JP3850257B2 - Low temperature forming method for brittle material structures - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a film-like (two-dimensional) or three-dimensional structure made of a brittle material such as ceramics or semiconductor.
[0002]
[Prior art]
In general, in order to form a ceramic (brittle material) structure, a liquid phase firing is performed in which a sintering aid is added to form a liquid phase near the interface between the particles in order to facilitate the bonding of the ceramic particles. The result is done.
[0003]
A hot press method is known as a method for forming a high-density sintered body without using a sintering aid, and a vapor deposition method such as PVD or CVD is used as a method for forming a film such as metal or ceramic on the surface of a substrate. As a relatively low temperature process, a sol-gel method or the like is also known.
[0004]
On the other hand, recently, as a new film formation method, the gas deposition method (Seiichiro Kashu: Metals, January 1989 issue) and electrostatic fine particle coating method (Igawa et al .: Preprint of the academic meeting of the Japan Society for Precision Machinery Fall 1977 )It has been known. In the former, ultrafine particles such as metals and ceramics are aerosolized by gas agitation and accelerated through a minute nozzle. When they collide with a substrate, part of the kinetic energy is converted into thermal energy, and between particles or between the particles and the substrate. The latter is based on the basic principle. The latter is charged with fine particles and accelerated using an electric field gradient. After that, similar to the gas deposition method, the latter is sintered using thermal energy generated at the time of collision. The basic principle is to do.
[0005]
Further, as prior arts improved from the above-described gas deposition method or electrostatic fine particle coating method, JP-A-8-81774, JP-A-10-202171, JP-A-11-21676, or JP-A-2000-212766. What is disclosed in the Gazette is known.
[0006]
In the technique disclosed in Japanese Patent Laid-Open No. 8-81774, two types of metals or organic substances having different melting points are heated and evaporated by resistance wire heating, electron beam heating, high frequency induction heating, sputtering, arc plasma, etc. By using a nozzle for each metal having a different melting point, the ultrafine particles are sprayed onto the substrate based on the cross-sectional CAD data of a three-dimensional shape. By repeating, a three-dimensional solid object composed of two types of metals having different melting points is formed, and then the low-melting point metal part is melted by heating the three-dimensional solid object at an intermediate temperature between the melting points of the two types of metals. It is removed to leave only the refractory metal part.
[0007]
The technique disclosed in Japanese Patent Application Laid-Open No. 10-202171 is for spraying ultrafine particles obtained by heating and evaporation using the resistance wire heating, electron beam heating, high frequency induction heating, sputtering, arc plasma, or the like toward the substrate. In this case, a three-dimensional object having no shoulder is obtained by performing through the opening of the mask.
[0008]
The technique disclosed in Japanese Patent Application Laid-Open No. 11-21677 prevents the ultrafine particles from aggregating into large particles when transporting the aerosol containing the ultrafine particles or when the metal or ceramic is heated and evaporated. In order to do so, a classifier is arranged in an intermediate path.
[0009]
The technique disclosed in Japanese Patent Application Laid-Open No. 2000-212766 discloses that an ultrafine particle having a particle diameter of 10 nm to 5 μm (not obtained by heating and evaporation unlike the prior art), an ion beam, an atomic beam, a molecular beam, or By irradiating with low temperature plasma etc., the ultrafine particles are activated without melting them, and sprayed onto the substrate in this state at a speed of 3 m / sec to 300 m / sec, thereby promoting the bonding between the ultrafine particles and the structure. Is formed.
[0010]
[Problems to be solved by the invention]
In liquid phase sintering using a general sintering aid, a glass phase containing the sintering aid is formed in the vicinity of the grain boundary, the purity of the resulting ceramic does not increase, and it is difficult to form a dense body.
[0011]
On the other hand, high-purity and dense ceramics can be formed by means such as atomization of ceramic particles, higher sintering temperature, firing in a pressurized environment such as hot pressing, and elimination of sintering aids. It has become. However, including these, firing means that the particles are joined together by diffusion of atoms, and even if the raw material powder is fine, grain growth occurs during heating, and the formed product is made of fine crystals. It is impossible to stop it. That is, it is difficult to form a polycrystalline body composed of nanometer-level crystal grains by firing.
Moreover, when baking using a sintering aid, a specific element raise | generates segregation in the interface of particle | grains, and has become the cause which obstructs achievement of a desired characteristic.
