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WO2000044679A1 - Procede de fabrication et de depot de particules fines par combinaison de flamme et d'un rayon laser - Google Patents

Procede de fabrication et de depot de particules fines par combinaison de flamme et d'un rayon laser Download PDF

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Publication number
WO2000044679A1
WO2000044679A1 PCT/KR2000/000049 KR0000049W WO0044679A1 WO 2000044679 A1 WO2000044679 A1 WO 2000044679A1 KR 0000049 W KR0000049 W KR 0000049W WO 0044679 A1 WO0044679 A1 WO 0044679A1
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particles
flame
laser beam
burner
laser
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Man Soo Choi
Dong Geun Lee
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Priority to DE10083901T priority Critical patent/DE10083901T1/de
Priority to JP2000595941A priority patent/JP3790105B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
    • C23C16/483—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation using coherent light, UV to IR, e.g. lasers
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C03B19/106—Forming solid beads by chemical vapour deposition; by liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
    • C03B19/1415—Reactant delivery systems
    • C03B19/1423—Reactant deposition burners
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
    • C03B37/01413—Reactant delivery systems
    • C03B37/0142—Reactant deposition burners
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/0025—Other surface treatment of glass not in the form of fibres or filaments by irradiation by a laser beam
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2207/00—Glass deposition burners
    • C03B2207/46—Comprising performance enhancing means, e.g. electrostatic charge or built-in heater

