JP5099298B2 - Method for producing composite fullerene particles, apparatus for producing the same, and composite fullerene particles - Google Patents

Description

  The present invention relates to a method for producing composite fullerene particles, and more specifically, composite fullerene particles having a narrow average particle size distribution range of nanoscale order and usable as various functional particles. The present invention relates to a manufacturing method and a manufacturing apparatus.

  Metal fine particles with a nano-scale particle size have unique properties not found in bulk metals, so photosensors in photographic materials, various catalysts in organic chemical synthesis, conductive materials in electronic circuits, magnetic recording media Are widely used in various fields such as magnetic materials.

  These metal fine particles have different required properties depending on their applications, but they have smaller particle sizes and particle size distribution ranges for the purpose of improving functionality in each application and developing new applications. A method for producing metal fine particles having a narrow width has been studied.

  Conventionally known methods for producing metal fine particles are roughly classified into a gas phase method and a liquid phase method.

  In the manufacturing method using the vapor phase method, since the reaction generally proceeds by evaporation and aggregation of raw materials, spherical particles are formed by the surface tension, but the reaction conditions are maintained so that the aggregated metal fine particles are not clustered. Is difficult, and there is a problem that the particle size distribution of the generated particles cannot be sufficiently controlled.

  In the liquid phase method, a single jet method in which a dispersing agent and a raw material for controlling primary agglomeration after fine particle formation are dissolved in a solvent and a reaction initiation solution is added thereto to cause a fine particle formation reaction, The double jet method is known in which the solution and the reaction initiator are simultaneously controlled and added to the dispersion medium solution in the reaction vessel. However, in the single jet method, the concentration in the reaction system during the addition of the reaction initiation solution is controlled. It is difficult to produce uniform fine particles because it is not possible, and in the double jet method, it is difficult to control the degree of supersaturation before and after the reaction, and after the fine particles formed in the reaction vessel circulate in the reaction vessel, Since it is returned to the formation region, it is difficult to keep the reaction environment constant, and it is also difficult to produce homogeneous fine particles.

JP-A-6-73401

  The present invention provides a new method and apparatus for producing composite fullerene particles having a nanoscale order, in particular, a particle size of about 1 to 10 nm and a very narrow particle size distribution (uniform particle size). It is another object of the present invention to provide composite fullerene particles which are functional particles having unprecedented structures and characteristics.

The present invention
A first step of heating fullerene to generate fullerene gas;
A second step of cooling the fullerene gas to granulate at least a part of the fullerene gas;
And a third step of generating composite fullerene particles by bringing the fullerene particles formed in the second step into contact with a first metal-containing gas generated by heating a metal or a metal oxide. A method for producing composite fullerene particles characterized in that (Claim 1), or a first heating unit that generates fullerene gas by heating fullerene,
A cooling unit that cools the fullerene gas and particles at least a part of the fullerene gas;
A second heating unit that generates composite fullerene particles by bringing the fullerene that has been granulated in the cooling unit into contact with a first metal-containing gas generated by heating a metal or a metal oxide. The above-mentioned object is achieved by a production apparatus for complex fullerene particles (Claim 7).

As the fullerene used in the present invention, fullerenes having an arbitrary carbon number such as fullerene C ₆₀ having 60 carbon atoms, fullerene C ₇₀ having 70 carbon atoms, fullerene C ₈₄ having 84 carbon atoms can be used. From the viewpoint of easy availability, fullerene C ₆₀ having 60 carbon atoms is particularly preferably used.

The first step or the first heating portion of the present invention is intended to generate a fullerene gas by evaporating by heating fullerene (sublimation), for example, when using fullerene C ₆₀ is any ambient pressure The fullerene gas can be generated under a temperature condition of 350 ° C. or higher, which is the sublimation point of fullerene C ₆₀ below, but from the viewpoint of controllability of the particle size and reaction rate of the generated composite fullerene particles, In particular, fullerene gas is preferably generated under an atmospheric pressure of 50 to 500 hPa and a temperature of about 400 to 480 ° C.

  The second step or cooling unit of the present invention cools the fullerene vaporized in the first step, thereby aggregating at least a part of the fullerene gas into particles.

