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WO2013132703A1 - Dispersion de nanoparticules, poudre porteuse de nanoparticules, et procédés de fabrication de ladite dispersion - Google Patents

Dispersion de nanoparticules, poudre porteuse de nanoparticules, et procédés de fabrication de ladite dispersion Download PDF

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Publication number
WO2013132703A1
WO2013132703A1 PCT/JP2012/079968 JP2012079968W WO2013132703A1 WO 2013132703 A1 WO2013132703 A1 WO 2013132703A1 JP 2012079968 W JP2012079968 W JP 2012079968W WO 2013132703 A1 WO2013132703 A1 WO 2013132703A1
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Prior art keywords
nanoparticle dispersion
crushed
nanoparticles
nanoparticle
liquid
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PCT/JP2012/079968
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English (en)
Japanese (ja)
Inventor
佐野　昌隆
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CERAFT Co Ltd
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CERAFT Co Ltd
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Priority to KR1020147023003A priority Critical patent/KR20140145116A/ko
Priority to JP2014503420A priority patent/JP6019102B2/ja
Priority to CN201280070412.1A priority patent/CN104271228A/zh
Publication of WO2013132703A1 publication Critical patent/WO2013132703A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • B02C19/18—Use of auxiliary physical effects, e.g. ultrasonics, irradiation, for disintegrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
    • B02C23/36—Adding fluid, other than for crushing or disintegrating by fluid energy the crushing or disintegrating zone being submerged in liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
    • B02C23/40—Adding fluid, other than for crushing or disintegrating by fluid energy with more than one means for adding fluid to the material being crushed or disintegrated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2202/00—Treatment under specific physical conditions
    • B22F2202/11—Use of irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a nanoparticle dispersion, a nanoparticle-supporting powder, and methods for producing them.
  • platinum Since platinum has a very chemically stable property and is excellent in a catalytic function for promoting a chemical reaction, it is used as a material for various applications such as automobile exhaust gas treatment and fuel cell electrodes. In addition, it is also used for biosensors utilizing the optical properties of platinum, and for foods and cosmetics utilizing antioxidant properties. Furthermore, for example, cisplatin or carboplatin is known as an antitumor agent of a platinum complex, and platinum has a wide range of applications. However, since platinum is very expensive, for example, when it is used as a catalyst, it is necessary to use a platinum material efficiently so that a high effect can be exhibited with as little amount as possible.
  • a platinum nanocolloid solution widely used as a platinum material is a solution in which platinum nanoparticles are dispersed and suspended in a solvent such as water and coated with a polymer such as citric acid, ascorbic acid, or sodium polyacrylate.
  • a solvent such as water
  • a polymer such as citric acid, ascorbic acid, or sodium polyacrylate.
  • a protective agent is usually included by coating around the metal nanoparticles using a polymer as a dispersion stabilizer (protective agent) for the metal nanoparticles.
  • a protective agent is usually included by coating around the metal nanoparticles using a polymer as a dispersion stabilizer (protective agent) for the metal nanoparticles.
  • the protective agent is adsorbed on the surface of the metal colloid particles, direct contact between the metal nanoparticles is suppressed, and aggregation and precipitation of the metal nanoparticles can be prevented.
  • Patent Document 1 discloses a platinum colloid solution that does not easily cause aggregation and precipitation and does not contain a protective agent that has excellent long-term stability.
  • Patent Document 1 discloses that in a colloidal platinum solution not containing a protective agent composed of platinum colloid composed of platinum particles and a solvent composed of water or a mixed solvent of water and an organic solvent, the platinum content in the platinum colloidal solution is 300 to A platinum colloid solution having 20000 ppm, pH 5.0 to 12.0, and electrical conductivity of 100 mS / m or less is disclosed.
  • Patent Document 1 there is a problem that an operation for adjusting pH and the like is complicated when preparing a platinum nanocolloid solution.
  • the conditions for producing the platinum colloid solution are limited.
  • functions such as the antioxidant power of platinum itself cannot be exhibited, and the original effects of platinum nanoparticles cannot be exhibited.
  • the present invention has been made in view of the above problems, and a method for producing a nanoparticle dispersion that can be stably dispersed without aggregation of nanoparticles such as platinum, and production of nanoparticle-supported powder It is an object of the present invention to provide nanoparticle dispersions and nanoparticle-supported powders obtained by the methods, and the production methods thereof.