Definitions

  • the present invention relates to a method for manufacturing fine particles including ceramic particles, metallic particles, glass particles or composite particles and a method of depositing the fine particles on a silica rod or wafer using a flame, and more particularly, to a method for controlling the size, morphology, phase and composition of fine particles produced in a flame combining a laser beam.
  • FIG. 1 schematically shows an apparatus for flame hydrolysis deposition (FHD) for generating and growing particles in a flame.
  • gases such as N 2 are introduced into containers la and lb containing the reactants to then be carried to a burner 4.
  • the reactants carried to the burner 4 are injected into a flame 5 generated by combustion of a fuel such as H 2 to thereby generate particles 6.
  • the containers la and lb containing the reactants, and the burner 4 are connected to each other by conduits, and valves 3 and mass flow controllers (MFCs) 2 are installed along the flow paths.
  • the reactants used in the apparatus vary according to a material to be manufactured, and multi-component composite particles may be produced using a plurality of reactants.
  • reactants such as SiCl 4 , GeCl 4 , or POCl 3 are used. Since these reactants have a low vapor pressure at room temperature, their flows are accurately adjusted by the MFCs 2 to then be supplied to the burner 4 via a carrier gas.
  • the reactants injected from the nozzle of the burner 4 react with H 2 O generated in the flame 5 due to combustion of hydrogen to thereby generate particles 6 such as SiO 2 , GeO 2 or P 2 O 5 . These particles 6 are deposited on a target substrate 10.
  • the carrier gas for the reactants is replaced with oxygen
  • a silica rod (not shown) is installed, instead of the target substrate 10 and rotated at a speed of about 60 rpm, and the burner 4 is made to reciprocate left and right so that the generated particles are adhered to the silica rod.
  • This is referred to as an outside vapor deposition (OND) method.
  • OND outside vapor deposition
  • a silicon wafer (not shown) is installed instead of the target substrate 10, and the wafer or the burner 4 is moved in a two-dimensional direction for deposition of particles.
  • the most influential factors in the optical characteristics of a finally produced optical device and sintering characteristics of a preform are the size, composition and morphology of particles at the time of deposition.
  • the formation of aggregates and the nonuniform distribution in the size of nanoparticles affects powder flow and packing, thereby forming porous pores, which adversely affect the mechanical strength, optical and magnetic characteristics of the device.
  • the fine powders having their own solid-state phases for example, TiO 2 powders have three phases of anatase, brookite and rutile
  • the phases are differently favored according to their applications. Examples of applications currently being investigated include catalytic materials, sensors, thin-film batteries and capacitors for electrical storage.
  • TiO 2 has proved to be the most active photocatalyst for the treatment of toxic and biologically persistent compounds, with the anatase phase showing higher activity than rutile phase.
  • Burners which are currently used in manufacturing various kinds of fine powders and optical devices include a coflow diffusion flame burner, a counterflow diffusion flame burner, a coflow premixed flame burner and so on. Depending on the type of burner, the temperature distribution and flow conditions vary considerably. However, the nucleation and growth mechanisms are basically the same as one another.
  • the particle size and morphology are determined by the ratio of coalescence time of the particles to interparticle collision time of the particles (see Y. Xiong et al., 1993, J. Aerosol Sci. , 24(3), pp. 301-303 and S.E. Pratsinis, 1988, Prog. Energy Combust. Sci., 24, pp. 197-219.).
  • coalescence occurs faster than collision, that is, if the flame temperature is relatively high, as shown in FIG. 2A, two or more particles connected to one another coalesce to form an isometrically spherical particle.
  • FIG. 2B particles are connected to one other like linear chains to form aggregates, instead of forming a sphere due to coalescence.
  • the time required for the aggregate volume to double is defined as the characteristic collision time ( ⁇ c ), which can be written in the following formula (see R. S. Windeler et al., 1997, Aerosol Sci. and Tech., 27, pp. 174-190.):
  • v is the average volume of aggregates
  • k is the Boltzmann constant
  • T is the temperature
  • p density
  • ⁇ is a constant depending on Df
  • d p is a diameter of an individual primary particle constituting an aggregate
  • ⁇ is the volumetric ratio of generated particles, that is, the ratio of a volume of generated particles to a volume of chemical carrier gases
  • Df is the fractal dimension of aggregates.
  • a Df value closer to 3 means that aggregates are substantially spherical
  • a Df value closer to 1 means that aggregates are formed like linear chains. In the case of aggregates manufactured using a flame, the Df value ranges from 1.6 to 2.0.
  • the collision time becomes smaller than the coalescence time.
  • a large aggregate is unavoidably formed due to collision among aggregates.
  • the time required for two spherical particles to completely coalesce to form an isometric sphere, as shown in FIG. 2A, is defined as the characteristic coalescence time ( ⁇ f ), which is largely classified into a solid state diffusion mechanism and a viscous flow mechanism according to the sintering mechanism of the particles.
  • ⁇ f characteristic coalescence time
