WO2005098090A1 - エアロゾルを用いた被膜の製造方法、そのための粒子混合物、ならびに被膜および複合材 - Google Patents
エアロゾルを用いた被膜の製造方法、そのための粒子混合物、ならびに被膜および複合材 Download PDFInfo
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- WO2005098090A1 WO2005098090A1 PCT/JP2005/005009 JP2005005009W WO2005098090A1 WO 2005098090 A1 WO2005098090 A1 WO 2005098090A1 JP 2005005009 W JP2005005009 W JP 2005005009W WO 2005098090 A1 WO2005098090 A1 WO 2005098090A1
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- fine particles
- average particle
- raw material
- particles
- particle size
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Classifications
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the present invention relates to a method for producing a coating such as a ceramic or semiconductor using an aerosol, a particle mixture used in the method, and a coating and a composite obtained by the method.
- an aerosol deposition method a method of forming a film using an aerosol, called an aerosol deposition method.
- an aerosol containing fine particles of a brittle material such as ceramics is formed, and the aerosol is sprayed on the surface of the base material to cause the fine particles to collide with the base material.
- a film is formed on the surface.
- a dense and high-hardness ceramic thick film having a thickness of 110 to several hundreds / zm can be directly formed at room temperature on a substrate surface such as a metal, ceramics, or glass material.
- a conventional film forming method such as a sol-gel method, a CVD method, or a PVD method.
- raw material fine particles used for aerosol fine particles for grinding having an average particle diameter of 0.5 to 5 m and brittle material fine particles having an average particle diameter of lOnm-1 m are used in combination.
- a method of obtaining a dense film at a low temperature is known (see, for example, JP-A-2001-3180).
- the present inventors have recently developed a raw material fine particle having a 50% average particle size (D50) based on a volume of 0.01 to 1.0 m, and a 50% average particle size based on a volume of 3.0 to 100 m.
- the aerosol formed using a particle mixture with auxiliary particles having a particle size (D50) is made to impinge on a substrate and deposited, so that a film with good film quality can be formed at an extremely high film formation rate. Obtained knowledge.
- an object of the present invention is to provide a method for producing a coating film using an aerosol, which can form a coating film having good film quality at an extremely high film forming rate.
- the method for producing a coating film using the aerosol of the present invention comprises:
- a method for producing a coating comprising:
- a raw material fine particle comprising the brittle material as a main component and having a 50% average particle size (D50) on a volume basis of 0.010 to 1.0 m, and a brittleness of the same or different type as the brittle material.
- auxiliary particles having a 50% average particle diameter (D50) based on a volume of 3.0 to 100 m, which is mainly composed of the material.
- the particle mixture of the present invention is a particle mixture used as a coating material in the above method,
- Raw material fine particles comprising a brittle material as a main component and having a 50% average particle size (D50) based on a volume of 0.010 to 1.0 m;
- a film produced by the above method there is provided a film produced by the above method. Further, according to the present invention, there is provided a composite material comprising a base material and a film formed on the base material and manufactured by the above method.
- FIG. 1 is a view showing one example of a film forming apparatus used in the method of the present invention.
- FIG. 2 is a view showing a particle size distribution based on volume of Sample 1 obtained in Example 1.
- FIG. 3 is a diagram showing a particle size distribution based on volume of Sample 2 obtained in Example 1.
- FIG. 4 is a diagram showing a particle size distribution based on volume of Comparative Sample 1 obtained in Example 2.
- FIG. 5 is a view showing a particle size distribution on a volume basis of Comparative Sample 2 obtained in Example 2. Detailed description of the invention
- the “50% average particle size (D50) on a volume basis” refers to the accumulation of fine particles from the small particle size and from the side in the particle size distribution measurement data measured using a laser diffraction type particle size distribution meter. Shows the particle size when the volume reaches 50%.
- 90% average particle size (D90) based on volume refers to the small particle size and the fine particle size from the side in the particle size distribution measurement data measured using a laser diffraction type particle size distribution meter. Shows the particle size when the cumulative volume of particles reaches 90%.
