubes with 2 to about 50 nested shells. The tubes are capped by polyhedral domes, sometimes having conical transitions to the cylindrical tube wall. All of these nanostructures contain the feature associated with fullerenes of a structure containing both six-member and five-member carbon rings.
  • Fullerenes C 60 and C 70 have been successfully synthesized and collected in flames (Howard et al., Nature 352:139-141, 1991). Evidence of high molecular weight ionic species consistent with an interpretation as being fullerenic structures was observed in low-pressure premixed benzene and acetylene flames (Baum et al., Ber. Bunsenges. Phys. Chem. 96:841-857, 1992). The presence of neutral giant fullerene molecules in flames has not been established, however. Carbon vaporization processes, while capable of making a wide variety of
  • Fullerenic structures are very inefficient and not amenable to large scale production of carbon nano-onions. It is desirable to develop a manufacturing process that is efficient and capable of processing large amounts of large spherical Fullerenic nanostructures. There is a long felt need in the art for the development of new sources and methods for purifying carbon nanoparticles and for cheaper purified carbon nano-onions. The present invention satisfies these needs.
  • the present invention relates to a novel carbon nano-material, an abundant source of said carbon nano-material, a method for large-scale production and purification, and its use in applications including those listed above and others.
  • Called carbon nano-onions the present invention provides an abundant and reproducible source of extremely hard solid-core spheres containing tightly bound layers of carbon and small quantities of other elements. These spheres are generally 20 to 40 nanometers in diameter. While other methods for producing carbon nano-onions have been attempted, their structure and the limited quantities that can be produced using these other methods distinguishes them from the present invention.
  • the carbon nano-onions of the present invention are far harder than amorphous carbon black and amorphous soot particles made using most combustion processes.
  • the invention provides a cheap and abundant source of carbon nano-onions.
  • the source is used diesel oil.
  • Typical used diesel engine oil contains 75 grams or more of carbon nano-onions per gallon, all of which have roughly the same size and properties. This source of carbon nano-onions is encompassed by the present invention.
  • the present invention provides a source and procedure for obtaining large quantities of carbon nanoparticles (i.e., soot particles) from used diesel engine oil. It also describes issues related to the logistics and economics of the process as well as recyclability of materials.
  • the resulting carbon nanoparticles may be used in a variety of applications, e.g., as strengthening nanoparticles in organic and inorganic nanocomposites, diamond-like abrasives for polishing and other applications where diamond-like carbon materials are used.
  • the invention provides compositions and methods to obtain and purify carbon nano-onion particulate efficiently and in high purity, and in another aspect, the invention provides high purity carbon nano-onion particulate.
  • the present invention provides for the use of used or spent diesel lubricating oil as an abundant source of solid-core, spherical, carbon nano-onions.
  • the used diesel lubricating oil is an abundant source of solid-core, spherical, graphitic carbon nano-onions having a diameter of approximately 10 to 50 nanometers.
  • purified carbon nano-onions of the invention are of uniform size, composition, and properties. In one aspect, carbon nano-onions of the invention are about 20-40 nm in diameter.
  • the purified carbon nano-onions comprise at least about 90% C. In another aspect, the purified carbon nano-onions comprise at least about 92% C. In one aspect, the carbon nano-onions comprise at least about 94% C. In one aspect, the carbon nano-onions comprise a composition of at least about 94% C, with O, Ca, P, and S as the other main elements present in the composition. In another aspect, the carbon nano-onions comprise at least about 96% C. In one aspect of the invention, the carbon nano-onions can be acid treated to remove contaminants, In one aspect, the removed contaminants comprise S, Ca, and P. hi one aspect, the acid is nitric acid. In one aspect, the carbon nano-onions can be alkaline treated to remove contaminants.
  • carbon nano-onions of the invention comprise a hardness of about 1150 ⁇ 250 kgf/square mm.
  • the carbon nano-onions of the invention comprise a surface area of at least about 1,000 m 2 /gram.
  • the carbon nano-onions of the invention are able to withstand strong acids.