  • a material to be crushed is immersed in a solvent in a processing vessel, and the material to be crushed is irradiated with a pulsed laser so that the material to be crushed is nano-sized.
  • a pulsed laser In order to prevent agglomeration of nanoparticles in the nanoparticle dispersion liquid, an ultrasonic wave is applied to the nanoparticle dispersion liquid.
  • a method for producing a nanoparticle dispersion to be irradiated comprising: The pulse laser has a wavelength longer than an absorption band caused by a specific electronic transition of the material to be crushed.
  • the method for producing a nanoparticle dispersion of the present invention is characterized in that, in (1), the surface of the material to be crushed is covered with a film having a laser absorption function.
  • the method for producing a nanoparticle dispersion of the present invention is characterized in that, in (1) or (2), the material to be crushed is plate-shaped.
  • the method for producing a nanoparticle dispersion of the present invention is characterized in that, in the above (1) to (3), the material to be crushed is particulate.
  • the method for producing a nanoparticle dispersion of the present invention is characterized in that, in the above (1) to (4), the solvent is water.
  • the method for producing a nanoparticle dispersion of the present invention is characterized in that, in the above (1) to (5), a temperature adjusting mechanism for adjusting the temperature of the nanoparticle dispersion is attached to the processing container. To do. (7)
  • a processing liquid introduction pipe is formed outside the processing container, and the solvent and the material to be crushed are used as the processing liquid. The material is introduced into an introduction pipe, and the pulsed laser is irradiated toward the treatment liquid introduction pipe to photocrush the material to be crushed into nano-sized particles.
  • the method for producing a nanoparticle-supported powder according to the present invention includes a substrate having an outer diameter larger than that of the nanoparticle dispersion liquid produced by any one of the production methods (1) to (7).
  • a mixed liquid in which particles are mixed is produced, and the mixed liquid is dried by a spray drying method to support the nanoparticles on the surface of the substrate particles.
  • the nanoparticle dispersion liquid of the present invention is obtained by immersing a material to be crushed into a solvent in a processing vessel and irradiating the material to be crushed with a pulsed laser to form a nanosized particle.
  • the nanoparticle dispersion liquid was irradiated with ultrasonic waves in the nanoparticle dispersion liquid in which the nanoparticles were dispersed in the solvent.
  • the pulsed laser has a wavelength longer than an absorption band caused by a characteristic electronic transition of the material to be crushed.
  • the nanoparticle dispersion of the present invention is characterized in that, in (9), the surface of the material to be crushed is covered with a film having a laser absorption function.
  • the nanoparticle dispersion of the present invention is characterized in that in (9) or (10), the material to be crushed is plate-shaped.
  • the nanoparticle dispersion of the present invention is characterized in that, in the above (9) to (11), the material to be crushed is particulate. (13)
  • the nanoparticle dispersion of the present invention is characterized in that, in the above (9) to (12), the solvent is water.
  • the nanoparticle dispersion of the present invention is characterized in that, in the above (9) to (13), a temperature adjusting mechanism for adjusting the temperature of the nanoparticle dispersion is attached to the processing container.
  • a processing liquid introduction pipe is formed outside the processing container, and the solvent and the material to be crushed are used as the processing liquid introduction pipe.
  • the nanoparticle-supported powder of the present invention is a mixed solution obtained by mixing the nanoparticle dispersion liquid according to any one of (9) to (15) above with base particles having an outer diameter larger than the nanoparticle. It is produced, and the mixed liquid is dried by a spray drying method, and the nanoparticles are supported on the surface of the substrate particles.
  • the material to be crushed can be efficiently photocrushed into nano-sized particles
  • Nanoparticles can be dispersed in a solvent such as water in the solvent.
  • the nanoparticle dispersion liquid obtained by this invention can be carry
  • the nanoparticle-supported powder obtained by the present invention has the effects of antioxidation, sterilization, deodorization and anticancer activity provided by the nanoparticles, and is supported on the surface of particles larger than the nanoparticles. By making it, the defect of a nanoparticle can be compensated.
  • a material to be crushed is immersed in a solvent in a processing vessel, and the material to be crushed is irradiated with a pulse laser to form the nanomaterial to be crushed.
  • a pulse laser In order to prevent agglomeration of nanoparticles in the nanoparticle dispersion liquid, an ultrasonic wave is applied to the nanoparticle dispersion liquid. Irradiation method.