  In the third step or the second heating unit in the present invention, the first metal-containing gas generated by heating and evaporating (sublimating) the metal or the metal oxide is granulated in the second step. A metal or metal oxide is aggregated and adhered to fullerene particles by bringing fullerene into contact therewith, so that composite fullerene particles having an extremely narrow particle size distribution with an average particle size of about 1 nm to 10 nm can be obtained. (Metallized fullerene particles) can be produced.

  In addition, the metal-containing gas in the present invention means a metal gas or metal oxide gas generated by evaporation (sublimation) of metal, or a metal oxide gas generated by evaporation (sublimation) of metal oxide.

  The particle size (average particle size) of the composite fullerene particles produced in the present invention increases monotonously by increasing the atmospheric pressure in the reaction system or increasing the heating temperature of fullerene in the first step or first heating section. Therefore, by controlling the atmospheric pressure in the reaction system and / or the heating temperature of the fullerene in the first step, the particle size of the composite fullerene particles to be generated can be freely controlled. Is possible.

  On the other hand, depending on the cooling conditions in the second step or cooling section and the heating conditions in the third step or second heating section, the particle size and particle size distribution of the produced composite fullerene particles are hardly affected. For this reason, in the manufacturing method or manufacturing apparatus of the present invention, it is possible to stably manufacture composite fullerene particles having a narrow particle size distribution on the nanoscale order.

  As a metal used in the third step or the second heating part of the present invention, lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), aluminum (Al), potassium (K), Calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Zinc (Zn), gallium (Ga), germanium (Ge), rubidium (Rb), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Silver (Ag), Cadmium (Cd), Indium (In), S (Sn), antimony (Sb), cesium (Cs), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), polonium (Po), francium (Fr), radium (Ra), actinium (Ac), tri (Th), protoactinium (Pa), uranium (U), neptunium (Np), plutonium (Pu), americium (Am), curium (Cm), barium (Bk), californium (Cf), einsteinium ( Es), Fermium (Fm), Mendelevium (Md), Nobelium (No), Lorencium (Lr), Rutherfordium (Rf), Dobnium (Db), Seaborgium (Sg), Borium (Bh), Hassium (Hs), Miterneum ( Mt), darmstatium (Ds) can be used, and the metal oxide used in the third step or the second heating part of the present invention can be the above metal oxide. it can.

  Among these, when using noble metals such as gold, silver, copper, platinum, palladium, iridium, rhodium, it is possible to obtain composite fullerene particles with high utility value as a reaction catalyst, photosensor, conductive material, Such composite fullerene particles have a very fine average particle size and a very narrow particle size distribution, so that they can be used as functional particles having excellent properties that have not been obtained in the past.

  Further, in the present invention, the fourth step of bringing the composite fullerene particles generated in the third step or the second heating unit into contact with the second metal-containing gas generated by heating the metal or the metal oxide. Alternatively, it is possible to further include a third heating section (claims 4 and 8), and thereby it is possible to generate composite fullerene particles in which a plurality of metal layers are laminated on the fullerene nucleus.

  The second metal-containing gas in the inventions of claims 4 and 8 is a metal gas or oxide metal generated by evaporation (sublimation) of the same or different metal as the metal used for the first metal-containing gas. It can be a gas, or it can be a metal oxide gas produced by evaporation (sublimation) of an oxide of the same or different metal from the metal oxide used in the first metal-containing gas.

  In the present invention, the fifth step or the fourth heating unit for bringing the composite fullerene particles generated in the third step or the second heating unit into contact with the fullerene gas generated by heating the fullerene, and the metal or A sixth step or a fifth heating unit for bringing particles generated by the fifth step or the fourth heating unit into contact with a third metal-containing gas generated by heating the metal oxide; (Claims 5 and 9), thereby generating composite fullerene particles in which a metal (or metal oxide) / fullerene / metal (or metal oxide) layer is laminated on the fullerene nucleus. It becomes possible to do.

  The third metal-containing gas in the inventions of claims 5 and 9 is a metal gas generated by evaporation (sublimation) of the same or different metal as the metal used for the first or second metal-containing group gas. It can be an oxide metal gas, or it can be a metal oxide gas generated by evaporation (sublimation) of an oxide of the same or different metal oxide particles used in the first or second metal-containing gas. Can be.