  • TiO 2 particles go with the solid state diffusion mechanism
  • SiO 2 particles go with the viscous flow mechanism.
  • the characteristic coalescence time of SiO 2 can be written as the following formula (2) (see W.D. Kingery et al. , 1976, Introduction to Ceramics, Wiley -Interscience, New York.):
  • Alternative method for controlling the particle size is to actively reduce the particle size by suppressing collision by directly applying a force to the particles, as shown in FIG. 3.
  • a strong direct-current (DC) electrical field is applied to the particles by electrodes 11a and lib at both sides, positively or negatively charged particles move to oppositely charged electrodes due to the electrical field.
  • the residence time of the particles in a high-temperature region of the flame is reduced and thus the coalescence rate of particles is reduced, the sizes of primary particles become smaller.
  • charged particles move from the flame to oppositely charged electrodes, which reduces the number density of the particles in the flame, the collision rate among particles is reduced so that the sizes of aggregates become smaller.
  • the sizes of both primary particles and aggregates are made smaller. However, it is not possible to avoid collision due to turbulence generated by the movement of the particles to both electrodes. Thus, even though the particle size is reduced, the formation of aggregates is unavoidable for the manufacture of high concentration aerosols. Also, since the produced particles are adhered to electrodes, the particle deposition efficiency is undesirably lowered (see S. Vemury et al. , J. Aerosol Sci., 1996, 27, pp. 951 and Y. Xiong et al., 1996, Combustion and Flame, 107, pp. 85.).
  • a method of manufacturing fine particles containing metallic fine powder, glass fine powder and composite fine powder comprising the steps of: supplying reactants into a burner forming a flame; generating particles from the reactants in the flame of the burner; and irradiating at least one laser beam into the particles generated in the flame to thereby heat and sinter the particles.
  • the wavelength of the laser beam coincides with the main absorption wavelength band of the particles generated in the flame.
  • a method for depositing fine particles containing metallic fine powder, glass fine powder and composite fine powder on a target substrate comprising the steps of: supplying reactants into a burner forming a flame; generating particles from the reactants in the flame of the burner; irradiating at least one laser beam into the particles generated in the flame to thereby heat and sinter the particles; and adhering the sintered particles to the target substrate to be deposited thereon.
  • FIG. 1 is a schematic diagram illustrating a conventional fine particle manufacturing apparatus
  • FIGS. 2 A and 2B illustrate particle growth mechanisms in a flame shown in FIG. 1;
  • FIG. 3 is a diagram for explaining a conventional method of manufacturing fine particles in order to control the growth of particles
  • FIG. 4 is a diagram for explaining another conventional method of manufacturing fine particles in order to control the growth of particles
  • FIG. 5 illustrates a fine particle manufacturing mechanisms according to the present invention
  • FIGS. 6 A through 6C illustrate examples of laser beams which can be employed in apparatus for performing a method of manufacturing fine particles according to the present invention
  • FIG. 7 is a diagram showing a detailed embodiment of an apparatus for performing a method of manufacturing fine particles according to the present invention
  • FIGS. 8 A and 8B illustrate the distribution of temperatures in a flame according to the fine particle manufacturing method of the present invention
  • FIGS. 9A and 9B are graphs illustrating the scattered intensity with respect to the incidence position of a laser beam, according to the fine particle manufacturing method of the present invention
  • FIG. 10 is a graph illustrating the weight fraction of the Rutile phase with respect to the collection position, in the absence of CO 2 laser irradiation
  • FIG. 11 is a graph illustrating the variation of X-ray diffraction patterns of samples of powder collected at a height of 65 mm when the power of the CO 2 laser beam is irradiated at a height of 35 mm from the burner end, according to the fine particle manufacturing method of the present invention
  • FIG. 12 is a graph illustrating weight fractions of the Rutile phase for different incidence positions of a laser beam, according to the fine particle manufacturing method of the present invention
  • a method of manufacturing fine particles according to the present invention and a method of manufacturing an optical device preform can be performed by using a conventional apparatus shown in FIG. 1.
  • the feature of the present invention lies in that a laser beam having a predetermined wavelength is irradiated when particles 6' are produced in a flame 5 at an end of a burner 4, as shown in FIG. 5.
  • fine spherical powder particles and an optical device preform are manufactured as follows. Using the apparatus shown in FIG. 1, hydrogen and oxygen are introduced to the burner 4 to form a flame 5 and reactants are sprayed from the central part of the burner 4 into the flame using nitrogen or oxygen. Then, vapor reactants sprayed into the flame 5 react with each other to form particle nuclei of about 0.5 nm near the end of the burner 4. These nuclei move along the flame 5 to form very small-sized aggregates by collision.
  • the collision time decreases in an order of T "1/2 as the temperature increases.