  • the pulse laser it is important that the pulse laser has a wavelength longer than the light absorption band caused by the characteristic electronic transition of the material to be crushed.
  • an infrared pulse laser can be used in consideration of reducing photodegradation of nanoparticles by utilizing the principle of the liquid phase laser ablation method.
  • Examples of the material to be crushed include metal materials and ceramics, and examples of metal materials include platinum, silver, copper, gold, palladium, cobalt, titanium, and alloys containing these.
  • Examples of the ceramic material include silica, alumina, zirconia, silicon carbide, titanium oxide, and composite ceramic materials containing these.
  • Platinum is a particle made of a platinum group metal and containing 99% by mass or more of platinum.
  • the average particle size when converted into nanoparticles is 5 to 50 nm, and particularly preferably 10 to 30 nm. In particular, when the average particle size is in the range of 10 to 30 nm, it is possible to enhance the effects of the platinum nanoparticles such as an antioxidant action, a sterilization action, and an anticancer activity action.
  • the form of the material to be crushed is preferably a plate or a particle because it forms nanoparticles in a solvent using a laser.
  • a plate-shaped raw material preferably has a thickness of about 0.1 mm to 1 mm, and a particulate raw material preferably has a diameter of about 0.1 mm to 1 mm.
  • the surface of the material to be crushed be covered with a film having a laser absorption function.
  • the energy of the pulsed laser can be absorbed efficiently, and light crushing can be performed efficiently.
  • the coating having a laser absorption function include coatings such as laser-absorbing dyes, pigment-based absorbing dyes (such as carbon black), and light-absorbing resins.
  • the solvent may be a liquid such as an organic solvent or water, but it is desirable to use water in consideration of cost and safety.
  • a dispersant can be added to the solvent.
  • a surfactant is preferably exemplified.
  • a temperature control mechanism for adjusting the temperature of the nanoparticle dispersion to the processing container. That is, it is possible to reduce the quality deterioration of the nanoparticles of the material to be crushed by cooling the processing container and to prevent dew condensation occurring on the surface of the processing container. When dew condensation occurs on the surface of the processing container, the laser light is scattered to reduce the efficiency of nanoparticulation, so this temperature control mechanism has a role as a dew condensation prevention function.
  • the temperature control mechanism include a processing chamber that cools the outer periphery of the processing container.
  • a processing liquid introducing pipe is formed outside the processing container, the solvent and the material to be crushed are introduced into the processing liquid introducing pipe, and the pulse laser is irradiated toward the processing liquid introducing pipe to crushed the material. Can be photocrushed into nano-sized particles. By passing the material to be crushed through the treatment liquid introduction pipe, the material to be crushed can be efficiently lightly crushed.
  • the method for producing a nanoparticle-supported powder according to the present invention produces a mixed solution in which a base particle having an outer diameter larger than the nanoparticle is mixed with the nanoparticle dispersion produced by any one of the production methods described above,
  • the mixed liquid is dried by a spray drying method so that the nanoparticles are supported on the surface of the substrate particles.
  • a plurality of nanoparticles can be supported on the surface of base particles having a large outer diameter by spray drying.
  • it is desirable to make the support of the nanoparticles strong by supporting a plurality of nanoparticles on the surface of the base particles and then drying at a high temperature of about 100 to 200 ° C.
  • Examples of the base particles include metal materials, ceramic materials, and organic materials.
  • Examples of the metal materials include platinum, silver, copper, gold, palladium, cobalt, titanium, and alloys containing these. , Silica, alumina, zirconia, silicon carbide, titanium oxide, aene oxide, calcium carbonate, or a composite ceramic material containing these.
  • Organic substances include foods, drugs, plastics and the like. Examples of foods and drugs include organic substances such as vitamin C, hyaluronic acid, collagen, astaxanthin, and placenta extract.
  • the size of the substrate particles is preferably about 1 to 100 ⁇ m, but the size is not limited as long as it is larger than the nanoparticles.
  • the nanoparticle dispersion and the base particle may be simply mixed.
  • Inorganic binders can also be added.
  • the organic binder include an adhesive
  • examples of the inorganic binder include colloidal silica.
  • FIG. 1 is a schematic explanatory view showing a method for producing a nanoparticle dispersion according to Embodiment 1 of the present invention.
  • reference numeral 1 ⁇ / b> A is a nanoparticle dispersion production apparatus for producing nanoparticles by photocrushing a material to be treated in a solvent of a treatment liquid.
