CA2303515C - Method of forming shaped body of brittle ultra fine particle at low temperature - Google Patents
Method of forming shaped body of brittle ultra fine particle at low temperature Download PDFInfo
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- CA2303515C CA2303515C CA002303515A CA2303515A CA2303515C CA 2303515 C CA2303515 C CA 2303515C CA 002303515 A CA002303515 A CA 002303515A CA 2303515 A CA2303515 A CA 2303515A CA 2303515 C CA2303515 C CA 2303515C
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- brittle
- ultrafine particles
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
Abstract
Disclosed is a method of forming a film or a microstructure having high density and high strength by bonding brittle ultrafine particles without heating them.
The brittle ultrafine particles are blown onto a substrate, and then subjected to a mechanical impact force in order to first break the particles, then bond the ultrafine particles together, thus forming a film or microstructure on the substrate.
The brittle ultrafine particles are blown onto a substrate, and then subjected to a mechanical impact force in order to first break the particles, then bond the ultrafine particles together, thus forming a film or microstructure on the substrate.
Description
METHOD OF FORMING SHAPED BODY OF BRITTLE ULTRAFINE PARTICLE
AT LOW TEMPERATURE
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to techniques of forming a shaped body such as a film or a microstructure on a substrate by applying ultrafine particles of a brittle material such as ceramics to the substrate.
AT LOW TEMPERATURE
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to techniques of forming a shaped body such as a film or a microstructure on a substrate by applying ultrafine particles of a brittle material such as ceramics to the substrate.
2. Description of the Related Art As a technique for forming a film or a microstructure on a substrate by using ultrafine particles of a brittle material such as ceramics, a method of forming a film or a microstructure by mixing brittle ultrafine particles with a carrier gas and blowing the gas toward a substrate via a fine nozzle has been proposed. In order to provide desired physical properties of the film or microstructure, it is essential that ultrafine particles in the film or microstructure have a desired bonding strength.
In practice, however, whether ultrafine particles can be bonded and molded at high density and strength at room temperature without any thermal assistance depends on the physical properties of ultrafine particles to be used, and the reason of this is not still clear. Therefore, in order to obtain sufficient physical properties (mechanical and electrical characteristics and the like) by using a conventional molding (film forming) method, it is usually required to heat a substrate to a temperature of several hundred degrees Celsius or higher and thereafter bake it at a high temperature near the sintering temperature of ceramics (brittle material). In general sintering ?27507-10 techniques for ceramics, it is also essential to bake the ceramic material at a high temperature (at least 900°C or higher) in order to bond ultrafine particles by utilizing thermal diffusion phenomenon such as a solid state reaction and a solid-liquid state reaction.
Since such heat treatment is necessary, it is impossible to apply ceramics directly to a substrate having a low-heat resistance such as a plastic substrate, and also it is necessary to prepare a sintering furnace which makes the manufacturing process complicated. Such heat treatment may also change the microscopic size characteristics or physical properties of a film or microstructure.
A method of forming a film or a microstructure without any heat treatment, which film or microstructure has high density and strength and is made of brittle ultrafine particles bonded at a desired bonding strength, has long been desired.
SUMMARY OF T~iE INVENTION
The invention has been made under such circumstances and aims at providing a method of forming a film or a microstructure without any heat treatment, which film or microstructure has high density and strength and other desired characteristics and is made of brittle ultrafine particles bonded at a desired bonding strength.
In order to achieve the above object, the invention provides a method of forming a brittle ultrafine particle shaped body at a low temperature, wherein a mechanical impact force is applied to the brittle ultrafine particles supplied to a substrate in order to break the particles and bond them together.
>27507-10 BREIF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic diagram showing a structure of an ultrafine particle film forming system.
Fig. 2 is a schematic diagram showing a structure of another ultrafine particle film forming system.
Fig. 3 is a schematic diagram showing a structure of yet another ultrafine particle film forming system.
Fig. 4 is a TEM image showing a cross section of an interface between a film formed at room temperature and a silicon substrate.
Fig. 5 is a TEM image showing a cross section of particles used as a source material and its electron beam diffraction image.
Fig. 6 is a TEM image showing a plan view of a film formed at room temperature and its electron beam diffraction image.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the invention will be described in detail with reference to the accompanying drawings.
Referring to Fig. 1, in a chamber 2 of an ultrafine particle film-forming system la, a substrate 3 and an ultrafine particle supply apparatus 4 are mounted. In this embodiment, a nozzle is used as the ultrafine particle supply apparatus 4. A film is to be formed on this substrate 3. If necessary, a mechanical impact force loading apparatus 5 is disposed along a motion direction of the substrate 3.
,27507-10 The nozzle 4 is used for applying brittle ultrafine particles to the substrate 3 to form an ultrafine particle deposit 11 or an ultrafine particle pressed body 16. The ultrafine particle deposit 11 is a deposit of ultrafine particles on the substrate 3 supplied from the nozzle 4, and not bonded to each other. The ultrafine particle pressed body 16 is a body of ultrafine particles blown from the nozzle 4 and bonded together by a mechanical impact force caused by the blowing force of the nozzle 4.
The substrate 3 is mounted on ~a substrate driver apparatus 6 so that it can be moved in the chamber 2 along a horizontal plane. The nozzle 4 may be made moveable in the chamber 2 relative to the substrate 3.
The mechanical impact force loading apparatus 5 is used for applying a mechanical impact force to the ultrafine particle deposit 11 on the substrate to break the brittle ultrafine particles 7 and form an ultrafine particle film 12.
Next, the operation of forming a film will be described. Ultrafine particles 7 are mixed with a carrier gas in the nozzle 4 and blown onto the substrate 3 while the substrate 3 is moved relative to the nozzle 4 to form the ultrafine particle deposit 11. Alternatively, ultrafine particles 7 are forced to collide with the substrate to break and bond to each other to form the ultrafine particle pressed body 16. If this ultrafine particle pressed body 16 has physical properties sufficient for the target ultrafine particle film 12, this pressed body 16 may be used as the final ultrafine particle film 12 and the film forming process may be terminated. If necessary, a mechanical impact force may be applied to the ultrafine particle pressed body 16 formed on the substrate to further break the ultrafine particles of the pressed body 16 to form an ,27507-10 ultrafine particle film 12 having a greater bonding strength. An ultrafine particle film will not be formed unless a mechanical impact force is applied to the ultrafine particle deposit 11.