- “10% average particle size (D10) on a number basis” refers to the small particle size and the fine particle from the side in the particle size distribution measurement data measured using a laser diffraction type particle size distribution meter. Shows the particle size when the cumulative number of particles reaches 10%.
- particles means primary particles, and is distinguished from a powder in which primary particles are naturally aggregated.
- the film forming method according to the present invention can be performed according to a method called an aerosol deposition method or an ultra-fine particle beam deposition method. Therefore, the method according to the present invention makes the basic principle substantially the same as, for example, the method described in WO01Z27348, the disclosure of which is part of the disclosure of this specification. In the case where the disclosure of the present invention differs from the disclosure described below, it goes without saying that the following description takes precedence and that the content is the present invention. [0017] In the method of the present invention, first, a particle mixture comprising raw material fine particles and auxiliary particles is prepared.
- Raw material fine particles are relatively small particles that are mainly composed of a brittle material and have a 50% average particle diameter (D50) based on a volume of 0.010 to 1.0 m, and mainly constitute a coating. Particles.
- the auxiliary particles are mainly composed of the same or different brittle material as the brittle material which is the main component of the raw material fine particles, and have a 50% average particle size based on a volume of 3.0 to 100 ⁇ m.
- Relatively large particles having (D50) mainly promoting the formation of a film, and do not necessarily constitute a film.
- an aerosol is formed by mixing a carrier gas with the particle mixture.
- a film is formed using a particle mixture obtained by combining specific particle sizes, whereby a film having a good film quality in terms of hardness and denseness is produced at an extremely high film forming speed. can do.
- a particle size such that the raw material fine particles alone cannot form a film or the film forming speed or film quality may be insufficient. Even so, there is an advantage that the film quality, particularly hardness and denseness, can be improved while significantly increasing the film forming speed.
- the formation of the coating film due to the collision of the particle mixture with the substrate is considered as follows.
- the following description is merely a hypothesis, and the present invention is not limited to this.
- ceramics have a strong covalent bond or ionic bond with few free electrons and are in an atomic bond state, so that they have high hardness but are weak to impact.
- Semiconductors such as silicon and germanium are also brittle materials that do not have ductility. Therefore, when a mechanical impact force is applied to the raw material fine particles containing such a brittle material as a main component, the crystal lattice is displaced or deformed along an open wall such as an interface between the crystallites, or is crushed. Or you can.
- This nascent surface is a surface where atoms that originally existed inside the microparticles and were bonded to other atoms were exposed.
- the layer of one atom of this new surface is exposed from an originally stable atomic bond state to an unstable surface state by an external force, and the surface energy becomes high.
- the active surface is bonded to the surface of the adjacent brittle material or the newly formed surface of the adjacent brittle material or the surface of the substrate, and shifts to a stable state.
- the coating according to the present invention obtained as described above is polycrystalline, and the crystals constituting the coating have substantially no crystal orientation, and At the interface of the members, there is substantially no grain boundary layer that also becomes glassy, and it is preferable that a part of the coating forms an anchor portion that penetrates and penetrates the substrate surface.
- a coating is a dense and high-hardness ceramic thick film, has excellent wear resistance and substrate adhesion, and can have high V and dielectric breakdown voltage.
- the raw material fine particles and the auxiliary particles according to the present invention are mainly composed of a material having a V and a brittleness with a deviation.
- the raw material fine particles and the auxiliary particles may be composed mainly of the same kind of brittle material or may be composed mainly of different kinds of brittle materials.
- the brittle material used in the present invention is not particularly limited as long as it has a property of being deposited as a film on the substrate by being crushed or deformed when colliding with the surface of the substrate as a raw material particulate aerosol. Although various materials can be used, nonmetallic inorganic materials are preferred.