  • the liquid to be treated 2 is composed of liquid phase water 4 as a solvent and particles (material to be crushed) 5 of a material to be formed into nanoparticles contained in the water 4.
  • a particulate material was used as the material to be crushed.
  • a manufacturing apparatus 1 ⁇ / b> A used in the method for manufacturing a nanoparticle dispersion liquid of Embodiment 1 includes a processing container 3 for storing a liquid 2 to be processed.
  • the processing container 3 is made of, for example, quartz.
  • a thermostatic device (temperature control mechanism) 13 is installed so as to cover the processing container 3.
  • the thermostatic device 13 has a function as a cooling means for cooling the liquid 2 to be processed in the processing container 3 and holds the liquid 2 to be processed cooled to a low temperature at a constant temperature.
  • the manufacturing apparatus 1A includes a high-power laser light source 10 that irradiates a liquid to be processed 2 contained in the processing container 3 with laser light having a predetermined wavelength.
  • the laser light source 10 supplies laser light having a wavelength suitable for converting the raw material particles 5 of the light-disrupted material in the water 4 of the liquid 2 to be processed into nanoparticles.
  • a fixed wavelength laser light source can be used when the wavelength to be set in the laser light is known in advance.
  • a wavelength tunable laser light source may be used as the laser light source 10.
  • optical intensity adjustment means such as an attenuation
  • a magnetic stick 11 is accommodated together with the liquid 2 to be processed.
  • the magnetic stick 11 and the magnetic stirrer 12 are used to disperse the raw material particles 5 in the water 4 by stirring the water 4 and the raw material particles 5 of the liquid 2 to be processed in the processing container 3.
  • the ultrasonic vibrator 20 and an ultrasonic vibrator driving device 25 that drives and controls the ultrasonic vibrator 20 are installed at predetermined positions outside the processing container 3.
  • the ultrasonic transducer 20 is an ultrasonic irradiation unit that irradiates the liquid to be processed 2 in the processing container 3 with ultrasonic waves to prevent aggregation of nanoparticles.
  • the processing container 3 is configured to be able to irradiate the liquid 2 to be processed with ultrasonic waves using resonance vibration.
  • the ultrasonic transducer 20 is disposed on one side surface of the processing container 3.
  • a microphone 30 is attached on the side surface of the processing container 3 opposite to the ultrasonic transducer 20.
  • the microphone 30 and the vibration amplitude measuring device 35 constitute vibration amplitude monitoring means for monitoring the vibration amplitude of the processing container 3 due to ultrasonic irradiation.
  • the laser light source 10 and the vibrator driving device 25 are connected to a control device 15 including a computer.
  • the control device 15 is also connected to the magnet stirrer 12, the thermostatic device 13, and the vibration amplitude measuring device 35.
  • the control device 15 controls the production of nanoparticles by controlling the operation of each part of the production device 1A.
  • the manufacturing apparatus includes equipment capable of performing laser light irradiation (light crushing) and ultrasonic irradiation while cooling the liquid to be processed. This makes it possible to efficiently produce a platinum nanoparticle dispersion (an aqueous solution in which platinum nanoparticles are dispersed) from platinum particles.
  • FIG. 2 is a production flow showing a method for producing a nanoparticle dispersion in which platinum nanoparticles as nanoparticles are dispersed in the present embodiment.
  • step S101 water 4 as a solvent and platinum particles (raw material particles 5) as raw materials are mixed to prepare a liquid 2 to be processed, and introduced into the processing container 3 (step S101).
  • the thermostatic device 13 is driven to cool the processing container 3 and the processing target liquid 2 in the processing container 3 to a predetermined low temperature (S102).
  • the magnetic stirrer 12 is operated, the liquid 2 to be treated is stirred by the magnetic stick 11, and the raw material particles 5 are dispersed in the water 4 (S103).
  • the frequency of the ultrasonic wave irradiated to the to-be-processed liquid 2 is set (S104).
  • the ultrasonic vibrator 20 is driven by the vibrator driving device 25 to reach the processing container 3 and the liquid 2 to be processed. Irradiate sound waves. Further, the vibration amplitude of the processing container 3 due to ultrasonic irradiation is monitored by the microphone 30, and an electric signal indicating the monitoring result is output to the control device 15 through the vibration amplitude measuring device 35.