  • the invention provides a process for extracting and purifying carbon nano-onions, said process comprising adding a solvent to used diesel lubricating oil, heating the oilrsolvent mixture, filtering the heated oihsolvent mixture, centrifuging the filtered oihsolvent mixture, heating the post-centrifuge carbon material to dry it and thus remove residual solvent and oil, and pulverizing, ball milling, or sonicating the resulting dried cinder-like carbon material to nano-scale particles.
  • the solvent is a carbon-based solvent such as toluene, heptane, decane, or chloroform.
  • the solvent is a paraffin solvent such as NorparTM 12 or NorparTM 15.
  • the solvent is an aliphatic ketone such as methylethyl ketone.
  • the invention provides a method for extracting and purifying carbon nano-onions from used diesel lube oil, wherein said process is thin film evaporation. In another embodiment, the invention provides a process for extracting and purifying carbon nano-onions from used diesel lube oil, wherein the process is a distillation process.
  • the invention provides a process for extracting and purifying carbon nano-onions, wherein said process includes altering or controlling the surface chemistry of the carbon nano-onions obtained from the source material by the hydrogen termination of their exterior surface. In another embodiment, the process includes altering or controlling the surface chemistry of the carbon nano-onions obtained from the source material by the fluorine termination of their exterior surface. In yet another embodiment, the invention provides a process of altering or controlling the surface chemistry of the carbon nano-onions obtained from the source material by the hydroxyl termination of their exterior surface. In yet a further embodiment, the invention provides a process of altering or controlling the surface chemistry of the carbon nano-onions obtained from the source material by the amine termination of their exterior surface.
  • the invention provides for the use of the carbon nano-onions derived from used diesel lube oil in tribological and nano-tribological applications.
  • the carbon nano-onions of the present invention are also useful in other applications, including, but not limited to, electronic devices, ultra-hard coatings, polymeric thin films, photovoltaic/solar cells, medical imaging, drug delivery, ultracapacitors, optical limiters, broad-band optical limiters (including broad band, IR, and NIR regions) and other optical devices, quantum dots, electrospun nano-fibers, MEMS and NEMS devices, adhesives, synthetic rubbers, polymers, ceramic composites, alloys, ceramic metal composites or cermets, metallic glass composites, lithography, aerosols, sputter coating, and as a nano- storage device for hydrogen or lithium.
  • the carbon nano-onions of the invention are useful as optical limiters, including, but not limited to such optical limiters as cockpit glass and materials and eyeglass lenses.
  • the cockpit glass and materials and eyeglass lenses are useful protection against lasers.
  • Figure 1 represents an image of an electron micrograph of carbon nano-onions found in used diesel lubricating oil; typically 20 to 40 nanometers in diameter.
  • Figure 2 graphically illustrates the size distribution of carbon nano-onions purified using a Norpar solvent. The ordinate represents Intensity (%) and the abscissa represents Size (d.nm).
  • Figure 3 graphically illustrates the size distribution of carbon nano-onions purified using a chloroform solvent. The ordinate represents Intensity (%) and the abscissa represents Size (d.nm).
  • Figure 4 graphically illustrates the results of a cycling test of electrical properties of carbon nano-onions under constant current (0.1 mA/cm 2 ).
  • the ordinate represents Voltage/Current (using volts and mA, respectively) and the abscissa represents Time in hours.
  • Series 1 is indicated by the line with peaks which has two arrows pointing to it and which has the higher of the two "0" indicators on the ordinate.
  • Series 2 is indicated by the lower of the two lines which begins at the lower of the two "0"s on the ordinate.
  • Figure 5 graphically illustrates the results of a Charge/Discharge capacity test of carbon nano-onions.
  • the ordinate represents Capacity (mAh/g) and the abscissa represents Cycle Number.
  • the filled in black diamonds ( ⁇ ) represent Series 1 and the filled in black squares ( ⁇ ) represent Series 2.
  • Figure 6 graphically represents an energy dispersive x-ray spectrum and chemical analysis of typical carbon nano-onion particles obtained from spent diesel oil.
  • the ordinate of the x-ray spectrum represents counts, and the abscissa represents x-ray energy in KeV. Peaks of the x-ray spectrum are labeled according to element (C, O, P, S, and Ca).
  • the ordinate represents CCD counts and the abscissa represents energy loss in eV.
  • the invention relates generally to a source and method for purifying carbon nanoparticles, as well as to their use as nanoparticles in a variety of nanotechnology applications.