  In the present invention, the first to sixth steps can be performed in an arbitrary atmospheric gas, and an arbitrary atmospheric gas can be used for the first to fifth heating parts and the cooling part. In some cases, it may be convenient to use an oxidizing atmosphere gas to produce composite fullerene adhered to the substrate, but in general, the safety of the process and the quality of the composite fullerene particles produced are stable. From the viewpoint, the first to sixth steps in the present invention are preferably performed in an inert gas atmosphere, and the first to fifth heating units and the cooling unit of the present invention are preferably maintained in an inert gas atmosphere.

  The present invention relates to a composite fullerene particle comprising a fullerene particle composed of an aggregate of a plurality of fullerene molecules and a plurality of metal particles or metal oxide particles attached to the surface of the fullerene particle (claim) The above problem can also be achieved by item 10).

  The fullerene particles in the invention of claim 10 typically have a particle size of typically several nm to several tens of nm formed by aggregation of several to several tens of fullerene molecules, preferably spherically. The metal particles or metal oxide particles are particles made of a metal or metal oxide having a particle size of typically about sub-nm to several nm attached to the surface of the fullerene particles.

  The composite fullerene particles having such a form have an extremely large surface area, and thus are excellent in reactivity and functionality, and are considered to be usable as functional particles having high utility value in various fields such as catalysts and optical sensors. It is done.

  The composite fullerene particles of claim 10 can be produced preferably using the method of claims 1-6 or the apparatus of claims 7-9.

  The composite fullerene particles according to claim 10, wherein the metal oxide particles are attached to the surface of the fullerene particles, and the oxide metal gas generated by heating the metal oxide is generated from the fullerene particles. It can also be generated by contacting with metal, and the metal gas generated by heating the metal is oxidized under appropriate conditions to form a metal oxide gas, which is generated by contacting the fullerene particles. It is also possible.

  Alternatively, by bringing the metal gas generated by heating the metal into contact with the fullerene particles, once the composite fullerene particles having the metal particles attached to the surface of the fullerene particles are generated and oxidized under appropriate conditions, It is also possible to obtain composite fullerene particles having metal oxide particles attached to the surface of fullerene particles.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is an explanatory diagram showing the configuration of an apparatus 1 for producing composite fullerene particles in the present invention.

  As illustrated, the apparatus 1 includes a first heating unit 20, a cooling unit 30, and a second heating unit 40 disposed on a quartz tube 10 through which a carrier gas serving as a reaction atmosphere gas passes. An alumina boat 21 in which fullerene is disposed and an electric furnace 22 for heating the alumina boat 21 are installed in the heating unit 20, and an alumina boat in which metal or metal oxide is disposed in the second heating unit 40. 41 and an electric furnace 42 for heating the alumina boat 41 are installed.

  The cooling unit 30 cools the fullerene evaporated (sublimated) by heating in the first heating unit 20 and at least partially aggregates the particles, and the path length of the cooling unit 30 is thus A suitable cooling device for cooling the quartz tube 10 of the cooling unit 30 is installed if necessary.

The heating conditions of the first heating unit 20 and the second heating unit 40 in this apparatus 1 and the pressure conditions in the quartz tube 10 by the carrier gas depend on the type of fullerene and metal or metal oxide arranged in the alumina boats 21 and 41. For example, when fullerene C ₆₀ is used as the fullerene of the alumina boat 21 and silver powder is used as the metal of the alumina boat 41, the heating temperature of the first heating unit 20 is set to 400 to By setting the heating temperature of the second heating unit 40 to 480 ° C., the pressure in the quartz tube 10 to about 50 to 450 hPa, the average particle size is about 4 to 10 nm, and the particle size distribution range is Very narrow composite fullerene particles can be obtained.

  Reference numeral 80 in FIG. 1 denotes a differential electric mobility measuring device (DMA) for measuring the particle size distribution and selecting the particle size of the composite fullerene particles produced by the device 1.