[0012]
On the other hand, in the case of PVD, CVD or thermal spraying, all require a high temperature environment of several hundred to 10,000 ° C., a large amount of energy is input, and the sol-gel method is a relatively low temperature process. The film thickness achieved in the process is on the order of several nm to several hundred nm, and this process needs to be repeated to form a thick film. At this time, in order to substantially strengthen the underlayer film, it is necessary to perform a heat treatment, and grain growth of the underlayer occurs. There is a problem that the density does not increase in the case of film formation at a low temperature that does not cause grain growth. Moreover, the problem that a crack occurs in the film after many film forming steps has not been solved. In addition, there are many wet methods for producing a fine-structure ceramic film such as the sol-gel method or the precipitation method in solution, and other solutes or solvents in the solution are mixed in the film, resulting in deterioration of film characteristics or compositional deviation. There is.
[0013]
Further, in the methods disclosed in JP-A-8-81774, JP-A-10-202171, and JP-A-11-21777, heating means for obtaining ultrafine particles (resistance wire heating, electron beam) Heating, high frequency induction heating, sputtering, arc plasma, etc.) are required. The basic principle is that kinetic energy is converted into thermal energy and sintered in the event of a collision. The particle size of the structure formed on the substrate becomes larger than the ultrafine particles of the raw material due to grain growth. End up.
[0014]
On the other hand, the technique disclosed in Japanese Patent Application Laid-Open No. 2000-212766 also forms a deposit of metal or ceramics by sintering. However, as a result of continuous investigations by the inventors, metal (extensible material) ) And brittle materials such as ceramics and semiconductors have been found to behave differently.
That is, in the case of a brittle material, it was possible to form a structure by bonding without sintering without irradiating an ion beam, an atomic beam, a molecular beam, low-temperature plasma, or the like. However, the peel strength of the structure is insufficient or partially peeled only when the particle size of the fine particles, which are the conditions described in the publication, is 10 nm to 5 μm and the collision speed is 3 m / sec to 300 m / sec. New problems arise, such as ease of use and non-uniform density.
[0015]
[Means for Solving the Problems]
The present invention has been made based on the following findings.
Ceramics are in an atomic bond state having a strong covalent bond or ionic bond with few free electrons. Therefore, the hardness is high, but it is vulnerable to impact. Semiconductors such as silicon and germanium are also brittle materials that do not have spreadability.
Therefore, when a mechanical impact force is applied to these brittle materials, for example, the crystal lattice shifts along the wall open surface such as the interface between crystallites, or is crushed. When these phenomena occur, the atoms that were originally present inside the slipping surface or fracture surface and were bonded to another atom are exposed, that is, a new surface is formed. The part of the atomic layer on this new surface is exposed to an unstable surface state by an external force from an originally stable atomic bond state. That is, the surface energy is high. The active surface joins the adjacent brittle material surface, the newly formed brittle material surface, or the substrate surface, and shifts to a stable state. The addition of a continuous mechanical impact force from the outside causes this phenomenon to occur continuously, and the joining progresses and the structure formed thereby is densified by repeated deformation and crushing of fine particles. In this way, a structure of brittle material is formed. Therefore, the above-mentioned structure is clearly different from a green compact which has no chemical bond between particles and has a low density in a state of being compressed by pressure.
[0016]
That is, in the case of brittle materials such as ceramics and semiconductors, the present invention has been made based on the knowledge that a brittle material structure can be formed even at room temperature by adjusting the conditions under which an active new surface is formed.
That is, the low temperature formation method of the brittle material structure according to the present invention is caused by applying an impact to the brittle material fine particles at room temperature and 1 torr or less, and deforming or crushing the fine particles by the impact, and the deformation or crushing. The fine particles were recombined through an active new surface to obtain a film or a three-dimensional object. Thus, an object of the present invention is to obtain a dense and high-strength brittle material structure without a heating / firing process.
[0017]
Normally, various deposits such as moisture and gas particles are present on the surface of fine particles in the atmosphere to stabilize the surface state. Therefore, no matter how close the fine particles are, they are not joined by these inclusions. Similarly, even if a mechanical impact force is applied to the fine particles to form a new surface, gas molecules in the atmosphere instantaneously adhere to the new surface in the atmosphere and inhibit recombination of the fine particles.