  • the control device 15 refers to the information on the ultrasonic frequency from the vibrator driving device 25 and the information on the monitor result from the vibration amplitude measuring device 35, and the vibration frequency of the radiating ultrasonic wave and the processing container 3.
  • the relationship with the vibration amplitude (vibration intensity) is obtained.
  • the frequency of the ultrasonic wave irradiated to the to-be-processed liquid 2 is set based on the relationship between a vibration frequency and an amplitude. Specifically, in the relationship between the obtained frequency and amplitude, the frequency at which the vibration amplitude is the maximum is the resonance vibration frequency in the processing container 3, so that the ultrasonic wave irradiated from the ultrasonic transducer 20 to the processing container 3. Is set to the resonance vibration frequency through the vibrator driving device 25.
  • the laser light source 10 is controlled by the control device 15, and laser light having a wavelength set according to the light absorption characteristics of the substances constituting the raw material particles 5 is irradiated from the laser light source 10 to the liquid 2 to be processed.
  • ultrasonic waves are applied to the processing container 3 and the liquid 2 to be processed by the ultrasonic vibrator 20. By this ultrasonic irradiation, aggregation of the nanoparticles generated in the water 4 is prevented (S105).
  • the progress state of the light crushing process in the to-be-processed liquid 2 is confirmed (S106). And if the progress state does not satisfy the completion conditions for the predetermined light crushing treatment (nanoparticle formation), the light crushing by laser irradiation is further continued. On the other hand, if it is determined that the progress state satisfies the conditions for completing the photodisruption treatment and the raw material particles are converted into nanoparticles in the entire liquid 2 to be treated, the laser light irradiation and the ultrasonic irradiation are stopped (S107), The light crushing process is terminated.
  • laser light irradiation by the laser light source 10 for forming nanoparticles and ultrasonic irradiation by the ultrasonic vibrator 20 for preventing aggregation are simultaneously performed on the liquid 2 to be processed including the raw material particles 5. ing. Thereby, in the water 4, it becomes possible to perform the light crushing process by laser beam irradiation, suppressing progress of aggregation of the produced
  • Such a method for producing a nanoparticle dispersion using ultrasonic irradiation is particularly effective when the concentration of a nanoparticle of a substance (material to be crushed) is efficiently increased by increasing the concentration of the nanoparticle. That is, in order to improve the efficiency of nanoparticulation by laser light irradiation, it may be necessary to perform the nanoparticulate treatment by increasing the concentration of nanoparticles produced in the solvent. However, in the presence of a high concentration of nanoparticles, the conditions tend to cause aggregation of the nanoparticles. For this reason, the efficiency of nanoparticulation is reduced by the scattering of the laser light from the aggregated nanoparticles, or the produced nanoparticles have a large variation in particle size. In contrast, by performing ultrasonic irradiation simultaneously with laser light irradiation as described above, the material to be crushed can be made into nanoparticles under good conditions even in the presence of such high concentration of nanoparticles. Is possible.
  • ultrasonic irradiation by the ultrasonic transducer 20 is performed using the resonance vibration of the processing container 3 that stores the liquid 2 to be processed.
  • the processing container 3 for example, it is preferable to use a container having a rectangular column shape, a cylindrical shape, or a spherical shape capable of resonance vibration.
  • resonance vibration when using resonance vibration in this way, the durability of the processing vessel 3 against large resonance vibration is required, but by using a container such as a cylinder or a sphere, by reducing joints that are vulnerable to vibration, Such durability can be enhanced.
  • the vibration amplitude of the processing container 3 is monitored by the microphone 30 and the vibration amplitude measuring device 35, and the frequency of the ultrasonic wave is set based on the monitoring result.
  • the frequency of the ultrasonic wave can be set to a suitable frequency such as a resonance vibration frequency in the processing container 3, and it becomes possible to reliably prevent the aggregation of the nanoparticles due to the ultrasonic irradiation.
  • the vibration amplitude monitoring means various sensors other than the microphone 30 can be used.
  • the aggregation of the nanoparticles in the solvent the lower the solubility of the nanoparticles, the higher the aggregation property. In such a case, the effect of preventing aggregation by the combined use of ultrasonic irradiation is great.
  • laser light irradiation and ultrasonic irradiation are performed while the liquid 2 is cooled by the thermostatic device 13.