The mechanical impact force to be applied to the ultrafine particle deposit 11 or ultrafine particle pressed body 16 in order to break ultrafine particles, may be realized by: accelerating brittle ultrafine particles by applying an electrostatic field or by using a gas carrier to blow them onto a substrate; by using a high rigidity brush or roller rotating at high speed, pressure needles moving up and down, or a piston moving at a high speed ultilizing an explosion compression force; or by using ultrasonic waves.
In this case, the carrier gas may be dry air without using a specific gas such as an inert gas.
It is necessary for the ultrafine particles to be broken easily by the mechanical impact force generated either by the blowing force of the nozzle 4 or by the mechanical impact force loading apparatus 5. To this end, it is essential that the generated mechanical impact force is dominant over a brittle fracture strength of the ultrafine particles.
In order to satisfy this condition, raw materials of ultrafine particles may be pre-processed: to adjust by changing the pre-sintering temperature of the brittle ultrafine particles; to form secondary cohesive particles of about several hundred nanometers in diameter by heating the brittle ultrafine particles of several ten nanometers or smaller in diameter which are formed by chemical methods such as alkoxide colloid pyrolysis, or by physical method such as using vapor deposition and sputtering; or to form particles with cracks by processing them for a long time in ,27507-10 a mill such as a ball mill, a jet mill, a bead mill or a vibration mill. By applying a mechanical impact force to such raw materials of the ultrafine particles, they can be broken down to have a diameter of 100 nm or smaller so that a clean new surface can be formed and low-temperature bonding becomes possible. In this manner, brittle ultrafine particles can be bonded at room temperature and a film having high density and strength can be formed. According to experiments performed by the inventor, it is considered that such breakage of ultrafine particles by the mechanical impact force is not likely to occur if the diameter of each brittle ultrafine particle of raw material is 50 nm or smaller. If the mechanical impact force is generated by the blowing force of the nozzle, this mechanical impact force is not sufficient for impact breakage if the particle diameter is too large. It is therefore preferable that the particle diameter is set in the range of from about 50 nm to 5 ~m for each of the above-described methods of applying the mechanical impact force.
When films were formed by using brittle ultrafine particles of lead zirconate titanate oxide (PZT) or titanium dioxide (TiOz) prepared in the above manner, dense films having a density that is 95% or more of the theoretical density were able to be formed, and the adhesion force to a silicon or stainless substrate was 5o MPa or higher.
A process of forming a brittle ultrafine particle film will be described by using as an example a process of colliding brittle ultrafine particles mixed with a carrier gas with a substrate to break the particles. The ultrafine particles which collide with the substrate first, anchor to the substrate (anchoring effect) to form an underlying layer. In this case, the ultrafine particles may be partially bonded depending upon the combination of the ,27507-10 _7_ materials of the particles and the substrate. However, this partial bonding is not necessarily required but it is sufficient if the underlying layer has such an adhesion force that the layer is not peeled off while brittle ultrafine particles collide with it thereafter. Ultrafine particles colliding with the underlying layer break apart, along with those particles on the surface of the underlying layer. Those broken particles are bonded together at a low temperature to form a strong deposit. In this manner, while the collided brittle ultrafine particles are being deposited over the substrate, breakage and bonding occur simultaneously. The thickness of a film of brittle ultrafine particles to be formed on the substrate is determined based upon whether or not the breakage impact force can be maintained effectively.
The method of applying the mechanical impact force includes, in addition to the method of blowing brittle ultrafine particles from a nozzle toward a substrate, a method of using a brush or roller rotating at high speed, or using pressure needles. In thinly depositing (developing) brittle ultrafine particles on a substrate, they may be pushed against the substrate by using the roller to press them without breakage, without necessarily using the nozzle.
In some case, they may be only gently dropped down and deposited.
As a method of. mechanically breaking brittle ultrafine particles, high intensity ultrasonic waves may be applied in a contact or non-contact manner. In this case, ultrasonic waves strong enough to break the particles are applied to the brittle ultrafine particles that are either thinly deposited on or mechanically pressed against a substrate, in order to break the particles by the impact force induced by the ultrasonic waves. Although ultrasonic ,27507-10 _g_ waves can be aplied in a contact or non-contact manner, sound energy can be transmitted more efficiently if the ultrasound source is made in direct contact with the pressed body or via an impedance matching medium. The ultrasonic wave may be spatially converged by using an ultrasonic lens to focus it to one point, thereby breaking ultrafine particles at this point. In this method, only a particular point of the particle pressed body may be bonded at a low temperature. If an ultrasonic wave is directly applied to a press mold or roller for molding a particle pressed body, the mechanical impact force by ultrasonic waves can be generated by a simple process.
An ultrafine particle film forming system 1b according to another embodiment shown in Fig. 2 has an ultrafine particle supply adjusting blade 17 and a mechanical impact force loading apparatus 5.
The ultrafine particle supply adjusting blade 17 adjusts the supply amount of brittle ultrafine particles 7 to a substrate 3 by scraping and planarizing the surface of an ultrafine particle deposit 11 or an ultrafine particle pressed body 16. The supply amount is controlled by adjusting the height of the blade 17.
The mechanical impact force loading apparatus 5 has, as shown in Fig. 2, an impact force loading roller 13 and a high intensity ultrasonic wave applying apparatus 14.
The impact force loading roller 13 is used for forming an ultafine particle film 12 by directly applying a mechanical impact force to the supply amount adjusted ultafine particle deposit 11 on the substrate 3. The high intensity ultrasonic wave applying apparatus 14 drives the impact force loading roller 13. The impact force loading roller 13 may be any other body so long as it can load the ,27507-10 _g_ mechanical impact force to the ultrafine particle deposit 11 or ultrafine particle pressed body 16. For example, in an ultrafine particle film forming apparatus of another embodiment shown in Fig. 3, a number of impact force loading needles 15 are used. The embodiment of the invention described above may be applied not only to forming a dense film but also to a porous film, by adjusting raw material particles and film forming conditions such as a film forming speed. A porous film is effective for applications requiring a large specific surface area, such as electrodes of a fuel battery and a super capacitor.