[0018]
Therefore, by setting the structure forming environment to an atmosphere of 1 torr or less and increasing the vacuum state, the time and amount of adhesion of the surface deposit after the formation of the new surface can be reduced, and the fine particles are formed. The surface can be kept active until the new surface contacts the surface of another adjacent fine particle or the new surface. That is, bonding occurs with the surface energy being high, which leads to strengthening of bonding strength.
[0019]
In order to reduce the formation environment of the structure under reduced pressure, a container such as a vacuum chamber is used, and a vacuum pump is connected to the container to exhaust the air in the vacuum chamber out of the system. The atmospheric pressure of the environment in which the structure is formed is a value measured by a vacuum gauge installed near the wall of the vacuum chamber.
[0020]
In order to form a structure by the method of the present invention, it is important to easily form a new surface by pretreating brittle material fine particles. As a technique for this, it is possible to give internal strain to the brittle material fine particles in advance by pretreatment.
The internal strain referred to here is the lattice strain contained in the fine particles, and is a value calculated using the Hall method in X-ray diffraction measurement. Display percentage. The internal strain is suitably in the range of 0.25% to 2.0%. Moreover, planetary grinders and mills are examples of pretreatment devices that impart internal strain.
[0021]
If cracks occur in the brittle material fine particles of the raw material, the internal strain is canceled, so it is preferable that there are no cracks. However, even if there is a crack, it is sufficient that a predetermined internal strain exists. In other words, the raw material fine particles in which the internal strain is accumulated until just before the crack is generated are most preferable.
[0022]
In addition, as described above, the present invention is basically based on recombination of brittle material fine particles through an active new surface. For this purpose, the particle size of the brittle material fine particles is also an important factor. The average particle size of the brittle material fine particles is suitably 0.1 to 5 μm. If the average particle size is less than 0.1 μm, the particle size is too small to cause crushing and deformation. On the other hand, if the thickness exceeds 5 μm, partial crushing occurs, but some large crushed pieces remain, reducing the efficiency of contact between the new surfaces to be formed, and causing a problem that bonding does not occur sufficiently. In addition, there is a case where the accumulation of the green compact of fine particles is stopped without being crushed.
[0023]
Moreover, as means for giving an impact to the brittle material fine particles, it is conceivable to cause the brittle material fine particles to collide with the base material at a high speed, or to give a mechanical impact force to the brittle material fine particles placed on the base material.
[0024]
Examples of the method of causing the brittle material fine particles to collide at high speed include a method using a carrier gas, a method of accelerating the fine particles using an electrostatic force, a thermal spraying method, a cluster ion beam method, and a cold spray method. Of these, the method using carrier gas is conventionally called the gas deposition method, in which an aerosol containing fine particles of metal, semiconductor, or ceramic is ejected from a nozzle and sprayed onto the substrate at a high speed to deposit the fine particles on the substrate. This is a structure forming method in which a deposited layer such as a green compact having a fine particle composition is formed. Of these, the method of directly forming a structure on a substrate is called an ultra-fine particle beam deposition method or an aerosol deposition method. In this specification, the fabrication method according to the present invention is described below. Called by this name.
[0025]
The magnitude of the impact is also closely related to the formation of the new surface, and the speed when the brittle material fine particles collide with the substrate in the ultrafine particle beam deposition method is 50 m / s to 450 m / s, preferably 150 m / s to 400 m. / S. At 50 m / s or less, a phenomenon in which the green compact is mixed into the structure is observed, and at 450 m / s or more, the etching effect becomes conspicuous and the structure forming efficiency is lowered. Here, the method for measuring the velocity of the fine particles is carried out by the method described in Example 4.
[0026]
In addition, as means for applying mechanical impact force to the brittle material fine particles, a high-strength brush or roller that rotates at high speed, a pressure needle that moves up and down at high speed, a piston that moves at high speed using the compression force of explosion, etc. Or by a process of spraying a hard granular object at high speed, or by applying ultrasonic waves, or a combination thereof.
