JP2017177037A - Nozzle for high pressure injection processing device, evaluation method for high pressure injection processing device, and high pressure injection processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control energy in a nozzle by combining various nozzle chips different in diameter, to realize efficient micronization processing, and to use the nozzle according to purposes, such as micronization processing and defiberizing processing.SOLUTION: The high pressure injection processing device nozzle that generate and micronizes cavitation by high-pressure injecting a raw material mixed liquid from the nozzle by prescribed pressure is provided with: a nozzle tip Nn having a through-hole; and a nozzle holder Nh, and characterized in that the ratio (Wn/Dn) of the thickness Wn of the through-hole of the nozzle tip to the diameter Dn of the through-hole of the nozzle tip is set to 10 or higher, the diameter Dn of the through-hole is set to 0.16 mm or less, and efficient micronization and various micronization modes are realized by dividing the tip and changing the diameter thereof.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a nozzle of a high-pressure injection processing apparatus, a method for evaluating a high-pressure injection processing apparatus, a high-pressure injection processing apparatus, and a high-pressure injection processing method that are used when performing wet micronization of raw materials.

Fine particles, especially nanoparticles, have an extremely large surface area due to their nanometer (nm) order size, and exhibit specific physical properties due to quantum size effects, and are being studied and used in various fields. Yes. These particles are being widely used in various material fields such as electronic parts, pigments, cosmetics, pharmaceuticals, foods, and agricultural chemicals. On the other hand, since nanoparticles easily aggregate, in order to effectively utilize the characteristics of the nanoparticles, appropriate dispersion and miniaturization treatment suitable for the properties of the nanoparticles are required. In recent years, an efficient defibration technology for making nanofibers such as cellulose has become an important technology for practical use of the material.
The high-pressure injection processing device is a device that refines the particles themselves by high-pressure jetting the raw material mixture mixed with the raw material particles from the nozzle, and has been widely put into practical use in order to disperse and refine these particles. Yes.

On the other hand, an in-situ evaluation method has not been established for the raw material mixture being processed by the high-pressure injection processing apparatus, and it has been very difficult to find the optimum process conditions. Until now, the solution processed by the high-pressure jet processing apparatus was sampled and evaluated by analyzing it with a laser particle size distribution apparatus. For this reason, it takes time to determine the conditions for the miniaturization process, and the high speed of this process cannot be fully utilized as compared with a process that requires media such as a bead mill.
In Patent Document 1, as an example of a method for detecting a cavitation occurrence state of water jet by submerged injection, an erosion test by water jet injection with different nozzles is performed on a work in a test tank, and jet generation sound is detected. That the waveform data is subjected to FFT processing and the cavitation evaluation for each nozzle is performed, and the waveform data in the frequency range of 0 to 12.5 kHz is subjected to FFT processing for the obtained signal. (Paragraphs 0026-0029).
Patent Document 2 relates to a method for producing fine particles of a material using a high-pressure pulverizer, and a temperature sensor, a pressure sensor, and an acoustic sensor are arranged at each stage of the pulverizer to collect data in the pulverization process and manage the product (See the abstract text).
Non-Patent Document 1 is a paper on ultrasonic spectroscopy, and reports on cases relating to the particle size of TiO ₂ suspension and attenuation of ultrasonic waves propagating therethrough.

  The above-mentioned patent document 1 detects a jet generated sound of a water jet injected in a liquid with a microphone, and since the maximum frequency of the detected and analyzed sound is 12.5 kHz, low energy generated at a low speed is detected. Sounds due to cavitation are measured. In this case, since the frequency is low, phenomena such as the particle diameter in the raw material mixture being processed by the high-pressure injection processing apparatus are not accurately evaluated. In addition, Patent Document 2 describes that a sensor is arranged at each stage of the high-pressure crusher, and data in the crushing process is collected and used for product management. There is no description about whether or not, and there is no description that suggests the type or frequency of the acoustic signal.

Actually, the signal due to cavitation generated in the low-pressure chamber located downstream of the nozzle of the high-pressure jet processing apparatus has a frequency band close to acoustic noise because of low energy. When refining the particles of the raw material mixture, the large force suitable for the refining process is the high pressure region such as impact due to high energy cavitation collapse generated in the high pressure part in the nozzle hole and shearing force of high-speed flow. It was thought that the phenomenon that caused the high-speed flow was mainly. Therefore, the present inventor considered that high energy phenomena such as cavitation collapse at high pressure can be selectively detected by attaching an AE sensor capable of detecting a limited high frequency to the high pressure injection processing apparatus.
The AE sensor is a sensor that detects an acoustic emission signal. Acoustic emission is generally a phenomenon in which sound generated when a solid is deformed or broken is emitted as an elastic wave, and this elastic wave is an ultrasonic wave also called an AE wave. This ultrasonic signal is detected by an AE sensor.
Cavitation occurs as a part where the pressure is locally low due to the disturbance of the flow of the liquid, and is generated as a bubble when the low pressure part falls below the vapor pressure of the liquid. When the bubble contracts and collapses, a large impact force is generated. It is a phenomenon that is born. Of course, the higher the atmosphere, the greater the decay energy. The cavitation with high destructive force generated in the high pressure region is utilized for the miniaturization process by high pressure injection. Therefore, to increase the efficiency of this device, it is necessary to realize a high-speed flow with the nozzle and to cause cavitation at as high a pressure as possible.
First, the present inventor tried to detect a signal by high-frequency cavitation generated by a nozzle by actually attaching an AE sensor to a high-pressure injection processing apparatus. As a result, it was possible to grasp the relationship between the detected high frequency signal and the particle size and viscosity of the treatment liquid. And the method of evaluating the raw material liquid mixture in process with a high-pressure-injection processing apparatus on the spot was discovered, and this was applied for a patent (Japanese Patent Application No. 2014-201744). Among these, it has been clarified that there are two types of AE signals to be measured due to the flow in the suspension and those due to the particles in the suspension. The AE signal generated by this flow is generated in a region where cavitation occurs at a place where the speed difference between the high-speed flow and the nozzle side surface is large, and a jet flow is formed based on the cavitation. At the boundary, a region where a large shear force is applied is formed. This part is strongly related to the miniaturization performance of the nozzle. That is, it is shown that by increasing the AE signal related to the flow, the miniaturization characteristics of the nozzle including the apparatus can be evaluated. This means that increasing this value increases the atomization characteristics of the device, and the suspension can be used for quantitative evaluation of the nozzle by evaluating only the solution, not the liquid containing particles. Is meant to be. In the present invention, the flow in the nozzle changes into laminar flow, turbulent flow, and jet flow including a gas layer at the boundary in the order of velocity.

  Various chambers and nozzles have been devised as conventional techniques. For example, Patent Document 3 states that a collision device that suppresses the attenuation of a high-speed jet and simultaneously obtains a good cavitation effect and can exhibit sufficient miniaturization performance with a high collision energy, is “injected from an injection nozzle. For a cylindrical high-speed flow path that receives and passes a high-speed jet and then jets from the outlet opening and collides with the surface of the hard body, the injection nozzle diameter is D1, and the injection pressure P1 for injecting fluid from the injection nozzle is 100 MPa or more. In the range where the Reynolds number Re is 45000 or more and 120,000 or less, the high-speed flow path diameter D2 satisfies Formula 1 and the high-speed flow path length L2 satisfies 25 mm ≦ L2 ≦ 55 mm. 1) and mention is made of the hole diameter and length.