(Experimental Examples) (1) Introduction For application of piezoelectric material to a micro actuator or the like, it is important to form a thick film of about 20 ~m and then finely pattern it. Lead zirconate titanate oxide (PZT) of about 0.1 ~m in diameter, typical piezoelectric material, was mixed with a gas to make it aerosol and blow it via a nozzle to a substrate in the form of a high speed jet flow to form a film. This method is more advantageous in that a dense thick film can be formed in a dry process without a binder and fine patterns can be formed easily, as compared to a screen printing method. Unlike general film-forming techniques, it can be considered that the electrical characteristics of a film formed by this method are greatly influenced by the heat treatment conditions and the structure change in ultrafine particles such as PZT particles caused when they collide with a substrate. The microscopic structure of films was investigated in order to clarify the film forming mechanism and improve the film characteristics.
(2) Experimental Method PZT ultrafine particles were ejected from a nozzle having an opening size of 5 mm x 0.3 mm and deposited on a substrate by using an aerosol gas deposition method. The substrate used included a silicon substrate, a SUS 304 substrate, and a Pt/Ti/SiOa/Si substrate. The PZT particles had a composition of Zr/Ti . 52/48, a specific surface area of 2.8 m2/g, and an average particle diameter of 0.3 Vim, and were heated and dried at a low pressure of 10-~ Torr. The l0 carrier gas was helium and dried high purity air, and the particle speed was controlled by the carrier gas flow rate.
The microscopic structure of a PZT film having a thickness of 20 ~.m formed in the above manner was observed as TEM
images and electron beam diffraction images.
(3) Results and Conclusions Fig. 4 is a TEM image showing the cross section of a film formed on an Si substrate at room temperature. There is a damage layer of about 0.15 ~.m at an interface between the Si substrate and a PZT layer, the damage layer being formed through collision of PZT ultrafine particles with the substrate. It can therefore be presumed that a mechanical impact force was generated by the collision of PZT ultrafine particles, the impact force exceeding the plastic flow pressure (Vickers hardness: 5 to 12 GPa) of Si. Since the brittle fracture strength of PZT ultrafine particles is 2.3 to 4 GPa, it can be expected that such a large mechanical impact force sufficiently broke PZT ultrafine particles and generated a new surface.
According to the composition analysis through EDX, thermal diffusion into the Si substrate was hardly recognized. Voids were hardly found in the film and at the ,27507-10 interface, indicating that the dense film was formed at room temperature.
Fig. 5 is a TEM image in cross section of raw material particles, and Fig. 6 is a TEM image in plan view of a film deposited at room temperature on a Pt/Ti/SiOz/Si substrate. Raw material particles were partially cohesive and had inner strain and defects. Particles were almost single crystals as determined from an electron beam diffraction image when considering the particle diameter near that observed by SEM. The crystal grain size was concentrated in a range of about 0.1 to 0.5 Vim. In contrast, an as-deposited film at the room temperature had a polycrystalline structure that there was no significant change in the composition of the film both in the cross sectional direction and in-plane direction, with large crystal particles of about 0.1 to 0.2 ~m approximately of the original size being embedded and surrounded with small crystal particles of about 10 to 40 nm, and also that a number of fine contrasts were observed which might be generated by strain. From these studies, it can be understood that some of PZT ultrafine particles are broken finely and form fine crystals of about several ten microns because of collision with the substrate during the film forming process.
As described above, according to the present invention, a mechanical strength (brittle fracture strength) of brittle ultrafine particles is adjusted in accordance with a mechanical impact force to be applied to the brittle ultrafine particles so that the impact breakage occurs, or the mechanical impact force is applied in accordance with the mechanical strength of the brittle ultrafine particles.
,27507-10 In this manner, a clean new surface is formed and the brittle ultrafine particles are bonded together so that an ultrafine particle film having high density and high strength can be formed at room temperature. The new surface formed through breakage of the brittle ultrafine particles is again bonded in a very short time on site by the pressure applied to the brittle ultrafine particles. Since the time taken to bond the particles again is very short, the film forming atmosphere may be the atmospheric air without using a-specific atmosphere such as an inert gas atmosphere. As the size of the brittle ultrafine particles becomes about several ten manometers, the surface energy increases to enhance bonding, and generation of voids can be prevented which are otherwise formed because of undefined shapes of particles. A dense film or microstructure in the order of several tens manometers in diameter can be obtained.
Since brittle material such as ceramics having a high melting point can be formed on a substrate at room temperature, the surface of a substrate made of a material having a low melting point such as plastics can be coated with ceramics. A vinyl film was attached to a stainless steel substrate, and brittle ultrafine particles of PZT were blown to the surface of the vinyl film. It was possible to form at room temperature a very rigid shaped body having a density of 97% and an adhesion force of at least 15 MPa. It was able to form a ceramic material having a manometer size crystal structure finer than its raw material ultrafine particles, through breakage impact. The density of the shaped body was higher than 95% of the theoretical density.
Therefore, the temperature of heat treatment for grain growth was able to be lowered. For example, in the case of lead zirconate titanate (PZT), the temperature was able to be lowered by about 300°C as compared to a usual sintering . X7507-10 temperature. A lowered grain growth temperature was thus confirmed.
As the brittle ultrafine particles broken into still finer particles having a size under 80 manometer have many fine new surfaces, the surface energy of the brittle ultrafine particles without heating increases to enhance bonding of them.
Therefore it is required that at least a part of brittle ultrafine particles supplied to a substrate to be broken into finer particles having a diameter of 80 manometer or less by applied mechanical impact force in the process of the present invention.
Further, by not applying heat to the shaped ceramic body, such as ceramic film having polycrystal structure with manometer order crystallite size formed by the process of the present invention, the fine crystallites in the body do not grow and are kept in fine broken size;
this brings improved elasticity and strength of the body, along with improved characteristics toughness.
As apparent from the above description of the invention, brittle ultrafine particles such as ceramics are broken into particles of about several ten manometers by applying a mechanical impact force. A clean new surface can be formed on site, and by utilizing this surface, ultrafine particles are bonded together. In this manner, a shaped body such as a film and a microstructure of high density and high strength can be formed without heating.
In practice, however, whether ultrafine particles can be bonded and molded at high density and strength at room temperature without any thermal assistance depends on the physical properties of ultrafine particles to be used, and the reason of this is not still clear. Therefore, in order to obtain sufficient physical properties (mechanical and electrical characteristics and the like) by using a conventional molding (film forming) method, it is usually required to heat a substrate to a temperature of several hundred degrees Celsius or higher and thereafter bake it at a high temperature near the sintering temperature of ceramics (brittle material). In general sintering ?27507-10 techniques for ceramics, it is also essential to bake the ceramic material at a high temperature (at least 900°C or higher) in order to bond ultrafine particles by utilizing thermal diffusion phenomenon such as a solid state reaction and a solid-liquid state reaction.