  • the coalescence time decreases exponentially, that is, much faster than the collision time, according to the increase in the temperature.
  • the particle temperature is sharply raised by irradiating a laser beam in the wavelength range in which particles readily absorb the laser beam into the tiny aggregates at an initial nucleation stage, coalescence of particles dominantly occurs, thereby generating small-sized spherical particles.
  • the raised temperature of the particles is lower than their melting point, thermodynamically stable phase can be obtained due to additionally supplying energy required the phase transformation to stable phase by irradiating the laser beam.
  • a metastable phase can be obtained because the metastable phase are favored during recrystallization form liquid phase to solid phase due to short residence time in a flame.
  • a target substrate 10 for example, a silica rod
  • a target substrate 10 is spaced 10 to 20 cm apart from the end of the burner 4 to then be rotated at a speed of about 60 rpm, thereby depositing particles of 10 to 40 nm in size on the target substrate 10.
  • the spherical particles have a much smaller collision area than the uncoalesced aggregates (see S.E. Pratsinis, 1998, Prog. Energy Combust. Sci., 24, pp.
  • the spherical particles exhibit lower collision rate while moving along the flame.
  • the particles become much smaller- sized spherical particles (6' of FIG. 5) compared to the those (6 of FIG. 4) without laser incidence.
  • the coalescence rate can be controlled independently of the collision rate, small-sized spherical particles can be produced even with an increase in the amount of a reactant carrier gas, and the deposition rate, quality of fine particles and optical device manufactured can be greatly improved.
  • Deposition is consistently performed while a burner is moved left and right in the range of 1 m at a speed of 15 cm/min.
  • a silicon wafer having a diameter of about 12 inches, instead of a silica rod, is installed and particles are deposited while rotating and moving the wafer.
  • a ceramic filter or an electrical dust collector is installed to collect the particles produced in the above- described process.
  • a laser beam can be made incident into a flame in various manners, as shown in FIGS. 6A through 6C.
  • single incidence FIG. 6A
  • multi-incidence of a laser beam is preferably employed, as shown in FIG. 6B, in order to enhance a laser incidence efficiency.
  • a plurality of laser beams may be irradiated.
  • laser beams may be cross-irradiated into a flame 5 by installing a plurality of mirrors 41 and 42.
  • co-axial incidence in which a laser beam is irradiated coaxially with the flame 5 may be employed.
  • Reference numerals 51, and 31 and 52 denote a mirror, and lenses for focusing a laser beam, respectively.
  • multi-incidence allows effective utilization of laser energy by irradiating a laser beam several times in accordance with the movement of particles.
  • particles consecutively absorb laser beams while moving along a flame by irradiating a laser beam through a transferring conduit of reactants in the burner, the same effect can be exerted with a low power laser.
  • the reactant supplying apparatus and a fuel flow controlling apparatus were installed in the same manner as in FIG. 1.
  • a flame stabilizer 4b such as a honeycomb structure was additionally installed at the outside of a coflow diffusion flame burner 4 consisting of four stainless steel tubes to form a stable laminar diffusion flame.
  • a mixed gas of SiCl 4 and N 2 was supplied to the central part of the burner 4 through a nozzle 4a.
  • nitrogen for shielding was injected through a plurality of holes formed around the nozzle 4a.
  • 61a through 61c denote polarizers, 62a through 62c lenses, 82 laser line filters, 63a and 63b pinhole openings, 64 a mirror, and 91a and 91b beam dumps.
  • a CO 2 laser 70 was installed a predetermined distance (referred to as h L ) above from the end of the burner 4 to irradiate a laser beam, and an Ar ion laser 60 was installed 5 mm above the CO 2 laser 70 to irradiate a laser beam having a wavelength of 514 nm. Then, scattered light signals produced by particles were stored in a personal computer (not shown) through a photomultiplier tube (PMT) 80.
  • PMT photomultiplier tube
  • the particles were thermophoretically sampled at the same height as the Ar ion laser beam and particle size and morphology were measured by transmission electron microscopy (TEM) to then be compared with scattered light intensity, thereby verifying how effective CO 2 laser beam incidence is in controlling the growth of particles produced in the flame.
  • the Ar ion laser 60 was installed predetermined distance, i.e., a sampled position (referred to as hp) above the end of the burner 4 and 5 mm above the CO 2 laser 70.
  • N is the number density of aggregates
  • n is the number of primary particles
  • x p is the ratio of a primary particle diameter (d p ) to a wavelength ( ⁇ ) of laser beam, i.e. , ⁇ d p / ⁇
  • R g is the radius of gyration of an aggregate, indicating how far primary particles are spaced apart from the mass center of the aggregate.
  • the scattered intensity increases in proportion to the primary particle diameter (d p ) raised to the sixth power and the number density of aggregates.
  • particles are thermophoretically sampled at local spots in a flame and the particle size and the change in the morphology can be quantitatively identified by TEM.
  • TEM TEM-based TEM
  • the low temperature at the flame center is caused by a cooling effect of the flame due to a shield gas injected for preventing the produced particles from adhering to the surface of the nozzle.