[0027]
Examples of the base material include glass, metal, ceramics, metalloid, semiconductor or organic compound, and brittle materials include aluminum oxide, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, yttrium oxide, and oxide. Oxides such as chromium, hafnium oxide, beryllium oxide, magnesium oxide, silicon oxide, diamond, boron carbide, silicon carbide, titanium carbide, zirconium carbide, vanadium carbide, niobium carbide, chromium carbide, tungsten carbide, molybdenum carbide, tantalum carbide, etc. Carbides, nitrides such as boron nitride, titanium nitride, aluminum nitride, silicon nitride, niobium nitride, tantalum nitride, boron, aluminum boride, silicon boride, titanium boride, zirconium boride, vanadium boride, niobium boride , Tantalum boride, chromium boride, molybdenum boride Borides such as titanium and tungsten boride, or mixtures and multi-component solid solutions, piezoelectric / pyroelectrics such as barium titanate, lead titanate, lithium titanate, strontium titanate, aluminum titanate, PZT, and PLZT Ceramics, high toughness ceramics such as sialon, cermet, biocompatible ceramics such as hydroxyapatite, calcium phosphate, silicon, germanium, or semiconductor materials to which various doping materials such as phosphorus are added, gallium arsenide, indium arsenide, Examples thereof include semiconductor compounds such as cadmium sulfide.
[0028]
In addition, with regard to adhesion and bonding to the base material, when the base material is a ductile material, it is not particularly necessary to deform the fine particles or form a new surface. It may be a factor. If this is considered as the underlayer, the subsequent structure formation is formed by the mechanism described above.
[0029]
BEST MODE FOR CARRYING OUT THE INVENTION
One embodiment of manufacturing a structure in the present invention will be described.
FIG. 1 shows a structure forming apparatus 1 connected to a decompression device such as a vacuum pump. The structure forming apparatus 1 includes a deposit 12 of fine particles developed on a substrate 11 and a substrate holding unit that holds the substrate 11. 13, a cylinder 14 made of a hard material and disposed opposite to the substrate 11 through a deposit 12 of fine particles, and a piston engine 15 that moves the cylinder 14 up and down.
[0030]
The cylinder 14 applies a predetermined impact force to the fine particle deposit 12 from above by vertical movement. The arrows in the figure indicate the state of movement of the cylinder 14. Due to this impact force, a part of the fine particles in the fine particle deposit 12 which is a brittle material is deformed to form a new surface, and then the fine particles are joined together. A dense structure (film body) of a brittle material is formed on the substrate 11.
The formation atmosphere of the dense structure (film body) is preferably under reduced pressure, and is not shown, but the structure forming apparatus 1 is placed in a vacuum chamber.
[0031]
The cylinder 14 portion may be formed from a large number of impact force addition needles, or may be combined with a powerful ultrasonic device to improve the formation efficiency of the structure. In addition to the dense body, the obtained film can be formed into a porous film with a limited joint portion by adjusting the raw material fine particles and adjusting the impact force.
[0032]
In the case described above, the structure is formed on the substrate, but the substrate portion is changed to a hard die having a recess, and the cylinder portion 14 is hit by filling the recess with raw material fine particles of a brittle material, It is also conceivable to produce a bulk structure.
[0033]
Next, another embodiment of the present invention will be described.
FIG. 2 shows the structure forming apparatus 2 described above. The structure forming apparatus 2 includes a deposit 22 of fine particles developed on the substrate 21, a substrate holding unit 23 that holds the substrate 21, and a substrate 21. The granular material injection device 24 is disposed so as to face each other via the fine particle deposit 22, and the granular material injection device 24 stores a hard granular material 25. These are housed in a vacuum chamber 26, and a vacuum pump 27 holds the vacuum chamber in a reduced pressure state of 1 torr or less.
[0034]
The hard granular material 25 is, for example, a ceramic powder of several tens to several hundreds of micrometers, and is ejected from the granular material injection device 24 toward the fine particle deposit 22 at a subsonic to supersonic high speed. The impact force caused by the collision of 25 deforms the fine particles constituting the fine particle deposit 22 to form a new surface, and the fine particles are joined together to form a structure. This method is particularly convenient for thin film formation. For acceleration of the granular material 25, a high-speed carrier gas may be used, or electrostatic attraction may be used. Even when the gas is used, by separating the granular material injection device 24 from the substrate 21, the light gas is discharged by the vacuum pump 27 toward the outside of the chamber. Since the inertial force is relatively large, it flies almost linearly toward the substrate 21. Therefore, there is little scattering of the particulate deposit 22 by the gas, and the vacuum degree in the vicinity thereof can be maintained relatively high. In addition, by using a granular material 25 of several tens to several hundreds of μm, it is possible to concentrate the impact force of the fine particles on the deposit 22 locally, and increase the efficiency of deformation of the fine particles and formation of a new surface. Can do.