  The DMA 80 is configured to receive a sample gas containing ionized charged particles, an outer cylinder part 81 and an inner cylinder part 82 to which a DC voltage is applied, a carrier gas passage 83 formed between the outer cylinder part 81 and the inner cylinder part 82. Sample gas introduction port 84 for introduction, sample gas capture port 85 provided on the downstream side of the carrier gas flow from sample gas introduction port 84, and electrostatic for collecting charged particles captured at sample gas capture port 85 It comprises a collector 86, a Faraday cup 87 for measuring the amount of charged particles trapped in the sample gas trap 85 as a current, and the flow rate of the carrier gas in the carrier gas passage 83 and the outer cylinder 81-inner cylinder. By controlling the applied voltage between the parts 82, only charged particles having a specific particle diameter are collected in the electrostatic collector 86, or the applied voltage between the outer cylinder part 81 and the inner cylinder part 82 is swept. Is it possible to measure the particle size distribution of the charged particles in the sample gas based on the current detected in the Faraday cup 87 when the.

Further, when measuring the particle size distribution by DMA80 or selecting the particle size of the composite fullerene particles produced by the apparatus 1, ²⁴¹ Am for ionizing the fullerene particles or the composite fullerene particles is appropriately disposed in the apparatus 1. For example, it can be arranged in the cooling unit 30.

(Experiment 1)
In the apparatus 1, nitrogen gas is used as a reaction atmosphere gas, fullerene C ₆₀ powder is disposed in the alumina boat 21, and silver powder is disposed in the alumina boat 41. The heating temperature of the first heating unit 20 is 420 ° C. and second heating. The composite fullerene particles were generated by setting the heating temperature of the section 40 to 900 ° C. and the pressure inside the quartz tube 10 to 270 hPa. FIG. 2 shows the measurement result of the particle size distribution of the produced composite fullerene particles by DMA80.

  As shown in FIG. 2, the generated composite fullerene particles have the maximum detection intensity of the Faraday cup 87 when the particle diameter is 5.8 nm, and the detection intensity becomes almost zero when the particle diameter is 4 nm or less or 10 nm or more. It can be seen that the produced composite fullerene particles have a very narrow particle size distribution.

In order to confirm that the particles generated by the apparatus 1 are not mere fullerene C ₆₀ particles but composite fullerenes in which fullerene C ₆₀ and silver are combined, the particles generated from Experiment 1 are electrostatically captured by particle size. When collected by the collector 86 and subjected to XPS measurement for the composite fullerene of each particle size, a peak derived from silver 3d electrons could be observed at any particle size.

FIG. 3A shows an image obtained by observing the composite fullerene produced in Experiment 1 with a STEM. One scale below the figure corresponds to 5 nm. From FIG. 3A, it can be seen that a plurality of silver particles of about several nanometers (portions appearing in white) are attached to the surface of the central fullerene (C ₆₀ ) particles.

FIG. 3B is an estimated structural model of composite fullerene particles (F _P ) created based on FIG. As shown in the figure, the composite fullerene particles (F _P ) produced by the apparatus 1 adhere to the surface of the fullerene particles, which are aggregates of several to several tens of fullerene molecules (F _M ). It is considered that is formed by the plurality of metal particles (Ag _P).

(Experiment 2)
The influence on the particle size of the fullerene particles when the heating temperature of the first and second heating units 20 and 40 in the apparatus 1 was changed was investigated. In this experiment, the heating temperature of the first heating unit 20 was changed between 900 ° C. and 1050 ° C. under three conditions of 400 ° C., 420 ° C., and 450 ° C. Also, nitrogen gas was used as the reaction atmosphere gas, fullerene C ₆₀ powder was placed in the alumina boat 21, silver powder was placed in the alumina boat 41, and the pressure inside the quartz tube 10 was 270 hPa. The particle size distribution of the produced composite fullerene particles was measured in the same manner as in Experiment 1, and the particle size at which the detection intensity by the Faraday cup 87 was maximized was plotted for each temperature condition, to obtain FIG.

  FIG. 4 shows that the particle size of the composite fullerene particles increases depending on the heating temperature of the first heating unit 20. Therefore, the particle size of the composite fullerene particles can be adjusted by controlling the heating temperature of the first heating unit 20.

  On the other hand, even if the heating temperature of the second heating unit 40 is raised, the particle size of the generated composite fullerene particles is substantially constant.