Since such heat treatment is necessary, it is impossible to apply ceramics directly to a substrate having a low-heat resistance such as a plastic substrate, and also it is necessary to prepare a sintering furnace which makes the manufacturing process complicated. Such heat treatment may also change the microscopic size characteristics or physical properties of a film or microstructure.
A method of forming a film or a microstructure without any heat treatment, which film or microstructure has high density and strength and is made of brittle ultrafine particles bonded at a desired bonding strength, has long been desired.
SUMMARY OF T~iE INVENTION
The invention has been made under such circumstances and aims at providing a method of forming a film or a microstructure without any heat treatment, which film or microstructure has high density and strength and other desired characteristics and is made of brittle ultrafine particles bonded at a desired bonding strength.
In order to achieve the above object, the invention provides a method of forming a brittle ultrafine particle shaped body at a low temperature, wherein a mechanical impact force is applied to the brittle ultrafine particles supplied to a substrate in order to break the particles and bond them together.
>27507-10 BREIF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic diagram showing a structure of an ultrafine particle film forming system.
Fig. 2 is a schematic diagram showing a structure of another ultrafine particle film forming system.
Fig. 3 is a schematic diagram showing a structure of yet another ultrafine particle film forming system.
Fig. 4 is a TEM image showing a cross section of an interface between a film formed at room temperature and a silicon substrate.
Fig. 5 is a TEM image showing a cross section of particles used as a source material and its electron beam diffraction image.
Fig. 6 is a TEM image showing a plan view of a film formed at room temperature and its electron beam diffraction image.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the invention will be described in detail with reference to the accompanying drawings.
Referring to Fig. 1, in a chamber 2 of an ultrafine particle film-forming system la, a substrate 3 and an ultrafine particle supply apparatus 4 are mounted. In this embodiment, a nozzle is used as the ultrafine particle supply apparatus 4. A film is to be formed on this substrate 3. If necessary, a mechanical impact force loading apparatus 5 is disposed along a motion direction of the substrate 3.
,27507-10 The nozzle 4 is used for applying brittle ultrafine particles to the substrate 3 to form an ultrafine particle deposit 11 or an ultrafine particle pressed body 16. The ultrafine particle deposit 11 is a deposit of ultrafine particles on the substrate 3 supplied from the nozzle 4, and not bonded to each other. The ultrafine particle pressed body 16 is a body of ultrafine particles blown from the nozzle 4 and bonded together by a mechanical impact force caused by the blowing force of the nozzle 4.
The substrate 3 is mounted on ~a substrate driver apparatus 6 so that it can be moved in the chamber 2 along a horizontal plane. The nozzle 4 may be made moveable in the chamber 2 relative to the substrate 3.
The mechanical impact force loading apparatus 5 is used for applying a mechanical impact force to the ultrafine particle deposit 11 on the substrate to break the brittle ultrafine particles 7 and form an ultrafine particle film 12.
Next, the operation of forming a film will be described. Ultrafine particles 7 are mixed with a carrier gas in the nozzle 4 and blown onto the substrate 3 while the substrate 3 is moved relative to the nozzle 4 to form the ultrafine particle deposit 11. Alternatively, ultrafine particles 7 are forced to collide with the substrate to break and bond to each other to form the ultrafine particle pressed body 16. If this ultrafine particle pressed body 16 has physical properties sufficient for the target ultrafine particle film 12, this pressed body 16 may be used as the final ultrafine particle film 12 and the film forming process may be terminated. If necessary, a mechanical impact force may be applied to the ultrafine particle pressed body 16 formed on the substrate to further break the ultrafine particles of the pressed body 16 to form an ,27507-10 ultrafine particle film 12 having a greater bonding strength. An ultrafine particle film will not be formed unless a mechanical impact force is applied to the ultrafine particle deposit 11.
The mechanical impact force to be applied to the ultrafine particle deposit 11 or ultrafine particle pressed body 16 in order to break ultrafine particles, may be realized by: accelerating brittle ultrafine particles by applying an electrostatic field or by using a gas carrier to blow them onto a substrate; by using a high rigidity brush or roller rotating at high speed, pressure needles moving up and down, or a piston moving at a high speed ultilizing an explosion compression force; or by using ultrasonic waves.
In this case, the carrier gas may be dry air without using a specific gas such as an inert gas.
It is necessary for the ultrafine particles to be broken easily by the mechanical impact force generated either by the blowing force of the nozzle 4 or by the mechanical impact force loading apparatus 5. To this end, it is essential that the generated mechanical impact force is dominant over a brittle fracture strength of the ultrafine particles.
In order to satisfy this condition, raw materials of ultrafine particles may be pre-processed: to adjust by changing the pre-sintering temperature of the brittle ultrafine particles; to form secondary cohesive particles of about several hundred nanometers in diameter by heating the brittle ultrafine particles of several ten nanometers or smaller in diameter which are formed by chemical methods such as alkoxide colloid pyrolysis, or by physical method such as using vapor deposition and sputtering; or to form particles with cracks by processing them for a long time in ,27507-10 a mill such as a ball mill, a jet mill, a bead mill or a vibration mill. By applying a mechanical impact force to such raw materials of the ultrafine particles, they can be broken down to have a diameter of 100 nm or smaller so that a clean new surface can be formed and low-temperature bonding becomes possible. In this manner, brittle ultrafine particles can be bonded at room temperature and a film having high density and strength can be formed. According to experiments performed by the inventor, it is considered that such breakage of ultrafine particles by the mechanical impact force is not likely to occur if the diameter of each brittle ultrafine particle of raw material is 50 nm or smaller. If the mechanical impact force is generated by the blowing force of the nozzle, this mechanical impact force is not sufficient for impact breakage if the particle diameter is too large. It is therefore preferable that the particle diameter is set in the range of from about 50 nm to 5 ~m for each of the above-described methods of applying the mechanical impact force.
When films were formed by using brittle ultrafine particles of lead zirconate titanate oxide (PZT) or titanium dioxide (TiOz) prepared in the above manner, dense films having a density that is 95% or more of the theoretical density were able to be formed, and the adhesion force to a silicon or stainless substrate was 5o MPa or higher.