[0035]
Next, a typical structure forming apparatus used when forming a structure by an ultrafine particle beam deposition method, which is another embodiment of the present invention, will be described.
FIG. 3 shows the structure forming apparatus 3. An aerosol generator 303 is installed at the tip of a nitrogen gas cylinder 301 through a gas transport pipe 302, and the structure is formed at the downstream side through an aerosol transport pipe 304. A nozzle 306 is installed in the chamber 305. The aerosol generator 303 is filled with brittle material fine particles, for example, aluminum oxide fine particle powder. A substrate 307 is disposed at the tip of the opening of the nozzle 306, and the substrate 307 is fixed to the XY stage 308. The structure formation chamber 305 is connected to a vacuum pump 309. A vacuum gauge 310 is installed from the wall surface of the structure forming chamber 305.
[0036]
The operation of the structure forming apparatus 3 will be described below. The nitrogen gas cylinder 301 is opened, the gas is sent into the aerosol generator 303, and at the same time, the aerosol generator 303 is operated to generate an aerosol in which brittle material fine particles and nitrogen gas are mixed in an appropriate ratio. Further, the vacuum pump 309 is operated to generate a differential pressure between the aerosol generator 303 and the structure forming chamber 305. The aerosol is accelerated through the aerosol transport pipe 304 and is ejected from the nozzle 306 toward the substrate 307. The substrate 307 is swung by the XY stage 308, and a film-like brittle material structure is formed on the substrate 307 by collision of fine particles while changing the aerosol collision position. By moving the nozzle 306 and the substrate 307 relatively, a brittle material structure is formed in a required area.
[0037]
【Example】
Example 1
FIG. 4 shows a TEM image of a lead zirconate titanate (PZT) structure formed on a silicon oxide substrate using the ultrafine particle beam deposition method, and FIG. 5 shows the ultrafine particle beam deposition method. FIG. 6 is a distribution diagram of the size of crystallites in the structure counted from the TEM image.
The internal strain of the raw material particles was about 1%, and the particle size of the raw material particles was several hundred nm. On the other hand, most of the structures obtained from the figure have a crystallite diameter of 40 nm or less, and it is observed that they are joined without a gap, and no orientation is observed in the crystal orientation, and further, There is no glass layer at the grain boundaries.
FIG. 7 is a SEM image observing the surface roughness of the silicon oxide substrate before forming the lead zirconate titanate (PZT) structure, and FIG. 8 is the oxidation after forming the lead zirconate titanate (PZT) structure. It is a TEM image of the boundary part with the silicon substrate, and it is recognized by comparing these figures that a part of the lead zirconate titanate (PZT) structure bites into the silicon oxide substrate and becomes an anchor part. It is done.
This structure has a Vickers hardness of 300 to 500 and has mechanical properties comparable to those of the fired body.
[0038]
(Example 2)
An aluminum oxide structure was formed on the brass substrate by using the ultrafine particle beam deposition method having substantially the same configuration as the structure forming apparatus 3 for performing the ultrafine particle beam deposition method described above. First, aluminum oxide fine particles having an average particle diameter of 0.6 μm were pulverized by a planetary mill and strain was applied. Next, the formation of the structure was attempted by filling the aerosol generator with the aluminum oxide fine particles and venting nitrogen gas at a gas flow rate of 5 liters per minute. When the value of the vacuum gauge at this time was 1 torr, the formation height of the formed structure was 10 μm and its Vickers hardness was 793. When the value of the vacuum gauge was 0.5 torr, the formation height of the formed structure was 13 μm and its Vickers hardness was 939.
[0039]
Example 3
FIG. 9 shows the results of experiments on the relationship between internal strain and film thickness. In the experiment, aluminum oxide fine particles having a purity of 99.6% were pulverized using a planetary mill to change the characterization of the fine particles, and then an ultrafine particle beam was used using an apparatus according to the structure forming apparatus 3 described above. A structure was formed on the aluminum substrate by a deposition method. The internal strain of the fine particles was measured by X-ray diffraction, and the amount of strain was determined based on 0% obtained by subjecting the fine particles to thermal aging to remove the internal strain.
Further, SEM photographs of fine particles at points A, B, and C in FIG. 9 (Hitachi in-lens SEM S-5000) are shown in FIGS. 10, 11 and 12. FIG.