Patent Document 4 discloses a raw material tank that contains a suspension containing raw material particles, and a raw material particle that is connected to the raw material tank by a serial circulation circuit and is given a rotational force in the suspension. In a miniaturization apparatus comprising: a bead mill that sandwiches and pulverizes; and a jet mill that is connected to the raw material tank in a series circulation circuit and jets a pressurized high-pressure suspension at high speed with a nozzle device, The jet mill has one or more nozzle devices that eject the high-pressure suspension at high speed, and a chamber that forms a micronized space in which the suspension is ejected from the nozzle device, and the bead mill includes the beads And a container in which the suspension flows from the inlet on one end side to the outlet on the other end, and a plurality of substantially disk-shaped rotating blades for stirring the beads and suspension in the container are spaced apart from each other. A rotating shaft provided on the center of the cylinder, and a drive device for rotating the rotating shaft. The container has a cylindrical shape, and the rotating shaft disposed on the central axis of the cylinder is perpendicular to the vertical direction. And a miniaturization apparatus that is inclined at a predetermined angle. (Claim 1) and "The nozzle device of the jet mill is provided with two or more orifice nozzles connected coaxially. (Claim 6) and "The nozzle device of the jet mill has an enlarged diameter portion at a downstream end of each of the two or more connected orifice nozzles." And the above-described miniaturization apparatus (Claim 7).

  Patent Document 5 states that “an ethylene monomer, a polymerization initiator, a surfactant having a critical micelle concentration of 0.5 times or less, and a dispersion stabilizer are added to an aqueous medium and stirred to give a simple substance. A primary suspension in which the monomer is dispersed as oil droplets is made, and this primary suspension is passed through a nanomizer (registered trademark), in which the pressure applied to the primary suspension is increased or decreased. A method for producing fine polymer particles having a uniform size is disclosed in which a secondary suspension is formed by adjusting the degree of coalescence, and this is heated and polymerized to obtain polymer particles.

JP 2006-300640 A US Pat. No. 6,318,649 JP 2010-036120 A JP 2013-163162 A JP 07-292003 A Japanese Patent No. 4301441

DUKHIN, A. S., GOETZ, P. J., (1996), Acoustic Spectroscopy for Concentrated Polydisperse Colloids with High Density Contrast, Langmuir, 12, pp. 4987-4997

In the refinement process using a conventional high-pressure jet processing apparatus, there are many cases where dozens of processes are required for cellulose defibration and nanoparticle pulverization / dispersion. Also, since multiple processes are required to form an emulsion, the equipment must be further miniaturized (strengthening destructive force) and more efficient (processing can be completed in fewer times than before). ing. Therefore, various kinds of apparatuses and methods have been proposed. One is improvement in the low-pressure chamber after high-speed injection, and the other is improvement in the nozzle part of the high-pressure part such as a high-pressure homogenizer and nanomizer.
Various chambers such as collision-type chambers (Patent Document 3 as collision type) and counter-chambers (Patent Documents 3 and 4 as counter-type) are considered to be effective for miniaturization of fluid collision phenomena in low-pressure chambers. Has been developed.
On the other hand, as an improvement of the nozzle portion, gorin type high-pressure homogenizer (injection pressure 34 to 55 MPa, nozzle meter 0.4 to 6 mm, flow rate 208 m / s) and nanomizer (injection pressure: maximum 200 MPa, slit width 0.16 to 0) (2 millimeters, maximum flow velocity 290 m / sec), and others have devised improvements in the nozzle portion, but the average velocity in the nozzles in these devices was as slow as 300 m / s or less. Furthermore, in the conventional patent document 3, the nozzles of the same diameter are multistaged, but the miniaturization mainly uses beads, and the nozzle configuration is a simple multistage configuration that is not very effective. .
According to the research and development of the present inventors, the large force involved in miniaturization of high-pressure injection processing (high-pressure jet mill processing) is not a phenomenon in the collision type or opposed type low-pressure chamber, mainly around the nozzle, The energy of pressure generated by the cylinder pressurized to high pressure is converted into kinetic energy, and the shearing force at the boundary due to the generation of the jet flow based on the cavitation generated by the high-speed flow, and the cavitation inside the jet flow I figured out what was happening in Therefore, if the pressure energy pressurized by the high-pressure cylinder can be converted into kinetic energy without reducing the speed, and the high-pressure region of the jet flow generated there can be increased, the miniaturization limit and the number of treatments in the high-pressure injection process can be reduced. Can be improved. That is, an effective miniaturization nozzle requires a configuration that can reduce the fluid resistance and increase the high-pressure region.
It is not simply a reduction in the nozzle hole diameter, nor is it simply multi-staged (see claims 6 and 7 of Patent Document 4), and is developed based on objective data on the mechanism of cavitation generation. It is a thing.

As a specific improvement of the conventional nozzle, a high-pressure wet medialess miniaturization apparatus called Nanomizer (registered trademark) has been developed (Patent Document 5). The principle of this nanomizer is to feed a sample into a high-pressure pump, create a high-speed flow, pass through a special nozzle (generator), and emulsify, disperse, and crush by the action of ultra-high-speed shearing force, shock wave, cavitation, etc. Is. In this apparatus, as shown in (Patent Document 5), the nozzle is a method of forming a slit in the substrate and allowing a high-speed flow to pass through the slit.
However, the shape like the above slits requires the production of diamonds on opposite planes and a technique for accurately processing hard materials such as diamonds to 0.2 mm or less, and reducing the nozzle diameter to 0.1 mm. Is difficult and expensive. Therefore, the effective slit width is increased, and it is difficult to obtain a high flow rate necessary for the miniaturization process, and an efficient miniaturization process cannot be performed. In addition, because of the structure in which diamond is bonded, it is difficult to disassemble the nozzle, and there is a problem with respect to maintenance when nozzle clogging occurs.

Patent Document 6 discloses a multi-stage emulsification / dispersion controller that performs emulsification / dispersion by liquid-liquid shearing using a jet flow in a technique relating to an apparatus and method for generating an emulsified dispersion by emulsifying / dispersing a desired material in a liquid. 1 and an absorption cell 21 arranged in the multi-stage emulsification / dispersion controller 1, and the multi-stage depressurization module 3 that reduces the pressure of the generated emulsification / dispersion liquid in multiple stages to a pressure that does not cause bubbling. An emulsification / dispersion system in which inner diameters D1, D2, and D3 of -1,21-2, 21-3, 21-4, 21-5, and 21-6 are D2>D1> D3 is disclosed.
However, the emulsification / dispersion system uses a multi-stage absorption cell so as not to generate bubbles, and is not applied to the high-speed flow and high-pressure cavitation of the present application, and the miniaturization process using the expansion of the high-pressure region, The size of the cell diameter used is too large at 0.5 mm-1.0 mm, so it is difficult to obtain a high-speed flow of 300 m / s, and the effect of sufficiently expanding the high-pressure region cannot be obtained. it is conceivable that.