  • the flame temperature distributions are parabola-shaped. This is caused by diffusion of oxygen and hydrogen in the flame.
  • W Watt
  • the gas temperature is raised by about 100 °C due to laser absorption of the intermediate products generated by the combustion of hydrogen.
  • laser absorption by gas was relatively small and a relatively small increase in the gas temperature, that is, about 40 °C, was shown, which was because the concentration of injected nitrogen was high and hydrogen was not sufficiently diffused at the center of the flame.
  • the infrared absorption bands of SiO 2 are 455 cm “1 , 1090 cm “1 and 800 cm “ 1 (see R. A. Nyquist et al. , Infrared Spectra of inorganic compounds, 4, Academic Press, Inc. , 1997.).
  • the frequency of the CO 2 laser beam is 934 cm "1 , at which frequency coincidence occurs more easily in particles than the case of the gas.
  • the size of a particle is at least 100 times greater than the size of a gas molecule.
  • the actual laser absorption of particles is much larger than that of the gas.
  • Laser beam incidence into particles results in a sharp increase in the particle temperature compared to in the gas temperature.
  • the scattered intensity sharply increased up to approximately 14 mm in the hp distance due to rapid nucleation and coagulation, which are caused by chemical reactions, while the scattered intensity gently increased at a position of over 14 mm.
  • laser incidence makes a quite different tendency in the scattered intensity variation.
  • the particle size was reduced from approximately 70 nm to approximately 40 nm while maintaining spherical shapes, as the CO 2 laser power increases. Also, when I equals 1170 W, due to evaporation and recondensation, very small particles of 5 nm in diameter were adhered to the surfaces of particles. In other words, it was verified that laser incidence into a flame satisfactorily changed the particle size.
  • particles was sampled at a position of 20 mm when the incidence position of a laser beam is 15 mm at a high flow rate of a carrier gas (150cc/min).
  • I 0 W
  • partially-sintered aggregates seen immediately before being completely sintered were observed.
  • the laser power was increased, the particles became smaller by about 60% while the shapes of the particles were still spherical. This is quite an encouraging result in terms of deposition rate.
  • the deposition rate linearly increases and thus small-sized spherical particles can be produced for deposition, which is in conformity to the objective of the present invention. Also, if the absorption wavelength of produced particles coincide with or is close to the frequency of the irradiated laser beam, the effect of manufacturing fine particles can be considerably increased by low power laser incidence.
  • TiO 2 particles are known to have three solid-state phases of anatase, brookite and rutile. Rutile is the only thermodynamically stable phase, whereas the others are metastable phases. Anatase is the most common product of low-temperature synthesis pathways and is an important component of nanocrystalline materials developed for gas-phase separation and catalysis (Amores et al., 1995, J. Materials Chem. , 5, pp. 1245-1249). Rutile content in TiO 2 particles was determined from the relative X-ray diffraction intensity corresponding to Anatase ⁇ 101 > and Rutile ⁇ 110 > reflection.
  • the scattered intensity was also varied with the power level and irradiation position of CO 2 laser, which was considerably similar to that of SiO2.
  • a CO 2 laser beam was irradiated at the suitable position where small aggregates existed, scattered intensity become decreased with increasing CO 2 laser power and the particles were also changed from a large aggregate to smaller spherical particles whose average diameters were less than 30 nm.
  • FIG. 11 shows the variation of X-ray diffraction patterns of TiO 2 powders collected at a height of 65mm when the power of the CO 2 laser beam is irradiated at a height of 35mm from the burner end.
  • A denotes anatase
  • R denotes rutile.
  • rutile contents were found to be slightly increased and then decreased with increasing CO 2 laser power. This could be explained by the possibility of melting the TiO 2 nano particles by irradiating CO 2 laser beam on particles generated in a flame.
  • Rutile can not be reversibly transformed to anatase in solid phases and rutile weight fraction was about 13% at 35mm (see Fig. 10). Decrease in the rutile weight fraction below 13 % could be explained only by melting the particles since anatase phase first appeared during recrystallization from liquid phase to solid phase. In FIG. 12, at all CO 2 laser irradiation positions, the similar tendency was found. If the raised temperature of the particles is lower than their melting point, thermodynamically stable phase, that is, rutile weight fraction should be increased due to additionally supplying energy required for the phase transformation into a stable phase by irradiating a laser beam.
  • the laser power is high enough to melt the particles, a metastable phase, anatase phase should be dominant since the metastable phase are favored during recrystallization from liquid phase to solid phase due to the short residence time in a flame.
  • the laser irradiation in a flame in the present invention can be used to control phase of nano crystalline particles.
  • a laser beam is irradiated into particles produced in a flame to facilitate sintering of the produced particles, thereby obtaining spherical nanoparticles at high concentrations , controlling the phase of the particles and improving the quality of the produced particles and the quality of a thin film formed by depositing the produced particles.