  • CNO carbon nano-onion
  • H represents hydrogen.
  • MBMS means molecular beam mass spectrometer
  • STM scanning tunneling microscopy
  • an element means one element or more than one element.
  • an "instructional material” includes a publication, a recording, a diagram, or any other medium of expression which can be used to communicate the usefulness of the invention.
  • the instructional material of the kit of the invention may, for example, be affixed to a container which contains the identified compound or be shipped together with a container which contains the identified compound. Alternatively, the instructional material may be shipped separately from the container with the intention that the instructional material and the compound be used cooperatively by the recipient.
  • the term “pulverize” refers to any method for breaking up larger particles or aggregates. For example, pulverize can be a mechanical method. Pulverize includes ball milling and sonicating.
  • the term “purified” and like terms relate to an enrichment of a molecule or compound relative to other components normally associated with the molecule or compound in a native environment.
  • the term “purified” does not necessarily indicate that complete purity of the particular molecule has been achieved during the process.
  • a compound is purified when at least 10%, more preferably at least 20%, more preferably at least 50%, more preferably at least 60%, more preferably at least 75%, more preferably at least 90%, and most preferably at least 99% of the total material (by volume, by wet or dry weight, or by mole percent or mole fraction) in a sample is the compound of interest.
  • reduce particle size to nanoparticle size refers to methods of reducing carbon particle or carbon nano-onion size such as breaking down aggregate particles to smaller aggregates and individual nano-onions.
  • resistant to strong acids or strong bases refers to the ability of carbon nano-onions purified from used diesel oil or other sources to be resistant to breakdown or being hollowed out by acid or alkaline treatment.
  • the phrase 'similar size refers to purified carbon nano-onions which fall within a similar size range.
  • the size of the nano-onions within a group of similar size nano-onions varies by about 75 nanometers in diameter.
  • the size of nano-onions within a group varies by about 50 nanometers in diameter.
  • the size of nano- onions within a group varies by about 25 nanometers in diameter.
  • the size of nano-onions within a group varies by about 15 nanometers in diameter.
  • the size of nano-onions within a group varies by about 10 nanometers in diameter.
  • the size of nano-onions within a group varies by about 5 nanometers in diameter.
  • Standard refers to something used for comparison.
  • a standard can be a known standard agent or compound which is administered or added to a control sample and used for comparing results when measuring said compound in a test sample.
  • Standard can also refer to an "internal standard,” such as an agent or compound which is added at known amounts to a sample and is useful in determining such things as purification or recovery rates when a sample is processed or subjected to purification or extraction procedures before a marker of interest is measured.
  • substantially pure describes a compound which has been separated from components which naturally accompany it.
  • a compound is substantially pure when at least 10%, more preferably at least 20%, more preferably at least 50%, more preferably at least 60%, more preferably at least 75%, more preferably at least 90%, and most preferably at least 99% of the total material (by volume, by wet or dry weight, or by mole percent or mole fraction) in a sample is the compound of interest. Purity can be measured by any appropriate method, e.g., in the case of polypeptides by column chromatography, gel electrophoresis, or HPLC analysis. A compound is also substantially purified when it is essentially free of naturally associated components or when it is separated from the native contaminants which accompany it in its natural state.
  • used diesel oil diesel engine lubricating oil which has been subjected to use in a diesel engine.
  • used diesel oil and "spent diesel oil” are used interchangeably herein.
  • conventional chemical and other techniques which are known to those of skill in the art. Such techniques are explained fully in the literature (see, for example, Jao et al., In Proceedings of the International Tribology Conference, vol. 3, pp. 1981-1986 (2001). Nagasaki, Japan: Japanese Society of
  • the first is the realization that used diesel engine oil is a cheap, abundant source for purification of carbon nanoparticles with similar sizes and properties.
  • the carbon nanoparticles can be used in a wide range of nanotechnology applications as described herein. Other uses for carbon nanoparticles not described herein are known or may become known.
  • the second aspect is a proposed scheme for extracting the nanoparticles from diesel engine oil.
  • One of skill in the art can imagine many possible alternative methods for extracting soot nanoparticles from diesel engine oil that may be new and patentable.