A process of forming a brittle ultrafine particle film will be described by using as an example a process of colliding brittle ultrafine particles mixed with a carrier gas with a substrate to break the particles. The ultrafine particles which collide with the substrate first, anchor to the substrate (anchoring effect) to form an underlying layer. In this case, the ultrafine particles may be partially bonded depending upon the combination of the ,27507-10 _7_ materials of the particles and the substrate. However, this partial bonding is not necessarily required but it is sufficient if the underlying layer has such an adhesion force that the layer is not peeled off while brittle ultrafine particles collide with it thereafter. Ultrafine particles colliding with the underlying layer break apart, along with those particles on the surface of the underlying layer. Those broken particles are bonded together at a low temperature to form a strong deposit. In this manner, while the collided brittle ultrafine particles are being deposited over the substrate, breakage and bonding occur simultaneously. The thickness of a film of brittle ultrafine particles to be formed on the substrate is determined based upon whether or not the breakage impact force can be maintained effectively.
The method of applying the mechanical impact force includes, in addition to the method of blowing brittle ultrafine particles from a nozzle toward a substrate, a method of using a brush or roller rotating at high speed, or using pressure needles. In thinly depositing (developing) brittle ultrafine particles on a substrate, they may be pushed against the substrate by using the roller to press them without breakage, without necessarily using the nozzle.
In some case, they may be only gently dropped down and deposited.
As a method of. mechanically breaking brittle ultrafine particles, high intensity ultrasonic waves may be applied in a contact or non-contact manner. In this case, ultrasonic waves strong enough to break the particles are applied to the brittle ultrafine particles that are either thinly deposited on or mechanically pressed against a substrate, in order to break the particles by the impact force induced by the ultrasonic waves. Although ultrasonic ,27507-10 _g_ waves can be aplied in a contact or non-contact manner, sound energy can be transmitted more efficiently if the ultrasound source is made in direct contact with the pressed body or via an impedance matching medium. The ultrasonic wave may be spatially converged by using an ultrasonic lens to focus it to one point, thereby breaking ultrafine particles at this point. In this method, only a particular point of the particle pressed body may be bonded at a low temperature. If an ultrasonic wave is directly applied to a press mold or roller for molding a particle pressed body, the mechanical impact force by ultrasonic waves can be generated by a simple process.
An ultrafine particle film forming system 1b according to another embodiment shown in Fig. 2 has an ultrafine particle supply adjusting blade 17 and a mechanical impact force loading apparatus 5.
The ultrafine particle supply adjusting blade 17 adjusts the supply amount of brittle ultrafine particles 7 to a substrate 3 by scraping and planarizing the surface of an ultrafine particle deposit 11 or an ultrafine particle pressed body 16. The supply amount is controlled by adjusting the height of the blade 17.
The mechanical impact force loading apparatus 5 has, as shown in Fig. 2, an impact force loading roller 13 and a high intensity ultrasonic wave applying apparatus 14.
The impact force loading roller 13 is used for forming an ultafine particle film 12 by directly applying a mechanical impact force to the supply amount adjusted ultafine particle deposit 11 on the substrate 3. The high intensity ultrasonic wave applying apparatus 14 drives the impact force loading roller 13. The impact force loading roller 13 may be any other body so long as it can load the ,27507-10 _g_ mechanical impact force to the ultrafine particle deposit 11 or ultrafine particle pressed body 16. For example, in an ultrafine particle film forming apparatus of another embodiment shown in Fig. 3, a number of impact force loading needles 15 are used. The embodiment of the invention described above may be applied not only to forming a dense film but also to a porous film, by adjusting raw material particles and film forming conditions such as a film forming speed. A porous film is effective for applications requiring a large specific surface area, such as electrodes of a fuel battery and a super capacitor.
(Experimental Examples) (1) Introduction For application of piezoelectric material to a micro actuator or the like, it is important to form a thick film of about 20 ~m and then finely pattern it. Lead zirconate titanate oxide (PZT) of about 0.1 ~m in diameter, typical piezoelectric material, was mixed with a gas to make it aerosol and blow it via a nozzle to a substrate in the form of a high speed jet flow to form a film. This method is more advantageous in that a dense thick film can be formed in a dry process without a binder and fine patterns can be formed easily, as compared to a screen printing method. Unlike general film-forming techniques, it can be considered that the electrical characteristics of a film formed by this method are greatly influenced by the heat treatment conditions and the structure change in ultrafine particles such as PZT particles caused when they collide with a substrate. The microscopic structure of films was investigated in order to clarify the film forming mechanism and improve the film characteristics.
(2) Experimental Method PZT ultrafine particles were ejected from a nozzle having an opening size of 5 mm x 0.3 mm and deposited on a substrate by using an aerosol gas deposition method. The substrate used included a silicon substrate, a SUS 304 substrate, and a Pt/Ti/SiOa/Si substrate. The PZT particles had a composition of Zr/Ti . 52/48, a specific surface area of 2.8 m2/g, and an average particle diameter of 0.3 Vim, and were heated and dried at a low pressure of 10-~ Torr. The l0 carrier gas was helium and dried high purity air, and the particle speed was controlled by the carrier gas flow rate.
The microscopic structure of a PZT film having a thickness of 20 ~.m formed in the above manner was observed as TEM
images and electron beam diffraction images.
(3) Results and Conclusions Fig. 4 is a TEM image showing the cross section of a film formed on an Si substrate at room temperature. There is a damage layer of about 0.15 ~.m at an interface between the Si substrate and a PZT layer, the damage layer being formed through collision of PZT ultrafine particles with the substrate. It can therefore be presumed that a mechanical impact force was generated by the collision of PZT ultrafine particles, the impact force exceeding the plastic flow pressure (Vickers hardness: 5 to 12 GPa) of Si. Since the brittle fracture strength of PZT ultrafine particles is 2.3 to 4 GPa, it can be expected that such a large mechanical impact force sufficiently broke PZT ultrafine particles and generated a new surface.
According to the composition analysis through EDX, thermal diffusion into the Si substrate was hardly recognized. Voids were hardly found in the film and at the ,27507-10 interface, indicating that the dense film was formed at room temperature.
Fig. 5 is a TEM image in cross section of raw material particles, and Fig. 6 is a TEM image in plan view of a film deposited at room temperature on a Pt/Ti/SiOz/Si substrate. Raw material particles were partially cohesive and had inner strain and defects. Particles were almost single crystals as determined from an electron beam diffraction image when considering the particle diameter near that observed by SEM. The crystal grain size was concentrated in a range of about 0.1 to 0.5 Vim. In contrast, an as-deposited film at the room temperature had a polycrystalline structure that there was no significant change in the composition of the film both in the cross sectional direction and in-plane direction, with large crystal particles of about 0.1 to 0.2 ~m approximately of the original size being embedded and surrounded with small crystal particles of about 10 to 40 nm, and also that a number of fine contrasts were observed which might be generated by strain. From these studies, it can be understood that some of PZT ultrafine particles are broken finely and form fine crystals of about several ten microns because of collision with the substrate during the film forming process.