  The present invention was developed by elucidating the phenomenon of high-pressure cavitation generation and shearing caused by jet flow based on it, and measuring the phenomenon of destruction in miniaturization by measuring the AE signal, etc., and has a through hole. High pressure injection processing method and high pressure injection that can improve the miniaturization characteristics such as the reduction of particle diameter and the number of treatments more than ever in the miniaturization process with a simple nozzle structure of hard diamond tip (nozzle tip) and nozzle holder It is to provide a nozzle of a processing apparatus. In addition, the present invention controls and adjusts the area where cavitation occurs, the area where jet flow and the surrounding laminar flow and vortex flow occur, and enables various types of micronization / defibration processing such as nanoparticles and fibers. And a nozzle for a high-pressure injection processing apparatus.

(Consideration of Inventor Nozzle Diameter)
Here, the term “cavitation” means that in a liquid flowing at high speed, a point where the pressure decreases as the speed increases is generated, and the phase of the liquid changes to a gas at that point, and the vapor pockets form in a very short time. Born and defined as a phenomenon in which this pocket collapses and disappears in a short time. Using the energy that collapses and disappears in a short time (impact based on the collapse of cavitation), the particles of the raw material mixture can be refined and defibrated.
Cavitation is a phenomenon with impact energy proportional to pressure. “High-pressure cavitation” refers to cavitation that occurs under high-pressure atmospheric conditions (atmospheric pressure is about 0.1 MPa, and a high pressure is several MPa that is 10 times or more of atmospheric pressure). Sometimes has impact energy proportional to pressure. In a nozzle pressurized to a high pressure by a cylinder, this pressure provides much greater impact energy than low pressure cavitation close to atmospheric pressure. Refinement of the raw material mixture is mainly performed using this high-pressure cavitation. This phenomenon occurs in and around the nozzle. According to the embodiment, such a high-pressure flow state includes not only laminar flow and turbulent flow but also a very high-speed jet flow. Furthermore, it was found that there are two types of states where there is a boundary between the jet flow and laminar flow inside the nozzle when the nozzle diameter is large, and where the jet flow and the side surface of the nozzle are the boundary when the nozzle is small. . The boundaries of these jet flows are more discontinuous than the turbulent flow including the air layer portion due to bubbles caused by cavitation. As shown in the examples, this phenomenon shows that the flow rate did not change even when the nozzle thickness was increased experimentally under certain conditions, and as the processing progressed in fiber-type material defibration such as cellulose, suspensions containing them were included. Even though the viscosity of the turbid liquid increased by 100 times or more, the flow rate of the suspension did not change. Therefore, this boundary portion is in a state of very low fluid resistance that does not contain much liquid. A strong shear force acts at this boundary portion, and a high energy AE signal proportional to the speed is also generated. Also, the size of the area is related to the size of the AE signal. Therefore, this peripheral state is an important region for strong miniaturization.
In general, a condition for causing cavitation is defined by the size of the cavitation number σ of the following equation. In this equation, cavitation occurs when σ is 1 or less, and super cavitation where the flow is almost bubbled when 0.6 or less. The important point in this equation is that cavitation is less likely to occur when the pressure increases. Therefore, a high-speed flow is necessary. In other words, near the nozzle, the solution is accelerated by changing the pressure energy to kinetic energy, and when the cavitation number becomes 1 or less as the pressure of the solution decreases, bubbles are generated. Will occur.

Next, the state is estimated.
In general, the cavitation number σ can be expressed by (Expression 2).
Here, P _N is the pressure of the nozzle, P _V is the vapor pressure of the fluid, ρ is the density of the fluid, and v _N is the velocity of the fluid. In this equation, it is known that when σ is 1, cavitation occurs, and when σ is 0.6 or less, super cavitation occurs.
In the vicinity of the nozzle, the energy of the injection pressure is converted into kinetic energy by the law of conservation of energy (Bernoulli's theorem), and the pressure is reduced according to the flow velocity. At that time, cavitation occurs when a certain pressure is reduced. That is, a place where σ is 1 is a cavitation occurrence point, and thereafter σ becomes 1 or less on the downstream side, and a lot of cavitation occurs.
Next, the generation conditions will be considered.
The pressure of the solution in the nozzle, from the initial injection pressure P _NI as the distance x progresses, eventually changed to P _NO atmospheric pressure. If the pressure conversion of pressure is P _Nv (x) as a function of x and the injection pressure is as high as one hundred MPa, the equations (3) and (4) can be derived if the vapor pressure _{Pv of the} solution is ignored. In (Expression 3), a condition that σ is 1 or less is added.
This equation shows that cavitation occurs in the pressure region where the pressure is converted into velocity around the nozzle subjected to high-pressure injection and becomes less than half of the injection pressure. In other words, there is an acceleration region in the vicinity of the nozzle where pressure is converted into kinetic energy, and when the initial injection pressure from the high-pressure cylinder is halved, a jet flow starting from cavitation is generated. ing. At this time, the maximum pressure of the high-pressure cavitation in the jet flow is half of the initial injection pressure. The pressurized solution will pass through the nozzle at this rate due to the flow continuity. Thereafter, the solution flows from the nozzle outlet into the low pressure chamber and the pressure is released. At this time, the pressure of the jet flow suddenly decreases and a state of super cavitation including many bubbles is obtained. At this time, since the flow is diffused, the flow velocity is reduced without increasing, so that a strong stirring state is formed in the vicinity thereof.
This indicates that in order to perform atomization using high-pressure cavitation and strong shearing force, it is important to expand the high-pressure area after the jet flow generation as much as possible and not create a super cavitation state. Yes.
Next, consider the detailed flow around the nozzle. From the model, cavitation due to high-speed flow occurs at a place where the injection pressure is ½ in the acceleration region near the nozzle entrance, and a jet flow is formed with these gas layers as a boundary. Here, the fluid resistance is low. A flow having a two-layer structure of a laminar flow and a jet flow is generated in the vicinity of the nozzle. When the diameter of the jet flow is larger than the nozzle diameter, the boundary becomes the nozzle side wall, and a strong shearing force acts on the particles in the liquid in the boundary region, thereby generating a strong refining action. On the other hand, when the diameter of the jet flow is smaller than the nozzle diameter, a laminar flow of the solution is sandwiched at the interface with the nozzle side surface, so that a larger shear force than that in the above case acts on the interface with the jet flow. There will be no. That is, the power of miniaturization is weaker than that in the above-described state, and the atomization characteristics greatly change with the diameter as a boundary.
At the nozzle outlet, the pressure decreases and the number of cavitations decreases, so that the state changes to a super cavitation state in which bubbles increase. In this region, the stirring action is stronger than the miniaturization action. This makes it possible to increase the miniaturization efficiency by increasing the thickness of the nozzle itself, or by increasing the area where the cavitation number is 0.6 to 1 on the downstream side of the nozzle that generates the jet flow. It is shown that. In the nozzle of the high-pressure jet processing apparatus of the present invention, this region is enlarged by increasing the nozzle tip and devising the nozzle configuration, and the atomization characteristics are improved.
In order to maintain and expand the high pressure region, not only the nozzle chip with a small through hole but also the configuration of the nozzle holder constituting the nozzle is important. In order not to lower the pressure, the diameter of the nozzle holder should be as small as possible, but in reality it is about 0.8 mm. With regard to the nozzle configuration, the configuration can be designed with a high degree of freedom by providing multiple nozzles. Specifically, by changing the combination of the nozzle tip diameter and the nozzle holder diameter and their thickness, the high pressure region of the jet flow can be widened and the atomization characteristics can be improved. At this time, since the speed of the solution is a very important parameter, a nozzle structure that can maintain a high speed is very important.