  The temperature region (900 to 1050 ° C.) in Experiment 2 is a region where the silver vapor pressure rapidly increases. When silver particles are aggregated from only silver vapor (fullerene is not disposed on the alumina boat 21 in the present apparatus 1, In the case where silver powder is arranged on the alumina boat 41), it is known that in this temperature range, the particle diameter of the silver particles generated increases as the heating temperature rises. From the result of 4, it can be considered that after a certain amount of silver particles adhere to the surface of the fullerene particles, some stable state is formed in which further aggregation of silver hardly occurs.

In the present device 1, using a fullerene _{C 60} as a fullerene alumina boat 21, in the case of using silver powder as the metal of the alumina boat 41 by increasing the pressure in the quartz tube 10 from 50hPa to 500hPa It has been experimentally confirmed that the particle size of the composite fullerene produced (the particle size at which the detection intensity by the Faraday cup 87 is maximized) can be increased from about 4 nm to about 10 nm.

(Experiment 3)
Using aluminum powder as the raw metal powder, the relationship between the heating temperature in the second heating unit 40 of the apparatus 1 and the particle size of the composite fullerene particles was investigated. Specifically, nitrogen gas was used as a reaction atmosphere gas, fullerene C ₆₀ powder was disposed in the alumina boat 21, and aluminum powder was disposed in the alumina boat 41. Moreover, the temperature of the 1st heating part was 420 degreeC, and the temperature of the 2nd heating part 40 was changed at 840-900 degreeC. The particle size distribution of the generated composite fullerene particles was measured in the same manner as in Experiment 1, and the particle size at which the detected intensity by the Faraday cup 87 was maximized was plotted for each temperature condition to obtain FIG.

(Experiment 4)
Using copper powder as the raw metal powder, the relationship between the heating temperature of the second heating unit 40 of the apparatus 1 and the pressure in the reaction tube 10 and the particle size of the composite fullerene particles was investigated. Specifically, nitrogen gas was used as a reaction atmosphere gas, fullerene C ₆₀ powder was disposed on the alumina boat 21, and copper powder was disposed on the alumina boat 41. Moreover, the temperature of the 1st heating part was 420 degreeC, the temperature of the 2nd heating part 40 was 1000-1200 degreeC, and the pressure in the reaction tube 10 was changed on three conditions of 135, 270, and 540 hPa. The particle size distribution of the generated composite fullerene particles was measured in the same manner as in Experiment 1, and the particle diameter at which the detected intensity by the Faraday cup 87 was maximized was plotted for each experimental condition to obtain FIG.

(Experiment 5)
Using gold powder as the raw metal powder, the relationship between the heating temperature in the second heating unit 40 of the apparatus 1 and the particle size of the composite fullerene particles was investigated. Specifically, nitrogen gas was used as a reaction atmosphere gas, fullerene C ₆₀ powder was disposed on the alumina boat 21, and gold powder was disposed on the alumina boat 41. Moreover, the temperature of the 1st heating part was 420 degreeC, and the temperature of the 2nd heating part 40 was changed at 1100-1170 degreeC. The particle size distribution of the generated composite fullerene particles was measured in the same manner as in Experiment 1, and the particle size at which the detection intensity by the Faraday cup 87 was maximized was plotted for each temperature condition, to obtain FIG.

(Experiment 6)
Using tin powder as the raw metal powder, the relationship between the heating temperature in the second heating unit 40 of the apparatus 1 and the particle size of the composite fullerene particles was investigated. Specifically, nitrogen gas was used as the reaction atmosphere gas, fullerene C ₆₀ powder was disposed on the alumina boat 21, and tin powder was disposed on the alumina boat 41. Moreover, the temperature of the 1st heating part was 400 degreeC, and the temperature of the 2nd heating part 40 was changed at 900-1050 degreeC. The particle size distribution of the generated composite fullerene particles was measured in the same manner as in Experiment 1, and the particle size at which the detection intensity by the Faraday cup 87 was maximized was plotted for each temperature condition to obtain FIG.