As described above, according to the present invention, a mechanical strength (brittle fracture strength) of brittle ultrafine particles is adjusted in accordance with a mechanical impact force to be applied to the brittle ultrafine particles so that the impact breakage occurs, or the mechanical impact force is applied in accordance with the mechanical strength of the brittle ultrafine particles.
,27507-10 In this manner, a clean new surface is formed and the brittle ultrafine particles are bonded together so that an ultrafine particle film having high density and high strength can be formed at room temperature. The new surface formed through breakage of the brittle ultrafine particles is again bonded in a very short time on site by the pressure applied to the brittle ultrafine particles. Since the time taken to bond the particles again is very short, the film forming atmosphere may be the atmospheric air without using a-specific atmosphere such as an inert gas atmosphere. As the size of the brittle ultrafine particles becomes about several ten manometers, the surface energy increases to enhance bonding, and generation of voids can be prevented which are otherwise formed because of undefined shapes of particles. A dense film or microstructure in the order of several tens manometers in diameter can be obtained.
Since brittle material such as ceramics having a high melting point can be formed on a substrate at room temperature, the surface of a substrate made of a material having a low melting point such as plastics can be coated with ceramics. A vinyl film was attached to a stainless steel substrate, and brittle ultrafine particles of PZT were blown to the surface of the vinyl film. It was possible to form at room temperature a very rigid shaped body having a density of 97% and an adhesion force of at least 15 MPa. It was able to form a ceramic material having a manometer size crystal structure finer than its raw material ultrafine particles, through breakage impact. The density of the shaped body was higher than 95% of the theoretical density.
Therefore, the temperature of heat treatment for grain growth was able to be lowered. For example, in the case of lead zirconate titanate (PZT), the temperature was able to be lowered by about 300°C as compared to a usual sintering . X7507-10 temperature. A lowered grain growth temperature was thus confirmed.
As the brittle ultrafine particles broken into still finer particles having a size under 80 manometer have many fine new surfaces, the surface energy of the brittle ultrafine particles without heating increases to enhance bonding of them.
Therefore it is required that at least a part of brittle ultrafine particles supplied to a substrate to be broken into finer particles having a diameter of 80 manometer or less by applied mechanical impact force in the process of the present invention.
Further, by not applying heat to the shaped ceramic body, such as ceramic film having polycrystal structure with manometer order crystallite size formed by the process of the present invention, the fine crystallites in the body do not grow and are kept in fine broken size;
this brings improved elasticity and strength of the body, along with improved characteristics toughness.
As apparent from the above description of the invention, brittle ultrafine particles such as ceramics are broken into particles of about several ten manometers by applying a mechanical impact force. A clean new surface can be formed on site, and by utilizing this surface, ultrafine particles are bonded together. In this manner, a shaped body such as a film and a microstructure of high density and high strength can be formed without heating.
Claims (13)
1. A method of forming a shaped body of brittle ultrafine particles without heating, which method comprises:
applying a mechanical impact force to raw brittle ultrafine particles supplied onto a surface of a substrate, (i) to break the raw brittle ultrafine particles, thereby forming broken brittle ultrafine particles finer than the raw brittle ultrafine particles and having clean new surfaces and immediately thereafter bond together the clean new surfaces of the broken brittle ultrafine particles without heating, or (ii) to break the brittle ultrafine particles, thereby forming broken brittle ultrafine particles finer than the raw brittle ultrafine particles and having clean new surfaces and immediately thereafter bond the clean new surfaces of the broken brittle ultrafine particles together as well as to the substrate without heating, thereby forming the shaped body of the brittle ultrafine particles on the surface of the substrate, wherein:
the raw brittle ultrafine particles have a particle diameter of 50 nm to 5 µm and a brittle fracture strength weaker than the applied mechanical impact force;
the broken brittle ultrafine particles have a diameter of 100 nm or less; and the formed shaped body of the brittle ultrafine particles has a density that is 95% or more of its theoretical density.
applying a mechanical impact force to raw brittle ultrafine particles supplied onto a surface of a substrate, (i) to break the raw brittle ultrafine particles, thereby forming broken brittle ultrafine particles finer than the raw brittle ultrafine particles and having clean new surfaces and immediately thereafter bond together the clean new surfaces of the broken brittle ultrafine particles without heating, or (ii) to break the brittle ultrafine particles, thereby forming broken brittle ultrafine particles finer than the raw brittle ultrafine particles and having clean new surfaces and immediately thereafter bond the clean new surfaces of the broken brittle ultrafine particles together as well as to the substrate without heating, thereby forming the shaped body of the brittle ultrafine particles on the surface of the substrate, wherein:
the raw brittle ultrafine particles have a particle diameter of 50 nm to 5 µm and a brittle fracture strength weaker than the applied mechanical impact force;
the broken brittle ultrafine particles have a diameter of 100 nm or less; and the formed shaped body of the brittle ultrafine particles has a density that is 95% or more of its theoretical density.
2. The method according to claim 1, wherein the mechanical impact force is applied by:
high-speed collision of the brittle ultrafine particles with the substrate by application of an electrostatic field or use of a jet of a carrier gas;
pressing the brittle fine particles by using a rotating high rigidity brush or roller, pressure needles moving up and down, or a piston moving by utilizing an explosion compression force; or ultrasonic waves.
high-speed collision of the brittle ultrafine particles with the substrate by application of an electrostatic field or use of a jet of a carrier gas;
pressing the brittle fine particles by using a rotating high rigidity brush or roller, pressure needles moving up and down, or a piston moving by utilizing an explosion compression force; or ultrasonic waves.
3. The method according to claim 1 or 2, wherein the brittle ultrafine particles have been pre-processed so that the mechanical impact force becomes dominant over a brittle fracture strength of the ultrafine particles.