  • Used diesel-engine oil contains billions of soot particles, perhaps constituting as much as 10% of the oil volume after prolonged use before the oil is changed. This soot is discarded with the used oil. Given the number of diesel engines currently being used in industrial nations throughout the world, used diesel engine oil appears to be an abundant, continuous source of soot, or carbon nanoparticles.
  • the invention as described herein provides a process for extracting soot nanoparticles from used diesel engine oil for nanotechnology applications. Since there are many ways in which this might be achieved, it is not so much the methodology, but the idea itself, i.e., that diesel engine oil is an abundant source of carbon nanoparticles, that is the novel and most valuable part of this invention.
  • a continuous supply of used diesel engine oil from various sources can be obtained for soot extraction.
  • a collection system can be set up for this relatively cheaply, since most garages, etc., need a place to dispose of used diesel engine oil.
  • soot is produced during combustion in all types of engines, so that sources of soot other than diesel engines are also available. Soot emitted from the engine exhaust is also a source of carbon nanoparticles. Because this soot contributes to air pollution and poses a health hazard, in one aspect of the invention, filters can be used to collect soot from engine exhausts as a source of carbon nanoparticles.
  • Carbon nanoparticles prepared according to the techniques of the invention are useful as carbon-based nanocomposite materials for use in air and space vehicles, as abrasives for polishing, can be used where diamond-like carbon is useful because of the inertness of soot and because of the optical properties of soot.
  • the advantages of purifying nanoparticles from soot include, but are not limited to, the low-cost of soot, high-volume production, the simple nanoparticle purification process, and the uniform sizes and properties of the purified carbon nanoparticles.
  • the carbon nanoparticles of the invention are useful in catalysis.
  • carbon nano-onions are useful as catalysts for increasing the yield of styrene during styrene synthesis.
  • the use of carbon nano-onions increases styrene yield by at least about 25%.
  • use of carbon nano- onions increases styrene yield by at least about 20%.
  • the use of carbon nano-onions increases styrene yield by at least about 15%.
  • the use of carbon nano-onions increases styrene yield by at least about 5%.
  • the use of carbon nano-onions as catalysts in the production of styrene allows for a decrease in the operating temperature by at least about 200°C.
  • the use of carbon nano-onions as catalysts in the production of styrene allows for a decrease in the operating temperature by at least about 150°C.
  • the use of carbon nano-onions as catalysts in the production of styrene allows for a decrease in the operating temperature by at least about 100°C.
  • the use of carbon nano-onions as catalysts in the production of styrene allows for a decrease in the operating temperature by at least about 50°C.
  • the invention provides the use of centrifugation techniques for removing soot from oil.
  • the invention provides a centrifuge oil filter, which, inter alia, includes a centrifuge filter housing and a replaceable centrifuge cartridge.
  • the centrifuge oil filter is adapted to remove soot from oil in engine applications.
  • a method for separating the carbon nano-onions is to dilute the used diesel lube oil with a petroleum-compatible solvent such as NorparTM (ExxonMobil), toluene, heptane, chloroform, decane, or other similar solvents to help reduce the viscosity of the oil.
  • a petroleum-compatible solvent such as NorparTM (ExxonMobil), toluene, heptane, chloroform, decane, or other similar solvents to help reduce the viscosity of the oil.
  • the solvent to oil ratio can typically be in a ratio of 1 to 1 to 4 to 1, using as little solvent as practical to reduce the viscosity as much as possible.
  • the solventroil mixture is then typically heated to between 50 to 90°C (higher temperatures may be used, depending on the solvent) and stirred continuously to lower the viscosity, typically close to 1.0 centipoise.
  • a technique useful for separating nano-onions from the solventoil mixture employs the use of 2 parts of Norpar 12 to 1 part used diesel lube oil.
  • the 2 to 1 solvent to oil mixture is heated to 60°C, at which point a viscosity of approximately 2.6 centipoise is achieved.
  • the heated solventoil mixture is then filtered using a small pore filter (e.g., Pall Profile II RM1F005H21 0.5 micron filter) to remove larger contaminant particles.
  • the filtered solventoil mixture is centrifuged using a very high-RPM, high g-force and a slow feed rate in order to remove the largest percentage of the carbon nano-onions possible.