- the pulverization or deformation means that the crystallite size of the coating is smaller than the crystallite size of the raw material fine particles in the crystallite size measured and calculated by the Scherrer method using X-ray diffraction. You can judge.
- the nonmetallic inorganic material is selected from inorganic oxides, inorganic carbides, inorganic nitrides, inorganic borides, multi-component solid solutions thereof, ceramics, and semiconductor materials. It is preferably at least one type.
- inorganic oxides Are aluminum oxide, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, yttrium oxide, chromium oxide, hafnium oxide, beryllium oxide, magnesium oxide, silicon oxide, etc. No.
- Examples of the inorganic carbide include diamond, boron carbide, silicon carbide, titanium carbide, zirconium carbide, vanadium carbide, niobium carbide, chromium carbide, tungsten carbide, molybdenum carbide, tantalum carbide, and the like.
- Examples of the inorganic nitride include boron nitride, titanium nitride, aluminum nitride, silicon nitride, niobium nitride, and tantalum nitride.
- inorganic borides are boron, aluminum boride, silicon boride, titanium boride, zirconium boride, vanadium boride, niobium boride, tantalum boride, chromium boride, molybdenum boride, tungsten boride. And the like.
- ceramics include piezoelectric or pyroelectric ceramics such as barium titanate, lead titanate, lithium titanate, strontium titanate, aluminum titanate, PZT and PLZT; high toughness ceramics such as sialon and cermet; Biocompatible ceramics such as mercury apatite and calcium phosphate are exemplified.
- the semiconductor substance examples include silicon, germanium, or a semiconductor substance obtained by adding various doping substances such as phosphorus to these substances; and semiconductor conjugates such as gallium arsenide, indium arsenide, and cadmium sulfate. Further, according to another preferred embodiment of the present invention, it is possible to use a brittle organic material such as hard vinyl chloride, polycarbonate, and acrylic.
- the raw material fine particles used in the present invention have a 50% average particle size (D50) on a volume basis of 0.010 to 1. O / zm, preferably 0.030 to 0.80 m, more preferably It is preferably 0.10 to 0.50 ⁇ m.
- the auxiliary particles used in the present invention have a 50% average particle size (D50) on a volume basis of 3.0 to 100 ⁇ m, preferably 5.0 to 50 ⁇ m, more preferably 7. 0—20 ⁇ m.
- the 10% average particle diameter (D10) based on the number of the particle mixture is 0.03 to 0.50 m, and the 90% average particle based on the volume of the particle mixture is 90%.
- the diameter (D90) is preferably from 3.00 to 25 m.
- the 10% average particle diameter (D10) based on a more preferable number of the particle mixture is 0.05 to 0.3011, more preferably 0.6 to 0. 90% average particle size based on more preferable volume of particle mixture
- the specific force of the number of raw material fine particles to the number of auxiliary particles in the particle mixture is preferably 1.0 ⁇ 10 2 —1.0 ⁇ 10 7. More preferably, it is 1.0 X 10 3 —1.0 X 10 7 , more preferably 1.0 X 10 4 —1.0 X 10 7 , and most preferably 1.0 X 10 4 ⁇ 1. is a OX 10 6.
- a mixture of fine particles of two or more brittle materials can be used as the raw material fine particles.
- a mixture of fine particles of two or more kinds of brittle materials may be used as auxiliary particles.
- the base material used in the method according to the present invention has an enough degree to give a sufficient mechanical impact force to pulverize or deform the fine particle raw material by spraying the aerosol thereon and colliding with the particle mixture. It is not limited as long as the material has hardness.
- examples of the base material include glass, metal, ceramics, semiconductor, and organic compound, and a composite material thereof may be used.
- a carrier gas is mixed with the particle mixture to form an aerosol.
- the aerosol is obtained by dispersing a particle mixture in a carrier gas, and is preferably in a state in which primary particles are dispersed, but may also include aggregated particles in which the primary particles are aggregated. .
- the formation of an aerosol can be carried out using a commercially available aerosol generator or the like according to a known method.