4. The method according to claim 3, wherein the pre-processing is conducted by:
adjusting a pre-sintering temperature of the brittle ultrafine particles;
formation of secondary cohesive particles of from 50 µm to 5µm in diameter by heating the brittle ultrafine particles; or formation of cracks in the brittle ultrafine particles by processing the particles by the use of a milling method selected from the group consisting of a ball mill, a jet mill, a bead mill and a vibration mill.
adjusting a pre-sintering temperature of the brittle ultrafine particles;
formation of secondary cohesive particles of from 50 µm to 5µm in diameter by heating the brittle ultrafine particles; or formation of cracks in the brittle ultrafine particles by processing the particles by the use of a milling method selected from the group consisting of a ball mill, a jet mill, a bead mill and a vibration mill.
5. The method according to any one of claims 1 to 4, wherein the applied mechanical impact force breaks down a portion of the ultrafine particles supplied to the substrate into particles with a diameter of 80 nm or less.
6. A method of forming a film of brittle ultrafine particles of a ceramic material onto a surface of a substrate, at least the surface of the substrate being made of a material selected from the group consisting of plastic, silicon, stainless steel and Pt/Ti/SiO2/Si, which method comprises:
applying a mechanical impact force to raw brittle ultrafine particles supplied onto the surface of the substrate to break the raw brittle ultrafine particles, forming smaller particles having clean and active new surfaces and to immediately thereafter bond the clean new surfaces of the smaller particles together as well as to the substrate, without heating, thereby forming the film, wherein the raw brittle ultrafine particles have a diameter of 50 nm to 5µm and a brittle fracture strength lower than the mechanical impact force and a plastic flow pressure of the material of the substrate surface;
wherein the smaller particles formed by breaking the raw brittle ultrafine particles have a diameter of 100 nm or less;
wherein the mechanical impact force is applied by at least one of:
(i) blowing the raw brittle ultrafine particles with a carrier gas onto the substrate surface;
(ii) pressing the raw brittle ultrafine particles onto the substrate surface by a rotating rigid brush or roller, pressure needles moving up and down or a piston moving by an explosion compression force; and (iii) ultrasonic waves; and wherein the formed film of the brittle ultrafine particles has a density that is at least 95% of a theoretical density of the ceramic material.
applying a mechanical impact force to raw brittle ultrafine particles supplied onto the surface of the substrate to break the raw brittle ultrafine particles, forming smaller particles having clean and active new surfaces and to immediately thereafter bond the clean new surfaces of the smaller particles together as well as to the substrate, without heating, thereby forming the film, wherein the raw brittle ultrafine particles have a diameter of 50 nm to 5µm and a brittle fracture strength lower than the mechanical impact force and a plastic flow pressure of the material of the substrate surface;
wherein the smaller particles formed by breaking the raw brittle ultrafine particles have a diameter of 100 nm or less;
wherein the mechanical impact force is applied by at least one of:
(i) blowing the raw brittle ultrafine particles with a carrier gas onto the substrate surface;
(ii) pressing the raw brittle ultrafine particles onto the substrate surface by a rotating rigid brush or roller, pressure needles moving up and down or a piston moving by an explosion compression force; and (iii) ultrasonic waves; and wherein the formed film of the brittle ultrafine particles has a density that is at least 95% of a theoretical density of the ceramic material.
7. The method according to claim 6, wherein the ceramic material is a member selected from the group consisting of lead zirconate titanate oxide (PZT) and titanium dioxide.
8. The method according to claim 6, wherein the ceramic material is lead zirconate titanate oxide (PZT).
9. The method according to any one of claims 6 to 8, wherein the raw brittle ultrafine particles have been pre-processed so that. they have a brittle fracture strength lower than the applied mechanical impact force, the pre-processing being conducted by:
(a) changing a pre-sintering temperature of the brittle ultrafine particles to adjust the brittle fracture strength;
(b) forming secondary cohesive particles of the brittle ultrafine particles which are formed by a chemical or physical method; or (c) forming cracks in the brittle ultrafine particles by processing the particles in a mill.
(a) changing a pre-sintering temperature of the brittle ultrafine particles to adjust the brittle fracture strength;
(b) forming secondary cohesive particles of the brittle ultrafine particles which are formed by a chemical or physical method; or (c) forming cracks in the brittle ultrafine particles by processing the particles in a mill.
10. The method according to any one of claims 6 to 9, wherein the mechanical impact force is applied to the raw brittle ultrafine particles by blowing the brittle ultrafine particles with a carrier gas against the substrate surface.
11. The method according to any one of claims 6 to 9, wherein the mechanical impact force is applied to the raw brittle ultrafine particles by pressing the brittle ultrafine particles laid on the substrate against the substrate by a rotating rigid brush or roller, by pressure needles moving up and down or by a piston moving by an explosion compression force.
12. The method according to any one of claims 6 to 9, wherein the mechanical impact force is applied to the raw brittle ultrafine particles by ultrasonic waves.