(Experiment 7)
When lead powder was used as the raw metal powder, the relationship between the heating temperature of the first and second heating units 20 and 40 of the apparatus 1 and the particle size of the composite fullerene particles was investigated. Specifically, nitrogen gas was used as the reaction atmosphere gas, fullerene C ₆₀ powder was disposed on the alumina boat 21, and lead powder was disposed on the alumina boat 41. The pressure in the reaction tube 10 was 270 hPa, the temperature of the first heating unit was changed at 400 and 450 ° C., and the temperature of the second heating unit 40 was changed at 600 to 700 ° C. The particle size distribution of the generated composite fullerene particles was measured in the same manner as in Experiment 1, and the particle size at which the detected intensity by the Faraday cup 87 was maximized was plotted for each temperature condition, to obtain FIG.

(Experiment 8)
In the apparatus 1, by using air as a reaction atmosphere gas, composite fullerene particles in which metal oxide particles were adhered to the surface of fullerene particles were generated. Specifically, air was used as the reaction atmosphere gas, and fullerene C ₆₀ powder was placed in the alumina boat 21 and silver powder was placed in the alumina boat 41. The pressure in the reaction tube 10 was 270 hPa, the temperature of the first heating unit was 420 ° C., and the temperature of the second heating unit 40 was changed at 900 to 1050 ° C. The particle size distribution of the generated composite fullerene particles was measured in the same manner as in Experiment 1, and the particle size at which the detected intensity by the Faraday cup 87 was maximized was plotted for each temperature condition, to obtain FIG.

The following can be said from the results of FIGS.
(1) According to the present invention, composite fullerene particles in which various metals (silver, aluminum, copper, gold, tin, lead) and metal oxides (silver oxide) including precious metals and non-metals are attached to the surface Can be generated.
(2) The amount of metal or metal oxide adhering to the composite fullerene particles produced by the present invention hardly changes depending on the heating temperature in the second heating unit 40. Therefore, according to the present invention, composite fullerene particles having homogeneous characteristics can be easily generated.
(3) The particle size of the composite fullerene particles can be controlled by the heating temperature of the first step or the first heating unit 20 or the pressure in the reaction tube 10. Therefore, a composite fullerene having a required particle size can be obtained by these parameters.

  FIG. 11 is an explanatory diagram showing a configuration of an apparatus 2 for producing composite fullerene particles according to the second embodiment of the present invention.

  As illustrated, the apparatus 2 includes a first heating unit 20, a cooling unit 30, a second heating unit 40, and a third heating unit 50 disposed on the quartz tube 10 through which the carrier gas passes.

  The first heating unit 20, the cooling unit 30, and the second heating unit 40 in the device 2 have the same configuration as the first heating unit 20, the cooling unit 30, and the second heating unit 40 in the device 1 described above. In the third heating unit 50, an alumina in which a metal of the same or different type as the metal arranged in the alumina boat 21 or a metal oxide of the same or different type as the metal oxide arranged in the alumina boat 21 is arranged. A boat 51 and an electric furnace 52 for heating the alumina boat 51 are provided.

  In this apparatus 2, the metal-containing material generated by heating the metal or metal oxide in the third heating part to the composite fullerene particles generated in the first heating part 20 to the second heating part 40 in the same manner as in the apparatus 1. By bringing the gas into contact, the particles are agglomerated and adhered, and as a result, composite fullerene particles in which the same or different metal or metal oxide is laminated on the fullerene particles are generated.

  The composite fullerene particles obtained in this way are similar to the fullerene particles in addition to the composite fullerene particles produced by the apparatus 1 having an average particle size on the nanoscale order and a very narrow particle size distribution. Alternatively, since it has a structure in which different kinds of metals or metal oxides are laminated, it is expected to have functional characteristics different from the composite fullerene particles produced by the apparatus 1.

  FIG. 12 is an explanatory diagram showing the configuration of the apparatus 3 for producing composite fullerene particles according to the third embodiment of the present invention.

  As illustrated, the apparatus 3 includes a first heating unit 20, a cooling unit 30, a second heating unit 40, a fourth heating unit 60, and a fifth heating unit 70 disposed on the quartz tube 10 through which the carrier gas passes. It is composed of

  The first heating unit 20, the cooling unit 30, and the second heating unit 40 in the apparatus 3 have the same configuration as the first heating unit 20, the cooling unit 30, and the second heating unit 40 in the apparatus 1 described above. The fourth heating unit 60 is provided with an alumina boat 61 in which fullerene is disposed and an electric furnace 62 for heating the alumina boat 61. The fifth heating unit 70 is provided with a metal disposed in the alumina boat 21. An alumina boat 71 in which the same or different type of metal or a metal oxide of the same or different type as the metal oxide arranged in the alumina boat 21 is disposed, and an electric furnace 72 for heating the alumina boat 71 are installed. Has been.