The inventor of the present application considered data by a monitoring device such as high-pressure cavitation of high-pressure injection (high-pressure jet mill) processing developed so far and phenomena when various materials were processed.
When the number of treatments was increased, the viscosity of the suspension changed greatly, but the treatment time, that is, the average speed in the nozzle hardly changed. Moreover, even if the thickness of the nozzle was changed, the processing time did not change greatly. From these experimental facts, it was considered that the inside of the nozzle was not in a normal laminar or turbulent state, but in a state of jet flow having a small fluid resistance with the gas layer as a boundary.
From these viewpoints, the phenomenon in the nozzle and the improvement method are considered as follows.
Cavitation occurs in the process of changing the pressure energy of the jet into kinetic energy, and is caused by the pressure drop accompanying the speed change. Therefore, the inside of the nozzle is divided into a jet flow area that is generated at the center of the nozzle and a laminar flow area that is slower than the jet flow area and the area around the side surface of the nozzle. A miniaturization effect has occurred.
In order to expand this effective area of finer scaling, (A) increasing the thickness of the nozzle hole in which cavitation occurs, (B) increasing the flow velocity in the nozzle (for example, the nozzle It is conceivable to reduce the diameter of the through hole or increase the pressure. In particular, (A) leads to an increase in the area of the miniaturization process, leading to a decrease in the number of processes. The size of the nozzle diameter in (B) leads to changing the ratio of the jet flow and the laminar flow, and becomes an important factor for mode switching described later. However, since the theoretical maximum value of the speed is determined from the energy conservation law (Bernoulli's theorem), there is a limit to the improvement in (B), so that a nozzle with as little fluid resistance as possible is suitable.
By using a high-pressure injection processing apparatus and nozzles that consider (A) and (B) above, the destructive force of miniaturization increases even in the configuration of conventional collision-type and counter-type low-pressure chambers, and is proportional to the thickness of the nozzle. Thus, an effective miniaturization process can be realized, and the number of processes can be greatly reduced and a finer graining process can be performed.
First, it is important to thicken the nozzle portion through which the solution passes. The nozzle material of this part requires a hard material in order to flow a high-speed fluid and a suspension containing hard ceramics at a high speed. Therefore, it is made of diamond to obtain a long life. However, it is very difficult to make a nozzle hole with a diameter of about 0.1 mm in a hard material by several tens of millimeters. In reality, several millimeters is the limit. Furthermore, in order to obtain a large shear force, the flow needs to be fast and the fluid resistance of the nozzle must be small. Therefore, it is necessary to optimize the nozzle tip diameter and the nozzle holder diameter and the nozzle configuration so as not to cause resistance to the jet flow generated from the flow continuity. For example, the centers of a plurality of nozzle diameters in the high pressure portion are arranged in the same line. In conventional collisions and oppositions at high-pressure parts, it is considered that a high-speed flow cannot be expected because the collision part becomes a resistance.
Also, as a result of experimentally elucidating the AE signal with a frequency that limited the phenomenon at the nozzle, the flow of fluid injected at a high pressure of several hundred MPa is not laminar or even turbulent, and bubbles are formed at the boundary in the center of the nozzle. The included jet stream was shown to be laminar around the nozzle. This AE signal was due to high-pressure cavitation, and was thought to be generated mainly at the boundary of the jet flow.
Further, the diameter of the jet flow did not exceed 0.17 mm when the pressure was in the range of 100 to 200 MPa. Therefore, it was found that effective miniaturization cannot be achieved unless the nozzle diameter is made smaller than that in order to make use of the large shearing force generated by the high-speed jet flow. On the other hand, when the thickness of the nozzle is increased more than necessary in order to expand the high pressure region, the average flow velocity in the nozzle is decreased, and a high miniaturization effect cannot be obtained. In other words, it has been experimentally found that the nozzle has an optimum shape.
As a nozzle that satisfies both conditions, the ratio of the nozzle diameter Dn to the thickness Wn (Wn / Dn) is very important for a single nozzle. Here, the “nozzle diameter Dn” is the diameter of the nozzle hole (through hole) of the nozzle tip, and the “nozzle thickness Wn” is the thickness (length) of the nozzle chip hole. (FIG. 3).
On the other hand, with a single nozzle, there is a limit to the processing of diamond chips and the like, so in order to realize a nozzle with a large Wn / Dn, it is necessary to stack nozzle chips or divide the nozzles to reduce the effective nozzle thickness. It becomes important to stretch. As this method, a configuration in which a single nozzle is multi-staged is conceivable, but a configuration in which the speed in the nozzle is not reduced is necessary. Simply by arranging a plurality of nozzles of the same diameter, the average speed decreased, the AE signal also decreased, and the atomization characteristics deteriorated. At this time, the maximum diameter of the jet flow obtained in the experiment was the boundary. Based on the size of this diameter, it was possible to classify the nozzle into two types: a miniaturized nozzle that positively applied a large shear force at the boundary with the jet flow, and a defibrating nozzle that uses laminar flow. For example, by using a nozzle having a diameter smaller than 0.16 mm of the jet flow diameter on the high pressure side and using a nozzle having a diameter larger than the jet flow diameter on the low pressure side thereafter, the resistance of the nozzle to the jet flow is increased. There was no speed reduction. Since the AE signal also increased, it was possible to create a state in which the high pressure region was expanded. As a result, the effect of miniaturization increased. In the latter stage nozzle, a jet flow and a laminar flow portion are formed, so that the stirring action of the solution is high, and further, the effect of miniaturization is enhanced.
On the other hand, by using the opposite configuration, it was possible to obtain a configuration suitable for defibration using a high-speed and high-speed laminar flow.

The nozzle of the high-pressure injection processing apparatus of the present invention is a nozzle of a high-pressure injection processing apparatus that performs high-pressure injection and refines the raw material mixture so that the average velocity in the nozzle is 300 m / s or more, and the nozzle has a through hole. The nozzle tip is composed of a nozzle holder and a nozzle holder. The diameter Dn of the through hole of the nozzle tip is 0.16 mm or less, and the ratio (Wn / Dn) of the thickness Wn of the through hole of the nozzle tip to the diameter Dn is 10 or more and 45. It is characterized by being less than.
Here, the “upstream side” refers to the “upstream side” that is in the upstream position by paying attention to the flow of the raw material mixture in the high-pressure injection processing apparatus.
Here, the “downstream side” refers to the “downstream side” that is in the downstream position with a focus on the flow of the raw material mixture in the high-pressure injection processing apparatus.
According to the experiments by the present inventors, the simplest nozzle structure in the miniaturization process is to increase the thickness of the through hole of the nozzle tip. Therefore, the ratio (Wn / Dn) of the thickness Wn of the nozzle tip to the diameter Dn of the nozzle tip through hole is set to 10 or more and less than 45, and the average flow velocity in the nozzle is set to 300 m / s or more. , Enabling efficient miniaturization processing.
Naturally, it is important to increase the speed in order to cause cavitation at high pressure. Although it depends on the capacity of the cylinder, it is also effective to reduce the nozzle diameter. On the other hand, due to the actual processing, when the nozzle diameter is reduced, the portion is likely to be clogged. From the viewpoint of the efficiency of processing work, it is desirable that the nozzle diameter should be at least 0.1 mm. From the example, when the nozzle diameter was large such as 0.2 mm, there were two types of laminar flow region and jet flow region inside the nozzle, and the average velocity decreased. At a practical 200 MPa injection pressure, the jet flow diameter has a maximum value, and even if the nozzle diameter is increased beyond that, the laminar flow area only increases and the average velocity tends to decrease. It was. When the nozzle diameter was 0.2 mm, the generated jet flow diameter was calculated to be 0.16 to 0.17 mm. Therefore, it was derived that a nozzle diameter smaller than that was effective for miniaturization. Even in the examples, the nozzle having a diameter of 0.2 mm did not show a high miniaturization effect.