- the particle mixture of the present invention may be filled in the aerosol generator in advance, or may be mixed with a carrier gas in the middle of a pipe facing the aerosol generator capillary nozzle, or the carrier gas may be mixed with the carrier gas.
- the carrier gas may be mixed between the nozzle and the substrate.
- the carrier gas is not particularly limited as long as it is a carrier gas that is inert to the particle mixture and does not adversely affect the composition of the coating.
- Preferred examples include nitrogen, helium, argon, oxygen, hydrogen, and Dry air, and mixtures thereof.
- the type of carrier gas and Z or the partial pressure are controlled.
- the composition in the coating or to control the position of the atoms. This makes it possible to control the electrical, mechanical, chemical, optical and magnetic properties of the coating.
- the aerosol is sprayed on the surface of the substrate to collide the particle mixture with the substrate, and the collision crushes or deforms the raw material fine particles to form a film on the substrate. Is formed.
- the temperature condition at this time may be determined as appropriate, but it can be performed at a temperature significantly lower than the sintering temperature of ordinary ceramics, for example, 0 to 100 ° C, typically at normal temperature.
- the injection of the aerosol onto the substrate is performed by moving the nozzle, which is preferably performed by injecting the aerosol from the nozzle, relative to the substrate. More preferably, the aerosol is ejected while scanning the nozzle with the nozzle over the substrate.
- the film formation rate at that time is preferably at least 1. O / zm'cmZ, more preferably at least 1.2 / zm'cmZ, still more preferably at least 1.4 / zm'cmZ. , Most preferably 1.6 m 'cmZ or more.
- the jetting speed of the aerosol is preferably in the range of 50 to 450 mZs, more preferably 150 to 400 mZs. Within such a range, a new surface is formed at the time of collision of the fine particles against the base material, and the film forming property is excellent immediately and the film forming speed is increased.
- the thickness of the coating is preferably 0.5 ⁇ m or more, more preferably 11 to 500 m, and still more preferably 3 to 100 m.
- it is possible to form a thick film as compared with other film forming methods such as the PVD method, the CVD method, and the sol-gel method.
- the film is formed under reduced pressure. Thereby, the activity of the new surface formed on the raw material fine particles can be maintained for a certain period of time.
- FIG. 1 shows an example of a film production apparatus for carrying out the method of the present invention.
- a nitrogen gas cylinder 101 is connected to an aerosol generator 103 containing aluminum oxide fine particles through a gas transfer pipe 102 and is installed in a forming chamber 105 through an aerosol transfer pipe 104.
- Nozzle 106 with an opening of 0.4 mm long and 17 mm wide It is connected.
- Various metal substrates 108 placed on an XY stage 107 are arranged at the end of the nozzle 106, and the forming chamber 105 is connected to a vacuum pump 109.
- the nitrogen gas cylinder 101 is opened, and high-purity nitrogen gas is introduced into the aerosol generator 103 through the gas transfer pipe 102 to generate an aerosol in which fine particles of silicon oxide and high-purity nitrogen gas are mixed.
- the aerosol is sent to the nozzle 106 through the aerosol transport pipe 104, and is ejected at a high speed from the opening of the nozzle 106.
- the aerosol sprayed from the nozzle 106 collides with the metal substrate 108 to form a film on this portion.
- the stage 107 is operated to swing the metal base material 108 to form a film on a predetermined area. This film formation can be performed at room temperature.
- raw material fine particles two types of commercially available Sani-Dai aluminum fine particles were prepared.
- the 50% average particle size on a volume basis of these fine particles was measured as follows. First, a small amount of aluminum oxide fine particles was collected, placed in a test tube, and several drops of an aqueous solution of sodium xametaphosphate were added dropwise to 3 ml of ion-exchanged water and 0.2%, followed by sufficient stirring. Next, this mixture is injected into the dispersion bath of a laser diffraction Z-scattering particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.), and irradiated with built-in ultrasonic waves (30 W) for 5 minutes to adjust the optical axis. After that, the measurement was performed. As a result, the 50% average particle size based on the volume of the two types of raw material fine particles was as follows.