  • Such cooling of the liquid to be treated 2 is effective in preventing the oxidation of the nanoparticles due to the laser light irradiation and improving the efficiency of the light fragmentation, and also reduces the cohesive force of the nanoparticles and the strong resonance vibration field. Also contributes to formation.
  • the wavelength of the laser light irradiated from the laser light source 10 to the liquid 2 to be processed is longer than the absorption band caused by the electronic transition of the substance to be nanoparticulate.
  • the wavelength is preferably in the infrared region, and more preferably 900 nm or more. Thereby, in light crushing processing, quality deterioration can be reduced and it can realize suitably.
  • the laser light source 10 a pulse laser light source is preferably used.
  • a pulsed laser light source having a low irradiation energy per pulse and a high repetition frequency.
  • the intensity and time of the laser light necessary for the light crushing process are obtained in advance, and the stop of laser light irradiation and ultrasonic irradiation can be controlled. it can. Or it is good also as installing the monitoring means which monitors the nanoparticle state of the raw material particle 5 in the to-be-processed liquid 2, and controlling according to the monitoring result.
  • FIG. 3 is a schematic explanatory view showing a method for producing a nanoparticle dispersion liquid of Embodiment 2.
  • the processing container 3 that contains the liquid to be processed 2 composed of the water 4 and the raw material particles 5 of the substance, the laser light source 10, the magnet stick 11, the magnet stirrer 12, the thermostat 13, And the structure of the control apparatus 15 is the same as that of 1 A of manufacturing apparatuses shown in FIG.
  • the ultrasonic transducer 21 that is an ultrasonic irradiation unit is disposed on the bottom surface side of the processing container 3.
  • an ultrasonic transducer driving device 26 that drives and controls the ultrasonic transducer 21 is installed for the ultrasonic transducer 21.
  • the signal from the vibrator driving device 26 is also input to the vibration amplitude measuring device 36.
  • the vibration amplitude measuring device 36 measures the vibration amplitude of the processing container 3 based on a signal from the vibrator driving device 26.
  • the ultrasonic vibrator 21, the vibrator driving device 26, and the vibration amplitude measuring device 36 constitute vibration amplitude monitoring means for monitoring the vibration amplitude of the processing container 3 due to ultrasonic irradiation. .
  • the ultrasonic vibrator 21 In the configuration in which the ultrasonic vibrator 21 is installed on the bottom surface of the processing container 3 as described above, resonance vibration is formed between the bottom surface and the top surface of the water 4. At this time, when the resonance vibration state is reached, the ultrasonic vibrator 21 vibrates greatly, and the voltage applied to the vibrator increases. Therefore, by monitoring the change in the amplitude of the voltage applied to the ultrasonic vibrator 21 by the vibration amplitude measuring device 36, the resonance vibration frequency in ultrasonic irradiation can be obtained. In this case, there is an advantage that the microphone 30 shown in FIG. 1 or the like need not be separately provided for monitoring the vibration amplitude.
  • FIG. 5 the manufacturing method of the nanoparticle dispersion liquid of Embodiment 3 is shown.
  • the processing liquid introduction pipe 40 is formed outside the processing container 3, and the liquid 2 to be processed is introduced into the processing liquid introduction pipe 40.
  • the material to be crushed can be photocrushed into nano-sized particles (nanoparticles) by irradiating a pulse laser toward the treatment liquid introduction pipe 40. By passing the material to be crushed dispersed in the liquid to be treated 2 through the treatment liquid introduction pipe in a narrow range, it is possible to concentrate the pulse laser and efficiently perform the light crushing.
  • FIG. 6 the manufacturing method of the nanoparticle dispersion liquid of Embodiment 4 is shown.
  • a plate 5 is used as a raw material as shown in FIG.
  • the thickness of the plate 5 is preferably about 0.1 mm to 1 mm considering the efficiency of light crushing with a laser.
  • the plate 5 serving as a raw material is erected in the processing container 3 and is irradiated with laser from a direction perpendicular to the surface of the plate 5.
  • the laser light source or the plate is moved by the control device 15 so that the laser is scanned over the entire surface of the plate 5.
  • the plate that is the raw material of the material to be crushed is usually set up in the processing container 3 so that one thin plate is perpendicular to the laser irradiation direction, but may be a laminate of a plurality of plates. .
  • the film 5a having a laser absorbing function include thin films such as a laser absorbing dye, a pigment-based absorbing dye (such as carbon black), and a light absorbing resin.
  • a stack of two or more raw material plates 5 may be erected.