The nozzle of the high-pressure jet processing apparatus of the present invention is a nozzle tip made of diamond in a nozzle of a high-pressure jet processing apparatus that finely sprays a raw material mixture so that the average velocity in the nozzle is 300 m / s or higher. is the nozzle to divide the thickness is composed of a plurality of nozzle chips and a plurality of nozzle holder with holes, at least one of the following 0.16 mm, and the diameter Dn _m through hole of the nozzle tip The ratio of the total thickness of the through holes of the plurality of nozzle chips to the smallest diameter among the diameters D _nm of the through holes of the nozzle chips is set to be 10 or more and less than 45.
When the nozzle tip is made of a hard material such as a diamond tip, it is very difficult and impractical to increase the thickness with a diameter of 0.16 mm or less. However, like the nozzle for the high-pressure injection processing apparatus of the present invention, when a simple nozzle configuration having a flat nozzle tip having a through hole and its holder, or a single nozzle in which nozzle tips are stacked, and a multistage configuration thereof, Easy to manufacture.

Nozzle of the high pressure injection apparatus of the present invention, the nozzle is characterized in that the size of the diameter Dn _m is composed of a plurality of different nozzle tips and a plurality of nozzle holder.
According to the present invention, (E) a combination of a plurality of nozzle tips, (F) a nozzle having a small diameter of the through hole is arranged on the most upstream side, and the other nozzles have a large diameter of the through hole. G) A nozzle having a small diameter of the through hole is arranged on the most downstream side, and the diameter of the through holes of the other nozzles is increased to some extent. By realizing the above (E), (F), and (G), efficient miniaturization processing becomes possible, and it is possible to obtain the same effect as when a nozzle tip having a substantially long through hole is used. become. In addition, by arranging a nozzle with a large through hole diameter on the upstream side and reducing the diameter of the other nozzles on the upstream side, cavitation is less likely to occur on the upstream high pressure side, and a laminar flow state with a large velocity gradient is formed. The low-energy cavitation and shear force generated by the decompressed downstream nozzle can be used. With this configuration, it is possible to perform defibration without cutting the fiber.
In this way, by combining various nozzle tips with different diameters, it becomes possible to control the flow in the vicinity of the nozzles, and use them properly depending on the application, such as nozzles suitable for miniaturization processing and nozzles suitable for defibration processing. It becomes possible.

In the nozzle of the high-pressure jet processing apparatus of the present invention, the plurality of nozzle chips are composed of a first nozzle chip and a second nozzle chip, and the second nozzle chip is downstream of the first nozzle chip. And the diameter of the through hole of the second nozzle chip is larger than the diameter of the through hole of the first nozzle chip, and is in the range of 0.16 mm or more and 0.8 mm or less. It is characterized by increasing the high-pressure region without lowering the average speed and enabling efficient miniaturization processing.
According to the present invention, in this configuration, it is not necessary to make a small hole long in a strong and hard material such as a single crystal diamond or a polycrystalline diamond used as a material for the nozzle tip, so that the manufacturing is simplified. Since it is not a complicated structure such as bonding diamond, it can be manufactured at low cost, and the flow rate can be increased because the structure is simple. For efficient miniaturization, it is very important to increase the flow speed, and stacking and multistage arrangement on a straight line are very effective.
According to the present invention, when a nozzle tip having a small diameter and large through hole cannot be formed, (E) a plurality of nozzle tips are combined, and (F) the nozzle having the small diameter of the through hole is the most upstream. By disposing the nozzles on the side and increasing the diameter of the through holes to some extent, and realizing the above (E) and (F), efficient miniaturization processing becomes possible, and a nozzle tip having a thick through hole is formed. It is possible to obtain the same effect as when used.

In the nozzle of the high-pressure jet processing apparatus of the present invention, the plurality of nozzle chips are composed of a third nozzle chip and a fourth nozzle chip arranged on the most upstream side, and the fourth nozzle chip is the first nozzle chip. And the diameter of the through hole of the third nozzle chip is larger than the diameter of the through hole of the fourth nozzle chip, and ranges from 0.16 mm to 0.8 mm. As a result, it is possible to perform a suitable defibrating process such as a fiber using a shearing force in a high-speed laminar flow without reducing the average speed in the nozzle.
According to the present invention, by disposing a nozzle tip having a large diameter on the upstream side, a state having a large laminar flow region can be formed, and defibration utilizing low energy cavitation and shear force reduced by the downstream nozzle. Processing is possible.
In this way, by combining various nozzle tips with different diameters, it becomes possible to control the energy in the nozzles, and use them properly depending on the application, such as nozzles suitable for miniaturization processing and nozzles suitable for defibration processing. It becomes possible.

In the nozzle of the high pressure injection processing apparatus of the present invention, the diameter of the through hole of the nozzle holder is 0.8 mm or less in order to maintain a high pressure region around the nozzle tip. In particular, this effect was effective when the injection pressure was as high as 200 MPa.
According to the present invention, it has been discovered that the effect of miniaturization is greater when a nozzle holder having a small diameter of the through hole is used. This is because when a nozzle holder (0.8 mm) with a small diameter of the through hole is used, the pressure drop when the raw material mixture 10 moves from the nozzle tip region to the nozzle holder region is small, so that the high pressure region is also present in the holder. This is because the portion to be refined is increased by expanding the high-pressure region.
On the other hand, when a nozzle holder (10 mm-30 mm) having a large diameter of the through hole is used, a sudden pressure change occurs when the raw material mixture 10 moves from the nozzle tip region to the nozzle holder region, and the flow is a jet flow. Rather, it was thought that it immediately shifted to a super cavitation state containing a lot of bubbles and the shearing force decreased.