- Raw material particles 2 0.60
- auxiliary particles two types of commercially available silicon oxide fine particles were prepared. For these particles, the 50% average particle size on a volume basis was measured in the same manner as described above. As a result, the 50% average particle size by volume of the two types of auxiliary particles was as follows.
- Auxiliary particles 1 5.9 m
- Auxiliary particle 2 11.O ⁇ m
- the raw material fine particles 1 and 2 and the auxiliary particles 1 and 2 were mixed in the following number ratio to obtain a sample 14 as a mixture of four types of particles.
- Example 1 Using Samples 1-4 of the aluminum oxide fine particles obtained in Example 1, a film was produced as follows. The sample obtained in Example 1 was loaded into the aerosol generator 103 of the production apparatus 10 shown in FIG. 1, and aerosol was generated while flowing helium gas as a carrier gas through the apparatus at a flow rate of 7 LZ. (SUS) Spouted on the substrate. Thus, an aluminum oxide film having a formation area of 10 mm ⁇ 17 mm was formed on the substrate.
- SUS 7 LZ.
- the thickness of the prepared aluminum oxide film was measured using a stylus type surface profiler (Dectak3030, manufactured by Nippon Vacuum Engineering Co., Ltd.), and the formation speed of the aluminum oxide film (m'cmZ minute) was measured. Was calculated.
- This film formation speed m'cmZ) means the thickness ( ⁇ m) of a film formed at a scan distance of lcm per minute.
- the Vickers hardness of the produced Sani-Dani aluminum film was measured using a dynamic ultra-micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation). The results of these measurements were as shown in Table 1.
- auxiliary particles 2 used in Example 1 were prepared as comparative samples 2 as auxiliary particles.
- the volume-based particle size distribution, the 10% average particle size (D10) on a number basis, and the 90% average particle size (D90) on a volume basis of Comparative Sample 2 were measured in the same manner as in Example 1.
- Figure 5 shows the particle size distribution of Comparative Sample 2 on a volume basis.
- Example 3 Raw material fine particles Example of using auxiliary particles of different materials (1)
- YO yttrium oxide
- the 50% average particle size on a volume basis of the fine particles is 0.47 m.
- the yttrium oxide coating was prepared and measured in the same manner as in Example 2 using the obtained particle mixture. As a result, a good film could be formed on the substrate.
- Example 4 Raw material fine particles early
- the 50% average particle size based on the volume of the raw material fine particles is 0.32 m.
- auxiliary particles fine particles of aluminum oxide having a 50% average particle size of 3.2 / zm on a volume basis were prepared.
- a forsterite film was prepared and measured in the same manner as in Example 2 using the obtained particle mixture. As a result, a dense film with a volume resistivity of 10 15 ( ⁇ ′ cm) was able to be manufactured at a high film formation rate of 2.0-3.
- Example 5 Raw material fine particles Example using auxiliary particles of different materials (3)
- raw material fine particles commercially available barium titanate (BaTi03) fine particles were prepared.
- the 50% average particle size based on the volume of the raw material particles is 0.13 m.
- auxiliary particles aluminum oxide fine particles having a volume-based 50% average particle size of 55 m were prepared.
- a barium titanate coating was prepared and measured in the same manner as in Example 2 using the obtained particle mixture. As a result, the film formation speed was 22. O / zm'cmZ, and the Vickers hardness of the barium titanate film was HV520, almost the same as that of the sintered body.
- a barium titanate coating film was prepared in the same manner as above using only the barium titanate fine particles.
- the Vickers hardness of the resulting coating was HV300, which was lower than the Vickers hardness HV520 when auxiliary particles (oxidized aluminum fine particles) were used in combination.