  In this device 3, composite fullerene particles are generated in the first heating unit 20 to the second heating unit 40 in the same manner as in the device 1, and the fullerene gas generated by heating the fullerene in the fourth heating unit is used as the composite fullerene. The particles are agglomerated and adhered by bringing them into contact with the particles, and the metal-containing gas generated by heating the metal or metal oxide in the fifth heating part is brought into contact with the surface to agglomerate and adhere to the fullerene particles. Composite fullerene particles in which metal (or metal oxide) / fullerene / metal (or metal oxide) is laminated are generated.

  The composite fullerene particles thus obtained, like the composite fullerene particles produced by the apparatus 1, have an average particle size on the nanoscale order and a very narrow particle size distribution. (Or metal oxide) / fullerene / metal (or metal oxide) has a laminated structure, and therefore has functional characteristics different from the composite fullerene particles produced by the device 1 or device 2. Be expected.

  As a further modification of the device 2 and the device 3, one or a plurality of heating units similar to the third heating unit in the device 2 are installed in the subsequent stage of the device 2 or the device 3, or the fourth in the device 3 is used. One or more sets of heating units similar to the heating unit and the fifth heating unit are installed, or the same heating unit as the third heating unit in the device 2 and the fourth heating unit and the fifth heating unit in the device 3 It is also possible to install a single heating element or a combination of a plurality of heating parts, and thereby, a composite fullerene particle in which a plurality of metal layers or metal oxide layers are laminated on a fullerene particle, or a metal on a fullerene particle. It is also possible to produce composite fullerene particles in which a plurality of composite layers comprising layers or metal oxide layers and fullerene layers are laminated.

  As mentioned above, although the production method and production apparatus of the composite fullerene particles of the present invention have been described with reference to some embodiments, the present invention is not limited to these embodiments, and the description of the claims It is possible to make various modifications within.

For example, in the above embodiment, the case where silver is aggregated on fullerene C ₆₀ particles has been described as an example. However, other fullerenes such as fullerene C ₇₄ and fullerene C ₈₀ may be used instead of fullerene C ₆₀ . In addition, it is also possible to attach other noble metals such as platinum, palladium, iridium, rhodium to the fullerene particles in addition to the metal or metal oxide specifically described in the experimental results in the examples. It is also possible to agglomerate magnetic metal such as nickel, cobalt, iron, etc., and the metallized fullerene produced thereby can be used as a new magnetic material having a new functional characteristic that has not existed before. Similarly, other metals such as transition metals, alkali metals, and base metals can be aggregated in the fullerene particles. , And the this metal fullerene produced by may be used as a new functional particles unprecedented.

In addition, ²⁴¹ Am in the above embodiment is simply disposed for the purpose of measuring the particle size distribution of the metallized fullerene produced by DMA, and intended to produce ionized metallized fullerene. The use of an ionization source such as ²⁴¹ Am is not an essential component of the present invention.

  According to the present invention, it exhibits excellent characteristics in applications such as photosensors in photographic materials, various catalysts in organic chemical synthesis, colorants such as pigments, conductive materials in electronic circuits, and magnetic materials such as magnetic recording media. It is possible to produce composite fullerene particles having a nano-scale order and a very narrow particle size distribution.