The evaluation method for a high-pressure injection processing apparatus of the present invention is an evaluation method for a high-pressure injection processing apparatus that generates high-pressure injection of a raw material mixture at a predetermined pressure to produce cavitation and refines the process, and is limited to the high-pressure injection processing apparatus. An AE sensor having the frequency described above is attached, an AE signal by cavitation is detected, and performance evaluation of atomization characteristics is performed from the magnitude of the value.
According to the present invention, since the state of cavitation or the like can be evaluated by an AE signal, an AE sensor is attached to the high-pressure injection processing device, and the AE signal due to cavitation is detected to evaluate the high-pressure injection processing device such as a nozzle or a high-pressure cylinder. Can be performed easily.
7. The nozzle according to claim 1, wherein the high-pressure injection processing apparatus of the present invention performs high-pressure injection of the raw material mixture so that the average velocity in the nozzle becomes 300 m / s or more to refine or defibrate. A high pressure pump that pressurizes the raw material mixture, a drive control unit that pressurizes the raw material mixture to 100 MPa or more by driving and controlling the high pressure pump, and a high pressure cylinder, The raw material mixed liquid pressurized to 100 MPa or more is sprayed to the nozzle connected to the high-pressure cylinder, thereby miniaturizing or defibrating.
The nozzle according to any one of claims 1 to 6, wherein in the high-pressure injection processing method of the present invention, the raw material mixture is injected under high pressure so that the average velocity in the nozzle is 300 m / s or more, and is refined or defibrated. A high-pressure pump that pressurizes the raw material mixture, a drive control unit that pressurizes the raw material mixture to 100 MPa or more by driving and controlling the high-pressure pump, and a high-pressure cylinder, The drive control unit and the high-pressure pump pressurize the raw material mixture to 100 MPa or more, and spray the raw material mixture into the nozzle connected to the high-pressure cylinder, thereby miniaturizing or defibrating the raw material mixture. .
According to the inventors' experiment, the ratio (Wn / Dn) of the thickness Wn of the nozzle tip to the diameter Dn of the nozzle tip through hole is 10 or more and less than 45, and the average flow velocity in the nozzle is 300 m. It has been found that an efficient miniaturization process can be achieved by setting it to / s or more. In order to increase the average flow velocity in the nozzle to 300 m / s or more, the raw material mixture is pressurized to 100 MPa or more in a high-pressure pump, and the ratio of the nozzle tip through-hole diameter Wn to the nozzle tip through-hole diameter Dn (Wn This was realized by using a nozzle having a / Dn) of 10 or more and less than 45. Therefore, an efficient miniaturization process is enabled by using a high-pressure pump that pressurizes the raw material mixture to 100 MPa or more and setting its average speed to 300 m / s or more.

Thus, when there are many combinations of nozzle tips and nozzle holders, it is necessary to quantitatively evaluate the performance of each nozzle, high-pressure cylinder, and other devices. However, it has been very difficult to evaluate the performance of conventional apparatuses for miniaturization, and various materials have been actually processed and then evaluated with a particle size distribution meter, an electron microscope, or the like. According to the invention in Japanese Patent Application No. 2014-201744, it has been clarified that there are two types of AE signals measured, which are due to flow and those due to particles in the solution. The AE signal generated by this flow is generated from a portion where a jet flow is formed with cavitation as a base point. This portion is mainly related to the range of shearing force on the side surface of the nozzle tip. This size is unique to the nozzle, and the larger the value of the AE signal, the wider the high-pressure region related to miniaturization, and the more efficient miniaturization processing can be performed.
By measuring this AE signal by processing only a solution such as water, the state of high-pressure cavitation, shearing force, etc. can be evaluated, so an AE sensor is attached to the high-pressure jet processing device to detect the signal and By comparing, it is possible to easily perform quantitative evaluation of the miniaturization performance of the nozzle including the performance of the high-pressure generating portion of an apparatus such as a high-pressure cylinder.

According to the nozzle of the high-pressure jet processing apparatus of the present invention, an efficient miniaturization process is made possible by increasing the flow speed and increasing the thickness of the nozzle chip through hole. In addition, according to the present invention, even when a nozzle tip having a large ratio of the through hole thickness Wn of the nozzle tip to the diameter Dn cannot be manufactured, (E) a plurality of nozzle tips are combined, and (F) the diameter of the through hole is (G) A nozzle with a small diameter of the through hole is arranged at the most downstream side, and the other nozzles are arranged at the most upstream side. Increase the diameter to some extent. By realizing the above (E), (F), and (G), efficient miniaturization processing becomes possible, and it is possible to obtain the same effect as when a nozzle chip having a long through hole is used. It became. Furthermore, since it is not necessary to make long holes in a hard and hard material such as single crystal diamond, sintered diamond, and polycrystalline diamond, which are the nozzle tip materials, manufacturing is simplified.
According to the present invention, by arranging a nozzle tip having a large diameter on the upstream side, it becomes difficult to cause cavitation at a high pressure, thereby creating a laminar flow state having a large velocity gradient and generating low in the downstream nozzle. Using energy cavitation and shearing force, it becomes possible to defibrate without cutting the fiber.
In this way, by combining various nozzle tips with different diameters, it becomes possible to control the flow in the vicinity of the nozzles, and use them properly depending on the application, such as nozzles suitable for miniaturization processing and nozzles suitable for defibration processing. It became possible.