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Abstract
Description
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US11/547,515 US20080274347A1 (en) | 2004-03-31 | 2005-03-18 | Method for Producing Film Using Aerosol, Particles Mixture Therefor, and Film and Composite Material |
Applications Claiming Priority (4)
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JP2004107256 | 2004-03-31 | ||
JP2004-107256 | 2004-03-31 | ||
JP2005073351A JP2005314801A (ja) | 2004-03-31 | 2005-03-15 | エアロゾルを用いた被膜の製造方法、そのための粒子混合物、ならびに被膜および複合材 |
JP2005-073351 | 2005-03-15 |
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WO2005098090A1 true WO2005098090A1 (ja) | 2005-10-20 |
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PCT/JP2005/005009 WO2005098090A1 (ja) | 2004-03-31 | 2005-03-18 | エアロゾルを用いた被膜の製造方法、そのための粒子混合物、ならびに被膜および複合材 |
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US (1) | US20080274347A1 (ja) |
JP (1) | JP2005314801A (ja) |
TW (1) | TW200536959A (ja) |
WO (1) | WO2005098090A1 (ja) |
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WO2008068942A1 (ja) * | 2006-12-07 | 2008-06-12 | National Institute For Materials Science | ウォームスプレーコーティング方法とその粒子 |
US8114473B2 (en) | 2007-04-27 | 2012-02-14 | Toto Ltd. | Composite structure and production method thereof |
WO2018217062A1 (ko) * | 2017-05-26 | 2018-11-29 | 아이원스 주식회사 | 플로라이드화 이트륨 옥사이드 코팅막의 형성 방법 및 이에 따른 플로라이드화 이트륨 옥사이드 코팅막 |
KR102062397B1 (ko) * | 2017-05-26 | 2020-01-03 | 아이원스 주식회사 | 플로라이드화 옥사이드 박막의 형성 방법 및 이에 따른 플로라이드화 옥사이드 박막 |
US11424140B2 (en) * | 2019-10-10 | 2022-08-23 | Samsung Electronics Co., Ltd. | Member, method of manufacturing the same, apparatus for manufacturing the same, and semiconductor manufacturing apparatus |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06116743A (ja) * | 1992-10-02 | 1994-04-26 | Vacuum Metallurgical Co Ltd | ガス・デポジション法による微粒子膜の形成法およびその形成装置 |
JP2001003180A (ja) * | 1999-04-23 | 2001-01-09 | Agency Of Ind Science & Technol | 脆性材料超微粒子成形体の低温成形法 |
WO2002036855A1 (fr) * | 2000-10-23 | 2002-05-10 | National Institute Of Advanced Industrial Science And Technology | Structure composite et procede de fabrication |
Family Cites Families (1)
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EP0792854B1 (en) * | 1996-02-28 | 2001-11-21 | Honda Giken Kogyo Kabushiki Kaisha | Silicon nitride sintered body |
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2005
- 2005-03-15 JP JP2005073351A patent/JP2005314801A/ja active Pending
- 2005-03-18 US US11/547,515 patent/US20080274347A1/en not_active Abandoned
- 2005-03-18 WO PCT/JP2005/005009 patent/WO2005098090A1/ja active Application Filing
- 2005-03-29 TW TW094109807A patent/TW200536959A/zh not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06116743A (ja) * | 1992-10-02 | 1994-04-26 | Vacuum Metallurgical Co Ltd | ガス・デポジション法による微粒子膜の形成法およびその形成装置 |
JP2001003180A (ja) * | 1999-04-23 | 2001-01-09 | Agency Of Ind Science & Technol | 脆性材料超微粒子成形体の低温成形法 |
WO2002036855A1 (fr) * | 2000-10-23 | 2002-05-10 | National Institute Of Advanced Industrial Science And Technology | Structure composite et procede de fabrication |
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US20080274347A1 (en) | 2008-11-06 |
JP2005314801A (ja) | 2005-11-10 |
TWI307727B (ja) | 2009-03-21 |
TW200536959A (en) | 2005-11-16 |
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