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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
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Abstract

L'invention porte sur un procédé de fabrication de particules fines comprenant des poudres métalliques, céramiques, de verre et composées, consistant à placer des réactifs dans le brûleur créant la flamme, à créer des particules à partir des réactifs placés dans la flamme d'un brûleur, puis à projeter un rayon laser sur les particules ainsi produites pour les réchauffer et les fritter.
PCT/KR2000/000049 1999-01-27 2000-01-22 Procede de fabrication et de depot de particules fines par combinaison de flamme et d'un rayon laser Ceased WO2000044679A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE10083901T DE10083901T1 (de) 1999-01-27 2000-01-22 Verfahren zur Herstellung und Ablagerung von Feinpartikeln mit Kombination von Flammen und Laserstrahlen
JP2000595941A JP3790105B2 (ja) 1999-01-27 2000-01-22 炎とレーザーとを用いた微粒子の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1019990002613A KR100308795B1 (ko) 1999-01-27 1999-01-27 화염과 레이저를 이용한 미세입자 제조방법 및 미세입자 증착방법
KR1999/2613 1999-01-27

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Publication Number Publication Date
WO2000044679A1 true WO2000044679A1 (fr) 2000-08-03

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PCT/KR2000/000049 Ceased WO2000044679A1 (fr) 1999-01-27 2000-01-22 Procede de fabrication et de depot de particules fines par combinaison de flamme et d'un rayon laser

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Country Link
JP (1) JP3790105B2 (fr)
KR (1) KR100308795B1 (fr)
DE (1) DE10083901T1 (fr)
WO (1) WO2000044679A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035496A3 (fr) * 2002-07-19 2004-07-22 Ppg Ind Ohio Inc Article a structure nano-proportionnee et procede de fabrication associe
WO2007110482A1 (fr) * 2006-03-27 2007-10-04 Beneq Oy procédé de fabrication de surfaces de verre fonctionnelles en modifiant la composition de la surface d'origine
EP2319955A1 (fr) * 2009-11-10 2011-05-11 Guardian Industries Corp. Brûleur de dépôt de combustion à distance et/ou procédés correspondants
WO2011147866A1 (fr) 2010-05-27 2011-12-01 Heraeus Quarzglas Gmbh & Co. Kg Procédé de production d'une granulation en verre quartzeux
US8440256B2 (en) 2007-12-17 2013-05-14 Guardian Industries Corp. Combustion deposition of metal oxide coatings deposited via infrared burners
US8679580B2 (en) 2003-07-18 2014-03-25 Ppg Industries Ohio, Inc. Nanostructured coatings and related methods