13. The method according to any one of claims 6 to 12, wherein the applied mechanical impact force is enough to break the raw brittle ultrafine particles into still finer particles, at least a part thereof having a diameter of 80 nm or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11732899 | 1999-04-23 | ||
| JP117328/1999 | 1999-04-23 |
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| CA2303515A1 CA2303515A1 (en) | 2000-10-23 |
| CA2303515C true CA2303515C (en) | 2005-05-17 |
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| CA002303515A Expired - Lifetime CA2303515C (en) | 1999-04-23 | 2000-03-30 | Method of forming shaped body of brittle ultra fine particle at low temperature |
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| US (1) | US6531187B2 (en) |
| EP (1) | EP1046484B1 (en) |
| AU (1) | AU740235B2 (en) |
| CA (1) | CA2303515C (en) |
| DE (1) | DE60044412D1 (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6827634B2 (en) * | 2000-05-22 | 2004-12-07 | Agency Of Industrial Science And Technology | Ultra fine particle film forming method and apparatus |
| CN100465340C (en) * | 1999-10-12 | 2009-03-04 | Toto株式会社 | Method and apparatus for manufacturing composite structure |
| US7346184B1 (en) | 2000-05-02 | 2008-03-18 | Digimarc Corporation | Processing methods combining multiple frames of image data |
| EP1280193B1 (en) * | 2000-05-02 | 2011-06-29 | JGC Catalysts and Chemicals Ltd. | Method of manufacturing integrated circuit, and substrate with integrated circuit formed by the method of manufacturing integrated circuit |
| US8986829B2 (en) * | 2000-05-22 | 2015-03-24 | National Institute Of Advanced Industrial Science And Technology | Layered body |
| EP1333935A4 (en) * | 2000-10-17 | 2008-04-02 | Nanogram Corp | Coating formation by reactive deposition |
| US7255934B2 (en) * | 2000-10-23 | 2007-08-14 | National Institute Of Advanced Industrial Science And Technology | Composite structure body and method and apparatus for manufacturing thereof |
| TWI334408B (en) * | 2002-05-28 | 2010-12-11 | Nat Inst Of Advanced Ind Scien | Brittle material formed of ultrafine particles |
| US7565723B2 (en) * | 2004-03-30 | 2009-07-28 | Brother Kogyo Kabushik Kaisha | Piezoelectric actuator and method of fabricating piezoelectric actuator |
| JP4849432B2 (en) * | 2004-03-30 | 2012-01-11 | ブラザー工業株式会社 | Piezoelectric film manufacturing method, laminated structure of substrate and piezoelectric film, piezoelectric actuator, and manufacturing method thereof |
| US20060255692A1 (en) * | 2005-03-22 | 2006-11-16 | Motohiro Yasui | Piezoelectric Actuator, Ink-Jet Head, Method Of Producing Piezoelectric Actuator, And Method Of Producing Ink-Jet Head |
| JP4675821B2 (en) * | 2006-04-28 | 2011-04-27 | 株式会社豊田中央研究所 | Brazing method |
| WO2008068942A1 (en) * | 2006-12-07 | 2008-06-12 | National Institute For Materials Science | Method of warm spray coating and particle therefor |
| JP5057457B2 (en) * | 2007-01-05 | 2012-10-24 | 独立行政法人産業技術総合研究所 | Magneto-optical material and manufacturing method thereof |
| US8114473B2 (en) * | 2007-04-27 | 2012-02-14 | Toto Ltd. | Composite structure and production method thereof |
| US8544408B2 (en) * | 2011-03-23 | 2013-10-01 | Kevin Wayne Ewers | System for applying metal particulate with hot pressurized air using a venturi chamber and a helical channel |
| WO2012161161A1 (en) * | 2011-05-20 | 2012-11-29 | 独立行政法人産業技術総合研究所 | Film forming method, body having film formed thereon, and dye-sensitized solar cell |
| FR2983217B1 (en) | 2011-11-25 | 2015-05-01 | Centre De Transfert De Tech Ceramiques C T T C | METHOD AND DEVICE FOR FORMING A DEPOSITION OF FRAGILE (X) MATERIAL (S) ON A POWDER PROJECTION SUBSTRATE |
| JP6134106B2 (en) * | 2012-08-20 | 2017-05-24 | 積水化学工業株式会社 | Method for producing porous membrane |
| JP6255222B2 (en) | 2013-11-27 | 2017-12-27 | 日東電工株式会社 | Metal oxide-polymer laminate and method for producing the same |
| CN104190584B (en) * | 2014-09-19 | 2016-06-22 | 苏州承源光电科技有限公司 | A kind of LED lamp heat sink is with being coated with heat-conducting silicone grease device |
| WO2016187510A1 (en) | 2015-05-20 | 2016-11-24 | Sion Power Corporation | Protective layers for electrodes |
| RU171295U1 (en) * | 2016-02-01 | 2017-05-29 | Федеральное государственное казенное военное образовательное учреждение высшего образования "ВОЕННАЯ АКАДЕМИЯ МАТЕРИАЛЬНО-ТЕХНИЧЕСКОГО ОБЕСПЕЧЕНИЯ имени генерала армии А.В. Хрулева" | DEVICE FOR ULTRASONIC COATING BASED ON MINERAL MATERIALS |
| US11225436B2 (en) | 2016-05-16 | 2022-01-18 | National Institute Of Advanced Industrial Science And Technology | Multilayer structure and method for producing same |
| WO2017201376A1 (en) | 2016-05-20 | 2017-11-23 | Sion Power Corporation | Protective layers for electrodes and electrochemical cells |
| US10792703B2 (en) | 2017-11-21 | 2020-10-06 | New Mexico Tech University Research Park Corporation | Aerosol method for coating |
| CN109129854A (en) * | 2018-09-13 | 2019-01-04 | 肇庆乐华陶瓷洁具有限公司 | A kind of ceramic tile glaze automatic filling system |
| CN112570085A (en) * | 2020-11-24 | 2021-03-30 | 安徽桑瑞斯环保新材料有限公司 | Reducing mechanism is used in powder coating production |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3100724A (en) * | 1958-09-22 | 1963-08-13 | Microseal Products Inc | Device for treating the surface of a workpiece |
| US4172558A (en) * | 1977-04-19 | 1979-10-30 | Bondarenko Alexandr S | Apparatus for explosive application of coatings |
| US4801411A (en) * | 1986-06-05 | 1989-01-31 | Southwest Research Institute | Method and apparatus for producing monosize ceramic particles |
| JPH02133377A (en) * | 1988-11-14 | 1990-05-22 | Isuzu Ceramics Kenkyusho:Kk | Impact sintering and automobile part production device using it |
| KR920004025B1 (en) * | 1988-12-28 | 1992-05-22 | 마쯔시다덴기산교 가부시기가이샤 | Ferrite magnets and making method thereof |
| JP2890599B2 (en) * | 1990-02-06 | 1999-05-17 | ソニー株式会社 | Processing method |
| WO1994025641A1 (en) * | 1993-04-26 | 1994-11-10 | Roger John Wedlake | Forming a hard layer on a substrate |
| US5795626A (en) * | 1995-04-28 | 1998-08-18 | Innovative Technology Inc. | Coating or ablation applicator with a debris recovery attachment |
| EP0860516A3 (en) * | 1997-02-04 | 1999-05-19 | Fuji Kihan Co., Ltd. | Method for forming metallic coat |
| JPH11152582A (en) * | 1997-11-14 | 1999-06-08 | Vacuum Metallurgical Co Ltd | Gas deposition method and device therefor |
| CN100465340C (en) * | 1999-10-12 | 2009-03-04 | Toto株式会社 | Method and apparatus for manufacturing composite structure |
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- 2000-03-29 US US09/538,332 patent/US6531187B2/en not_active Expired - Lifetime
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| EP1046484A3 (en) | 2003-01-02 |
| AU2521000A (en) | 2000-11-16 |
| EP1046484A2 (en) | 2000-10-25 |
| US20020071905A1 (en) | 2002-06-13 |
| AU740235B2 (en) | 2001-11-01 |
| EP1046484B1 (en) | 2010-05-19 |
| DE60044412D1 (en) | 2010-07-01 |
| US6531187B2 (en) | 2003-03-11 |
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