  • the high-speed centrifuge can be a closed-bowl centrifuge, which must be cleaned manually, or a self-cleaning, disk-stack centrifuge. If a closed-bowl centrifuge such as the Sharpies Model AS-26 is used, the wet, black, post-centrifuge material must be removed manually, by using a stainless steel scraper, for example. At this point, the wet, black centrifuged material still contains residual quantities of oil and solvent, so one method for purifying the carbon nano-onions entails baking the wet, post-centrifuge material in atmospheric conditions, or in the presence of an inert gas such as argon at 250°C for 90 minutes.
  • an inert gas such as argon at 250°C for 90 minutes.
  • the process can be varied by adjusting such parameters as revolutions per minute of the centrifuge and rotors to regulate the g-force, and various feed rates of the sample.
  • the method of the invention provides high revolutions per minute, with high g-force, and a slow feed rate.
  • Another source of producing carbon nano-onions envisioned in the present invention is exhaust pipes, mufflers, exhaust filters and other particulate filters used on diesel engine vehicles. These carbon nano-onions can be removed using solvents such as those mentioned above, followed by the purification steps like those outlined herein.
  • the carbon nano-onions found in the exhaust soot are slightly different in structure and hardness and may thus require other kinds of treatment, such as irradiation or some other method to make them harder if extreme hardness is a desired trait. Larger quantities of used diesel lube oil (and thus carbon nano-onions) are available and accessible than exhaust pipes and filters. For example, used diesel lube oil can be obtained and treated in one location such as an oil recycling firm.
  • the composition and structure of the carbon nano-onions found in the engine oil is unique and thus, so are their chemical and physical properties.
  • acid and alkaline concentrations can vary, depending on the particular acid or base used the particular contaminant to be removed, hi one aspect, the concentration may be as much as about 50%. In another aspect, the concentration may be as much as about 40%. In yet another aspect, the concentration may be as much as about 30%. In a further aspect, the concentration may be as much as about 20%. In yet another aspect, the concentration may be as much as about 15%. In another aspect, the concentration may be as much as about 10%. In yet another aspect, the concentration may be as much as about 5%. In one aspect, the treatment is for a time period of up to twenty-four hours or more. In another aspect, the treatment is for up to 18 hours. In one aspect, the samples are sonicated during acid and alkaline treatment.
  • strong acid or alkaline treatment of purified carbon nano- onions of the present invention does not alter the structure of the carbon nano-onions. That is, the carbon nano-onions remain solid after treatment, as opposed to carbon black nano-particles which do not hold up to exposure to nitric acid and can become hollow upon such treatment.
  • the invention should not be construed to be limited solely to the assays and methods described herein, but should be construed to include other methods and assays as well.
  • One of ordinary skill in the art will know that other assays and methods are available to perform the procedures described herein. Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize the present invention and practice the claimed methods. The following working examples therefore, specifically point out the preferred embodiments of the present invention, and are not to be construed as limiting in any way the remainder of the disclosure.
  • soot particles from diesel engine oil is described in four steps below. It is important to realize that there are many potential variations on this process, many of which have not been explored, but which might improve the output, reproducibility and recyclability of the process.
  • Other processes for extraction, such as filtering, precipitation, etc., and other sources of carbon nanoparticles are also available.
  • Used diesel engine oil is mixed with a diluent, such as heptane, to decrease the viscosity of the oil.
  • a diluent such as heptane
  • the ratio of diluent to oil will depend on a number of factors, such as the chemical used for dilution, the length of time used for centrifuging, etc. These features would be optimized for a given process, typically using as little diluent and time as possible in the process.
  • the oil/diluent mixture is then centrifuged in a tube or bowl using commercially available ultracentrifuges at a speed of about 10,000 to about 100,000 revolutions per minute, depending on other conditions such as the rotor or centrifuge used. Typically, 17,000 revolutions per minute are used. Such a speed produces a force of about 20,000 xg. This causes the soot particles to settle and collect at the bottom of the tube or bowl. The rate at which settling occurs depends on the centrifuge speed, mixture viscosity, particle sizes, etc., and centrifuging may last for several hours. After centrifuging, the remaining liquid is decanted from the tube or bowl.