Explanatory drawing which shows the structure of the composite fullerene particle manufacturing apparatus which concerns on one Embodiment of this invention. Explanatory drawing which shows the particle size distribution of the composite fullerene particle produced | generated by this invention. The SEM image (A), STEM image (B), and presumed structure model (C) of the composite fullerene particle produced | generated by this invention. In this invention, explanatory drawing which shows the particle size fluctuation | variation of a composite fullerene particle when the temperature of a 1st, 2nd heating part is changed. In this invention, aluminum is used as material metal powder, and explanatory drawing which shows the particle size fluctuation | variation of a composite fullerene particle when changing the temperature of a 2nd heating part. In this invention, copper is used as material metal powder, and explanatory drawing which shows the particle size fluctuation | variation of a composite fullerene particle when changing the temperature of a 2nd heating part, and the pressure in a reaction tube. Explanatory drawing which shows the particle size fluctuation | variation of a composite fullerene particle when using gold as a material metal powder and changing the temperature of a 2nd heating part in this invention. In this invention, tin is used as material metal powder, and explanatory drawing which shows the particle size fluctuation | variation of a composite fullerene particle when changing the temperature of a 2nd heating part. In this invention, the explanatory drawing which shows the particle size fluctuation | variation of the composite fullerene particle when lead is used as material metal powder and the temperature of the 2nd heating part is changed. In this invention, silver is used as material metal powder, and explanatory drawing which shows the particle size fluctuation | variation of a composite fullerene particle when using air as reaction atmosphere gas and changing the temperature of a 2nd heating part. Explanatory drawing which shows the structure of the composite fullerene particle manufacturing apparatus which concerns on other embodiment of this invention. Explanatory drawing which shows the structure of the composite fullerene particle manufacturing apparatus which concerns on other embodiment of this invention.

Explanation of symbols

1-3 ... Composite fullerene particle manufacturing apparatus 10 ... Quartz tube 20 ... 1st heating part 30 ... Cooling part 40 ... 2nd heating part 50 ... 3rd heating part 60 ... -4th heating part 70 ... 5th heating part 21, 41, 51, 61, 71 ... Alumina boat 22, 42, 52, 62, 72 ... Electric furnace 80 ... DMA

Claims (10)

A first step of heating fullerene to generate fullerene gas;
A second step of cooling the fullerene gas to granulate at least a part of the fullerene gas;
And a third step of generating composite fullerene particles by bringing the fullerene particles formed in the second step into contact with a first metal-containing gas generated by heating a metal or a metal oxide. A method for producing composite fullerene particles.   The metal is lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, Niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, cesium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, Thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, water , Thallium, lead, bismuth, polonium, francium, radium, actinium, thorium, protoactinium, uranium, neptunium, plutonium, americium, curium, barium, californium, einsteinium, fermium, mendelevium, nobelium, laurenium, rutherhodium, dobnium, 2. The method for producing composite fullerene particles according to claim 1, wherein the composite fullerene particles are one or more metals selected from seaborgium, bolium, hashium, mitnelium, and darmstatium.   The method for producing composite fullerene particles according to claim 1 or 2, wherein a heating temperature for generating fullerene gas in the first step is 400 to 480 ° C.   The method further comprises a fourth step of bringing the composite fullerene particles generated in the third step into contact with a second metal-containing gas generated by heating a metal or a metal oxide. The manufacturing method of the composite fullerene particle as described in any one of 1-3. A fifth step of bringing the composite fullerene particles produced in the third step into contact with the fullerene gas generated by heating the fullerene;
The method further comprises a sixth step of bringing particles generated by the fifth step into contact with a third gas generated by heating a metal or a metal oxide. 5. The method for producing composite fullerene particles according to any one of 4 above.   The method for producing composite fullerene particles according to any one of claims 1 to 5, wherein the first to sixth steps are performed in an atmospheric gas of 50 to 500 hPa. A first heating unit for heating fullerene to generate fullerene gas;
A cooling unit that cools the fullerene gas and particles at least a part of the fullerene gas;
A second heating unit that generates composite fullerene particles by bringing the fullerene that has been granulated in the cooling unit into contact with a first metal-containing gas generated by heating a metal or a metal oxide. An apparatus for producing composite fullerene particles.   The third heating unit for bringing the composite fullerene particles generated in the second heating unit into contact with a second metal-containing gas generated by heating a metal or a metal oxide. 8. The apparatus for producing composite fullerene particles according to 7. A fourth heating unit for bringing the fullerene gas generated in the second heating unit into contact with the fullerene gas generated by heating the fullerene;
5. A fifth heating unit for bringing particles generated in the fourth heating unit into contact with a third metal-containing gas generated by heating a metal or a metal oxide. The apparatus for producing composite fullerene particles according to 7 or 8. The composite fullerene particle manufactured by the manufacturing method as described in any one of Claims 1-6.

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