It can be seen from FIG. 9 that the internal strain is preferably 0.25% to 2.0%. Regarding the relationship between cracks and internal strain, when there is no internal strain, cracks do not occur as shown in FIG. 10, but in the state shown in FIG. 11, some cracks are generated, but sufficient internal strain remains. ing. Then, when the internal strain is a certain value or more, in this case, 2.0% or more, cracks are completely formed, and the fragments that fall off adhere to the surface and re-aggregate as shown in FIG. End up.
[0040]
Example 4
Example 4 describes the measurement of the speed of fine particles during structure formation.
The following method was used to measure the velocity of the fine particles. FIG. 13 shows a fine particle velocity measuring apparatus. A nozzle 41 for injecting aerosol into a chamber (not shown) is installed with the opening facing upward, and a substrate 43 installed at the tip of a rotary blade 42 that is rotated by a motor and a substrate surface 19 mm below the substrate surface. A fine particle velocity measuring device 4 having a slit 44 having a notch having a fixed width of 0.5 mm is arranged. The distance from the opening of the nozzle 41 to the substrate surface is 24 mm.
Next, the fine particle velocity measurement method will be described. The aerosol is sprayed according to the actual composite structure manufacturing method. In place of the substrate on which the structure is formed in the structure forming chamber, the fine particle velocity measuring device 4 shown in the figure is preferably installed. A chamber (not shown) is placed under reduced pressure, aerosol containing fine particles is ejected from the nozzle 41, and the fine particle velocity measuring device 4 is operated at a constant rotational speed in this state. Part of the fine particles that have jumped out from the opening of the nozzle 41 collide with the surface of the substrate through the gaps in the slit 44 when the substrate 43 comes to the top of the nozzle 41, and the structure ( Collision marks) are formed. Since the position of the substrate 43 is changed by the rotation of the rotary blade 42 while the fine particles reach the substrate surface 19 mm away from the slit, the amount of displacement is larger than the perpendicular crossing position from the notch of the slit 44 on the substrate 43. Collide with the displaced position. The distance from the perpendicular crossing position to the structure formed by the collision is measured by surface unevenness measurement, and using this distance, the distance from the slit 44 and the substrate surface, and the value of the rotational speed of the rotary blade 42, the nozzle 41 is measured. As the velocity of the fine particles ejected from the nozzle 41, the average velocity from a location 5 mm away from the opening of the nozzle 41 to a location 24 mm away was calculated, and this was used as the velocity of the fine particles in this case.
[0041]
【The invention's effect】
As described above, the brittle material structure according to the present invention can be used to form a brittle material structure without firing. Therefore, when the structure is formed on the substrate, a metal or plastic material having a low melting point can be used.
[Brief description of the drawings]
FIG. 1 is an apparatus diagram of a structure forming apparatus according to an embodiment of the present invention.
FIG. 2 is an apparatus diagram of a structure forming apparatus according to an embodiment of the present invention.
FIG. 3 is an apparatus diagram of a structure forming apparatus using a fine particle beam deposition method according to an embodiment of the present invention.
FIG. 4 is a TEM image of a lead zirconate titanate (PZT) structure.
FIG. 5 is a TEM image of raw material particles of PZT.
FIG. 6 is a distribution diagram of crystallite sizes in a structure counted from a TEM image.
FIG. 7 is an SEM image of a silicon oxide substrate before forming a lead zirconate titanate (PZT) structure.
FIG. 8 is a TEM image of a boundary portion with a silicon oxide substrate after formation of a lead zirconate titanate (PZT) structure.
FIG. 9 is a graph showing the relationship between internal strain and film thickness of raw material fine particles.
10 is an SEM image of fine particles corresponding to point A in FIG.
11 is an SEM image of fine particles corresponding to point B in FIG.
12 is an SEM image of fine particles corresponding to point C in FIG.
FIG. 13 is a fine particle velocity measuring device.
[Explanation of symbols]
1 Structure forming device
11 Substrate
12 Sediment
13 Substrate holder
14 cylinders
15 piston engine

Claims (1)

An impact is applied to the brittle material fine particles at room temperature and under 1 torr, the fine particles are deformed or crushed by the impact, and the fine particles are recombined with each other through an active new surface generated by the deformation or crushing to form a film. a low temperature method of forming a brittle material structures and objects or three-dimensional shaped article, that the internal strain of the advance 0.25% to 2. 0% of the range by the brittle material fine particles pretreatment is applied A low temperature forming method of a characteristic brittle material structure.

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