It is a block diagram which shows schematic structure of the high pressure cylinder 500 of the high pressure injection processing apparatus of this invention, the low pressure chamber 40, and the nozzle 400 periphery. It is a schematic diagram which shows the schematic structural example of the nozzle 400 of the said embodiment, (a) shows the nozzle comprised by one nozzle tip and the nozzle holder among the single nozzles N1, (b) shows the multistage nozzle N2. (Nozzle for refinement processing) is shown, (c) shows a multi-stage nozzle N3 (nozzle for defibrating treatment), and (d) shows a nozzle in which nozzle chips are stacked among the single nozzles N1. It is the schematic which shows the single nozzle N1 which is the 1st Embodiment of this invention, (a) is sectional drawing which shows the nozzle N1, (b) is thickness Wn with respect to the diameter Dn of the through-hole of a nozzle chip. In this example, the ratio (Wn / Dn) is 10. It is sectional drawing which shows the multistage nozzle N2 which is the 2nd Embodiment of this invention. It is sectional drawing which shows the multistage nozzle N3 which is the 3rd Embodiment of this invention. It is the schematic which shows the state of the fluid which generate | occur | produces in the nozzle tip Nn_sample of a nozzle, and is sectional drawing cut | disconnected by the plane parallel to the axis | shaft of a through-hole. It is a conceptual diagram which shows the state of the fluid which generate | occur | produces in the nozzle tip Nn_sample of a nozzle, and is sectional drawing cut | disconnected by the plane perpendicular | vertical to the axis of a through-hole. It is a conceptual diagram which shows the jet flow and laminar flow in a through hole at the time of using the nozzle tip from which the diameter of a through-hole differs, (a) is the inside of a through-hole at the time of using a nozzle tip with a large diameter of a through-hole. A jet flow and a laminar flow are shown, and (b) shows a jet flow and a laminar flow in the through hole when a nozzle tip having a small diameter is used. It is a graph showing the time course change of the voltage _V rms [mV] of the AE signals of various injection pressure _{P N} at the nozzle a. Is a graph showing the time course change of the voltage _V rms [mV] of the AE signals of various injection pressure _{P N} at the nozzle b. Is a graph showing the time course change of the voltage _V rms [mV] of the AE signals of various injection pressure _{P N} at the nozzle c. Is a graph showing the time course change of the voltage _V rms [mV] of the AE signals of various injection pressure _{P N} at the nozzle d. Nozzle to d, a graph representing the average velocity _v N [m / sec] changes due to various injection pressure _{P N} in h and i. Is a graph showing the voltage _V rms [mV] of the AE signal by the various injection pressure _{P N} at the nozzle to d. Is a graph showing the time course change of the voltage _V rms [mV] of the AE signals of various injection pressure _{P N} at the nozzle e. Is a graph showing the time course change of the voltage _V rms [mV] of the AE signals of various injection pressure _{P N} at the nozzle f. Is a graph showing the time course change of the voltage _V rms [mV] of the AE signals of various injection pressure _{P N} at the nozzle g. It is a graph representing the average velocity _v N changes in [m / sec] by various injection pressure _{P N} at the nozzle D-G. Nozzle c, is a graph showing the voltage _V rms [mV] change in AE signal by the various injection pressure _{P N} at E to G. It is the schematic which shows the flow of the solution which generate | occur | produces in a multistage nozzle (what combined multiple nozzle tips of the same diameter), and is sectional drawing cut | disconnected by the plane parallel to the axis | shaft of a through-hole. It is the schematic which shows the flow of the solution which generate | occur | produces in a multistage nozzle (what arrange | positioned the nozzle tip with a small diameter upstream), and is sectional drawing cut | disconnected by the plane parallel to the axis | shaft of a through-hole. It is the schematic which shows the flow of the solution which generate | occur | produces in a multistage nozzle (what arrange | positioned the nozzle tip with a large diameter upstream), and is sectional drawing cut | disconnected by the plane parallel to the axis | shaft of a through-hole. It is a flowchart which shows the operation | movement procedure of the monitoring method of the high pressure injection processing apparatus of embodiment to which this invention is applied. It is a conceptual diagram which shows the cavitation which generate | occur | produces in the nozzle part of the high pressure injection processing apparatus of embodiment to which this invention is applied. It is a figure which shows typically the process in which the particle | grains in the raw material liquid mixture injected by high pressure are atomized by cavitation collapse. It is a figure which shows the spectrum (b) of the frequency characteristic (a) of the AE sensor which concerns on this invention, and the AE signal measured at the time of injection. Is a graph showing the percentage of the cellulosic fiber diameter (nm) (Frequency percentage) ( %) present in the suspension 20 in the case of using nozzles c, and d, (a) is injection number _{N P} is 5 a case, (b) shows the case of injection number _{N P} is 20. Is a graph showing the percentage of the cellulosic fiber diameter (nm) (Frequency percentage) ( %) present in the suspension 20 in the case of using a nozzle b, c, h, (a ) is _{N P} is 5 (B) is a case where _NP is 20. Is a graph showing the nozzle b, c, a N _P dependence of the average diameter D of the cellulose fibers in the suspension 20 of the high-pressure injection process in h. _{N P} when changing the through hole diameter of the nozzle holder is a graph showing cellulose insulation diameter of 20 percent of the (nm) a (Frequency percentage) (%). It is a conceptual diagram showing the phenomenon in a nozzle by the difference in the diameter of the through-hole of a nozzle holder, (a) is a case where the diameter of the through-hole of a nozzle holder is small (0.8 mm), (b) is a nozzle holder This is the case where the diameter of the through hole is large (10 mm-30 mm). It is a graph which shows the percentage (Frequency percentage) (%) of the cellulose fiber diameter (nm) at the time of using the nozzles c, e, f, and g, (a) is a case where _NP is 5, (b ) Is the case where _NP is 20. Is a graph showing the N _P dependence of the average diameter D of the cellulose fibers when used nozzles c, e, f, and g. Is a graph showing the N _P dependence of the viscosity of the cellulose η when using various nozzles N1, N2, N3, (a ) is a case of using a single nozzle N1, the (b) multi-stage nozzle This is the case. It is a figure which shows the X-ray-diffraction pattern of the cellulose membrane produced by using the nozzle N1, N2, and N3, performing 20 times, and then drying a cellulose suspension. It is the electron microscope image of a cellulose at the time of performing a high pressure injection process using the nozzle e (M010202), (a) is a 300 times magnified image, (b) is a 5000 times magnified image. It is the electron microscope image of the cellulose which performed the high pressure injection process using the nozzle g (M020201), (a) is a 300 times magnified image, (b) is a 5000 times magnified image. It is a graph which shows the percentage (Frequency percentage) (%) of the diameter (nm) of the PZT powder at the time of using the nozzles b and c. It is a graph which shows the percentage (Frequency percentage) (%) of the diameter (nm) of the alumina fine particle at the time of using the nozzles b and c, (a) is a case where _NP is 5, (b) is N The case where _P is 10 and (c) is the case where _NP is 20. It is a graph showing the mean diameter D of the alumina particles in the suspension 20 in the injection number N _P of the high-pressure injection. Is a graph showing the relationship between the average velocity v _N in the nozzle which is measured with the injection pressure P _N, (a) is shows the actual measurement value and the theoretical value v _NJ nozzles c, (b) the nozzle d shows the actual measurement value and the theoretical value v _NJ, shows the actual measurement value and the theoretical value v _NJ (c), the nozzle i. The average velocity _v is a graph showing the relationship N [m / sec] and the AE signal voltage _V rms (effective value of AE signal voltage), (a) data of the nozzles of varying diameter and thickness of the nozzle tip through hole (B) shows the data for the multi-layer nozzle and the multi-stage nozzle, and (c) shows the data for the multi-stage nozzle. Is a graph showing the time course change of the AE signal voltage at each injection number N _P.

Hereinafter, embodiments to which the present invention is applied will be described in detail with reference to the drawings.
The inventors of the present application attach an AE sensor to the high-pressure injection processing device, detect an AE signal having a frequency of 0.2 MHz or more generated from the nozzle during high-pressure injection, and the difference in the AE signal due to the difference in nozzle hole diameter and thickness. It was investigated. When a single nozzle is used, an AE signal intensity when only water is sprayed as a solution, and a miniaturization experiment when various materials are made into suspensions having a concentration of 2 to 20%. Their relationship was examined.

(Regarding AE signal)
As described above, it has been found that the miniaturization phenomenon in the high-pressure injection processing is mainly due to cavitation and shear force generated in the high-pressure portion. Cavitation generated in the high-pressure jet processing equipment is classified into (C) low energy cavitation generated on the low pressure side, (D) high energy cavitation generated in the nozzle (C), (D). Is done. In the refinement of the particles of the raw material mixture, an essential strong action is an impact based on the collapse of the cavitation described in (D) above. Therefore, an AE signal by cavitation in (D), that is, a high frequency signal (0.2 MHz or higher) ) By using an AE sensor, the degree of particle miniaturization, the pulverization force due to the flow, and the like can be evaluated.