  • step 3 A small amount of fresh diluent is then added to the tube or bowl and they are ultrasonicated to clean the soot nanoparticles, break up agglomerates, and disperse them in the diluent. This solution is then ultracentrifuged as in step 2), but for a shorter time. The process is repeated several times.
  • the used diesel lube oil was diluted with a petroleum-compatible solvent, NorparTM (Exxon-Mobil), to help reduce the viscosity of the oil, using 2 parts of Norpar 12 to 1 part used diesel lube oil.
  • the 2 to 1 solvent to oil mixture was heated to 60°C, at which point a viscosity of approximately 2.6 centipoise was achieved.
  • the heated solvent:oil mixture was then filtered using a small pore filter (e.g., Pall Profile II RM1F005H21 0.5 micron filter) to remove larger contaminant particles.
  • the filtered solventroil mixture was centrifuged using a very high-RPM, high g-force and a slow feed rate in order to remove the largest percentage of the carbon nano-onions possible. Samples were then oven-dried at about 50 0 C.
  • the values and conditions for the analysis included toluene as a dispersant, viscosity (cP) of 1.6300, dispersant RI of 1.42, material RI of 1.59, material absorption of 0.01, 25°C, count rate (kcps) of 332.9, 60 second duration, 1.25 measurement position (mm), and attenuator at 6.
  • the results include a Z-average (d.nm) of 185, PdI of 0.256, intercept of 0.942, and peak values as shown in Table 1. Table 1.
  • the values and conditions for the analysis included chloroform as a dispersant, viscosity (cP) of 0.5300, dispersant RI of 1.443, material RI of 1.59, material absorption of 0.01, 25°C, count rate (kcps) of 221.1, 70 second duration, 1.25 measurement position (mm), and attenuator at 5.
  • the results include a Z-average (d.nm) of 153, PdI of 0.143, intercept of 0.957, and peak values as shown in Table 2.
  • Figure 4 demonstrates the results of a constant current cycling test. It should be noted that there is a sloping insertion reaction, with Li added as voltage drops, and that there is a single phase reaction with no obvious staging reactions (see Figure 4).
  • Figure 5 demonstrates the results of experiments to determine charge/discharge capacities of carbon nano-onions. There was 79% irreversible capacity, that is, 79% of the Li added during the first reaction never came back. The value for the first discharge was 666.5 mAh/g and for the first charge it was 138 mAh/g. The carbon was found to have poor capacity retention and no obvious insertion plateaus. The cycling profile was similar to a hard carbon.
  • the inset graph of Figure 6 represents an electron energy-loss spectrum. Chemical alteration of carbon nano-onion composition-
  • Methods are available for altering the composition of the purified carbon nano- onions of the invention described above, including acid treatment and alkaline treatment of purified carbon nano-onions.
  • carbon nano-onions were prepared as described in the Examples herein and then subjected to nitric acid treatment to remove contaminants. It was found that nitric acid treatment removes the S, Ca, and P, leaving only C and O. Furthermore, such treatment did not change the structure of the carbon nano-onions.
  • nitric acid, sulfuric acid, and hydrogen peroxide (up to 30%) treatments for up to 18 hours, with sonication have been used effectively to remove contaminants without altering the structure of the carbon nano-onions (results not shown).
  • the invention disclosed herein provides a rich source of carbon nanoparticles (i.e., used diesel engine oil) and demonstrates a new method for purifying carbon nanoparticles from used diesel engine oil, for use in nanotechnology applications.
  • the invention should not be construed to be limited solely to the assays and methods described herein, but should be construed to include other methods and assays as well.
  • One of skill in the art will know that other assays and methods are available to perform the procedures described herein.

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Abstract

La présente invention concerne un nouveau procédé d'obtention et de purification de nanoparticules de carbone, y-compris les nano-oignons de carbone. L'invention propose le gazole usagé comme source bon marché et abondante de nano-oignons de carbone, et leur utilisation dans diverses applications des nanotechnologies.
PCT/US2005/036348 2004-10-07 2005-10-07 Compositions et procedes pour les utilisations et la production a grande echelle de nano-oignons de carbone WO2007001412A2 (fr)

Applications Claiming Priority (2)

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