  • the raw material plate 5 may be of a different type.
  • the film 5a can also be sandwiched between the laminated plates.
  • FIG. 8 is a production flow showing a method for producing a nanoparticle dispersion in which platinum nanoparticles as nanoparticles are dispersed in the fourth embodiment.
  • step S201 water 4 as a solvent and a plate 5 as an object to be processed are immersed in the processing container 3 (step S201).
  • the thermostatic device 13 is driven to cool the processing container 3 and the solvent in the processing container 3 to a predetermined low temperature (S202).
  • the magnetic stirrer 12 is operated and the solvent is stirred by the magnetic stick 11 (S203).
  • the frequency of the ultrasonic wave irradiated to the board 5 used as a to-be-processed object is set (S204).
  • the ultrasonic vibrator 20 is driven by the vibrator driving device 25 to irradiate the processing container 3 and the solvent with ultrasonic waves. To do. Further, the vibration amplitude of the processing container 3 due to ultrasonic irradiation is monitored by the microphone 30, and an electric signal indicating the monitoring result is output to the control device 15 through the vibration amplitude measuring device 35.
  • the control device 15 refers to the information on the ultrasonic frequency from the vibrator driving device 25 and the information on the monitor result from the vibration amplitude measuring device 35, and the vibration frequency of the radiating ultrasonic wave and the processing container 3.
  • the relationship with the vibration amplitude (vibration intensity) is obtained.
  • the frequency of the ultrasonic wave irradiated to the to-be-processed liquid 2 is set based on the relationship between a vibration frequency and an amplitude. Specifically, in the relationship between the obtained frequency and amplitude, the frequency at which the vibration amplitude is the maximum is the resonance vibration frequency in the processing container 3, so that the ultrasonic wave irradiated from the ultrasonic transducer 20 to the processing container 3. Is set to the resonance vibration frequency through the vibrator driving device 25.
  • the laser light source 10 is controlled by the control device 15, and laser light having a wavelength set according to the light absorption characteristics of the substances constituting the raw material plate 5 is irradiated from the laser light source 10 to the raw material plate 5. .
  • the raw material plate 5 in the water 4 in the processing container 3 is photo-crushed into nano size.
  • the ultrasonic vibrator 20 irradiates the processing container 3 and the solvent with ultrasonic waves. By this ultrasonic irradiation, aggregation of nanoparticles generated in the water 4 is prevented (S205).
  • the progress state of the light crushing process in a processing container is confirmed (S206). And if the progress state does not satisfy the completion conditions for the predetermined light crushing treatment (nanoparticle formation), the light crushing by laser irradiation is further continued. On the other hand, if it is determined that the progress state satisfies the conditions for completing the light crushing process and that the raw material particles are converted into nanoparticles as a whole, the laser light irradiation and the ultrasonic wave irradiation are stopped (S207), and the light crushing process is completed. To do.
  • FIG. 9 is a schematic explanatory view showing the appearance of the nanoparticle-supported powder of the present invention.
  • the nanoparticle-supported powder Q shown in FIG. 9 is produced by mixing a nanoparticle dispersion produced by any of the above production methods with a base particle C having an outer diameter larger than that of the nanoparticle P.
  • the mixed liquid is dried by a spray drying method, and the nanoparticles P are supported on the surface of the base particle C.
  • the nanoparticle-supported powder Q dried by the spray drying method is dried at a high temperature of about 100 to 200 ° C. to firmly support the plurality of nanoparticles P on the surface of the base particle C.
  • the nanoparticle-supported powder Q shown in FIG. 9 has platinum P (size: 10 nm) supported on the surface of silica (size: 10 ⁇ m) as the base particles C.
  • platinum particles were used as the raw material particles 5 to be made into nanoparticles. Platinum is a pigment that is very insoluble in water (poor solvent), and exhibits high cohesiveness in water when it is made into nanoparticles.
  • six samples were prepared in which 3 ml of platinum raw material particles having a particle diameter of 10 to 70 ⁇ m were placed in a quartz square cell as the processing vessel 3 in a high concentration suspension state with a concentration of 1 mg / ml.
  • a quartz square cell having a size of 10 mm ⁇ 10 mm ⁇ 40 mm was used, and a piezoelectric vibrator having a diameter of 16 mm and a thickness of 3 mm was attached to the bottom surface thereof as an ultrasonic vibrator 21 (see FIG. 3).