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100330626B1 (ko) * 2000-03-07 2002-03-29 곽영훈 기상화학 반응에 의한 나노사이즈 실리카 초미분체 제조방법
KR100385574B1 (ko) * 2001-02-10 2003-05-27 최만수 쉘 형상의 탄소 미세입자 제조방법
KR20040000830A (ko) * 2002-06-25 2004-01-07 한국지질자원연구원 실란계 화합물로부터 기상 산화 반응에 의한 실리카초미분체 제조방법
KR100989941B1 (ko) 2003-07-16 2010-10-26 주식회사 케이씨씨 실리카 미분체의 제조방법 및 장치
JP7579530B2 (ja) * 2020-08-06 2024-11-08 国立大学法人京都大学 粒体を製造する方法および装置

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JPS55158143A (en) * 1979-05-28 1980-12-09 Nippon Telegr & Teleph Corp <Ntt> Manufacture of optical fiber base material
JPS6311539A (ja) * 1986-06-30 1988-01-19 Sumitomo Electric Ind Ltd 光フアイバ用母材の製造方法
KR950003201A (ko) * 1993-07-22 1995-02-16 쿠라우찌 노리타카 가스생성장치와 이를 이용한 광도파관 및 광파이버모재의 제조방법 및 장치

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55158143A (en) * 1979-05-28 1980-12-09 Nippon Telegr & Teleph Corp <Ntt> Manufacture of optical fiber base material
JPS6311539A (ja) * 1986-06-30 1988-01-19 Sumitomo Electric Ind Ltd 光フアイバ用母材の製造方法
KR950003201A (ko) * 1993-07-22 1995-02-16 쿠라우찌 노리타카 가스생성장치와 이를 이용한 광도파관 및 광파이버모재의 제조방법 및 장치

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035496A3 (fr) * 2002-07-19 2004-07-22 Ppg Ind Ohio Inc Article a structure nano-proportionnee et procede de fabrication associe
CN100335434C (zh) * 2002-07-19 2007-09-05 Ppg工业俄亥俄公司 具有纳米级结构的玻璃制品及其生产方法
US8679580B2 (en) 2003-07-18 2014-03-25 Ppg Industries Ohio, Inc. Nanostructured coatings and related methods
WO2007110482A1 (fr) * 2006-03-27 2007-10-04 Beneq Oy procédé de fabrication de surfaces de verre fonctionnelles en modifiant la composition de la surface d'origine
EA013365B1 (ru) * 2006-03-27 2010-04-30 Бенек Ой Способ получения функциональных стеклянных поверхностей путем изменения композиции исходной поверхности
US8440256B2 (en) 2007-12-17 2013-05-14 Guardian Industries Corp. Combustion deposition of metal oxide coatings deposited via infrared burners
US8563097B2 (en) 2007-12-17 2013-10-22 Guardian Industries Corp. Remote combustion deposition burner and/or related methods
EP2319955A1 (fr) * 2009-11-10 2011-05-11 Guardian Industries Corp. Brûleur de dépôt de combustion à distance et/ou procédés correspondants
WO2011147866A1 (fr) 2010-05-27 2011-12-01 Heraeus Quarzglas Gmbh & Co. Kg Procédé de production d'une granulation en verre quartzeux
DE102010021693A1 (de) * 2010-05-27 2011-12-01 Heraeus Quarzglas Gmbh & Co. Kg Verfahren zur Herstellung von Quarzglaskörnung
DE112011101801B4 (de) * 2010-05-27 2015-06-11 Heraeus Quarzglas Gmbh & Co. Kg Verfahren zur Herstellung von Quarzglaskörnung

Also Published As

Publication number Publication date
JP3790105B2 (ja) 2006-06-28
DE10083901T1 (de) 2002-01-03
KR100308795B1 (ko) 2001-09-26
KR20000051909A (ko) 2000-08-16
JP2002535236A (ja) 2002-10-22

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