  • “ultrasonic treatment” was performed for 30 minutes by operating an ultrasonic transducer at 30 kHz outside the resonance vibration frequency.
  • the ultrasonic vibrator was operated at a resonance vibration frequency of 51 kHz, and the treatment was performed for 30 minutes.
  • the laser light irradiation conditions in the light crushing process are as follows: wavelength 1064 nm, light intensity 688 mJ / cm 2 per pulse of pulsed laser light, laser beam spot diameter ⁇ 5 mm (irradiation area 0.196 cm 2 ), repetition frequency 10 Hz, The treatment was performed with a pulse width of FWHM 4 ns and an irradiation time of 30 minutes.
  • a surfactant Nonidet P-40: trade name Igapal CA-630, molecular weight 602, critical micelle concentration 0.29 mM
  • 100 ⁇ l was added to the liquid to be treated, and the particle size distribution was measured under the condition that the reaggregation of nanoparticles was suppressed.
  • the water temperature at the time of measurement was room temperature 25 ° C.
  • FIG. 4 is a graph showing the particle size distribution of the platinum nanoparticles subjected to the above-described treatments.
  • the horizontal axis indicates the particle diameter ( ⁇ m) of platinum, and the vertical axis indicates the relative particle amount in terms of volume.
  • Graphs A1 to A6 correspond to processes (a) to (f), respectively.
  • the ultrasonic wave is compared with the laser light irradiation. It can be confirmed that the efficiency of nanoparticulation is increased by using irradiation in combination.
  • the vibration amplitude is larger than that of normal ultrasonic irradiation, so that the action of redispersing the aggregated nanoparticles is strong. Scattering loss is reduced, and the efficiency of nanoparticulation is particularly high. Based on the above, it was confirmed that using ultrasonic irradiation in combination with laser light irradiation is effective in increasing the efficiency of nanoparticle formation when performing photocrushing in a state where nanoparticles are likely to aggregate. .
  • the method for producing a nanoparticle dispersion liquid according to the present invention efficiently irradiates a material to be crushed into nano-sized particles by performing irradiation with laser light for light crushing on a liquid to be treated and ultrasonic irradiation for preventing aggregation. And a dispersion liquid in which nanoparticles are dispersed in the solvent can be produced.
  • a mixed liquid in which the obtained nanoparticle dispersion is mixed with base particles having an outer diameter larger than that of the nanoparticles is produced, and the mixed liquid is dried by a spray drying method, so that the surface of the base particles is A nanoparticle-supported powder can be produced by supporting nanoparticles.
  • the nanoparticle dispersion and the nanoparticle-supported powder obtained by the production method of the present invention can easily provide effects such as an antioxidative action, a sterilizing action, a deodorizing action, and an anticancer activity action that each material has. It can be expressed and has high industrial applicability.
  • Nanoparticle dispersion production apparatus 2 ... Liquid to be treated 3 ... Treatment vessel 4 ... Water (solvent) 5 ... Raw material particles (material to be crushed) DESCRIPTION OF SYMBOLS 10 ... Laser light source 11 ... Magnet stick 12 ... Magnet stirrer 13 ... Constant temperature apparatus 15 ... Control apparatus 20, 21 ... Ultrasonic vibrator 25, 26 ... Ultrasonic vibrator drive apparatus 30 ... Microphone 35, 36 ... Vibration amplitude measuring apparatus 40 ... Pipe P ... Nanoparticle C ... Base particle Q ... Nanoparticle-supported powder

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PCT/JP2012/079968 2012-03-09 2012-11-19 Dispersion de nanoparticules, poudre porteuse de nanoparticules, et procédés de fabrication de ladite dispersion Ceased WO2013132703A1 (fr)

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JP2018148055A (ja) * 2017-03-06 2018-09-20 国立大学法人九州大学 液相レーザーアブレーションを利用したナノ粒子の製造方法
JP2020084345A (ja) * 2018-11-19 2020-06-04 株式会社セラフト ナノプラチナ粒子含有樹脂繊維
CN115346749A (zh) * 2021-05-13 2022-11-15 精工爱普生株式会社 软磁性粉末、压粉磁芯、磁性元件、电子设备以及移动体

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KR102485978B1 (ko) * 2020-09-24 2023-01-06 경상국립대학교산학협력단 펄스 레이저 조사를 이용하는 리그닌-금속 나노입자의 제조방법

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