High-pressure injection apparatus Figure 1 for use in the present invention, the high-pressure cylinder 500 of the high-pressure injection apparatus of the present invention, is a block diagram showing the schematic configuration of the peripheral low pressure chamber 40 and nozzle 400.
In the present invention, the high-pressure injection processing device is a drive control unit for pressurizing the raw material mixture to 100 MPa or more by driving and controlling the high-pressure pump, a high-pressure pump for pressurizing the raw material mixture 10 to 100 MPa or more, It is an apparatus equipped with a raw material tank into which the raw material mixture 10 is charged and a high-pressure cylinder. The raw material mixture (and the particles 1a in 10) that has been charged and pressurized to 100 MPa or more is accelerated around the nozzle 400, and when passing through the vicinity of the nozzle, it becomes a high-speed flow and cavitation occurs. At that time, the flow is laminar, turbulent, and further, cavitation occurs at a place where the initial injection pressure is half, and a jet flow is generated. Inside the jet stream, the particles 1a are pulverized into particles 1c by high-pressure cavitation. Thereafter, in the low pressure chamber 40, a super cavitation state with a lot of bubbles is generated, and the suspension 20 having the stirred and dispersed particles 1c is generated. Here, since the pressure energy of injection is converted into kinetic energy and eventually becomes heat, a heat exchanger or the like for cooling the suspension is inserted. A known apparatus can be applied as the high-pressure jet processing apparatus. An arrow indicated by reference numeral 600 indicates a main propagation path of the AE signal.
Next, the raw material mixed solution 10 is charged into the raw material tank, the raw material mixed solution 10 is pressurized to 100 MPa or more with the high-pressure pump, and the raw material mixed solution 10 is injected from the nozzle 400, whereby particles 1 a is further refined to become fine particles 1 b, which are made into a suspension 20, and the suspension 20 is discharged from the outlet 402. This process is repeated until 1c in FIG. 25C or until the limit of miniaturization. This is referred to as injection number _{N P.} The process is highly effective, saying that N _P for obtaining the fine particles of the same diameter is small.
The chamber 40 includes various types such as a single nozzle chamber, an oblique collision chamber, and a ball collision chamber.
Further, it is possible to perform performance evaluation of devices such as nozzles and high pressure cylinders by attaching the monitoring device 1 of the high pressure injection processing device to the high pressure injection processing device. In that case, an AE sensor 9 attached to the high-pressure injection processing device and an AE signal detected from the AE sensor 9 are processed to include signal processing determination means 8 for determining performance evaluation of the device.

  The raw material mixture 10 is, for example, a mixed solution of particles 1a (raw material) and water or an organic solvent. Depending on the application, a surfactant may be included. In the present invention, the particles 1a (raw material) contained in the raw material mixture 10 are titanium oxide, barium titanate, ferrite, alumina, silica, PZT (lead zirconate titanate), and other known metals, oxides, and carbides. Fine particles are mentioned. It is also possible to use a fiber-shaped material such as cellulose or carbon nanotube CNT. The raw material mixture 10 is a suspension liquid containing the fine particles and their aggregates.

FIG. 2 is a schematic diagram illustrating a schematic configuration example of the nozzle 400 of the above-described embodiment, in which (a) illustrates a nozzle composed of one nozzle tip and a nozzle holder, and (b) illustrates a single nozzle N1. A multi-stage nozzle N2 (miniaturization nozzle) is shown, (c) is a multi-stage nozzle N3 (defibration nozzle), and (d) is a nozzle in which nozzle chips are stacked in the single nozzle N1. Indicates.
The nozzle N1 is a single nozzle, and is composed of a nozzle (FIG. 2A) composed of one nozzle chip Nn and one nozzle holder Nh, a plurality of stacked nozzle chips Nn and one nozzle holder Nh. There is a nozzle (FIG. 2 (d)).
The nozzles N2 and N3 (FIGS. 2B and 2C) include a plurality (multi-stage) nozzle tips Nn _m (m = 1, 2,..., M) and a plurality (multi-stage) nozzle holders Nh _m ( m = 1, 2,..., M) to form nozzles N2, N3.
The nozzle N2 is reduced most the diameter Dn ₁ through hole nozzle tip Nn ₁ located most upstream side, the other nozzle tip _{Nn 2,} Nn 3, · · ·, the diameter of the through hole of Nn _M Dn ₂ , Dn ₃ ,..., Dn _M are nozzles that can be efficiently miniaturized by making the value larger than the diameter Dn ₁ of the through hole of the nozzle tip Nn _1. .
The nozzle N3 is to reduce the diameter Dn _M through hole of the nozzle tip Nn _M located most downstream side, the other nozzle tip _{Nn 1,} Nn 2, · · ·, the through hole of _{Nn M-1} diameter Dn ₁ , Dn ₂ ,..., Dn _M-1 are nozzles that are optimal for the defibrating process by making the values larger than the diameter Dn _M.

(First embodiment of the present invention)
As a high-pressure injection device, a starburst mini HJP-25001 from Sugino Machine was used, and a ball collision chamber was used for all low-pressure cambers.
Nozzle FIGS. 3A and 3B are schematic views showing a single nozzle N1 according to the first embodiment of the present invention, FIG. In this example, the ratio of the thickness Wn to Dn (Wn / Dn) is 10.
The nozzle N1 is a single nozzle composed of a nozzle tip Nn having a thickness Wn and a through hole diameter Dn, and a nozzle holder Nh having a through hole thickness Wh and a through hole diameter Dh.
The nozzle tip Nn is connected to the raw material tank 103 on the upstream side and the nozzle holder Nh on the downstream side, and a cylindrical through hole is provided at the center of the nozzle tip Nn. The nozzle tip Nn is made of a hard material such as single crystal diamond, polycrystalline diamond, or sintered diamond.
The nozzle holder Nh is a holder for fixing the nozzle tip Nn, the upstream side is attached to the high pressure cylinder portion, and the downstream side is connected to the low pressure chamber 4. Similarly to the nozzle tip Nn, a cylindrical through hole is provided at the center of the nozzle holder Nh. The material of the nozzle tip Nh is a SUS metal such as SUS630.
A single nozzle is composed of one nozzle chip Nn and one nozzle holder Nh (FIG. 2A), or a nozzle composed of a plurality of stacked nozzle chips Nn and one nozzle holder Nh (see FIG. 2). 2 (d)).
Here, Dh of the nozzle holder is the diameter of the through hole where the nozzle tip Nn is not fixed, and Wh of the nozzle holder is the thickness of the through hole where the nozzle chip Nn is not fixed. It is.
Dn of the nozzle tip is preferably 0.2 mm or less, more preferably 0.1 mm to 0.16 mm (0.16 mm or less) in order to increase the flow rate in the nozzle N1. The Wn of the nozzle chip is determined so that the ratio (Wn / Dn) of Dn and Wn of the nozzle chip is 10 or more (FIG. 3B). Actually, since the through-hole does not have a uniform diameter, the minimum diameter is denoted as Dn.
The nozzle tip Dn and the nozzle holder Dh are formed such that the nozzle tip through hole diameter Dn ≦ the nozzle holder through hole diameter Dh. In an embodiment of the present invention, Dn of the nozzle tip is 0.1 mm, and Dh of the nozzle holder is 0.8 mm. The nozzle tip Wn is 0.9 to 4.5 mm, and the nozzle holder Wh is 5 mm.

(Experimental example 1)
Experimental example 1 of single nozzle N1
In Experimental Example 1, the nozzle a which is a conventional product and the nozzles b, c and d of the high pressure injection processing apparatus of the present invention (Table 1) are used, and the AE sensor is used as the nozzle a to the high pressure injection processing apparatus. It is attached to a place where ultrasonic waves generated at d can be detected, and the injection pressure P _N [MPa] (P _N : 50, 100, 150, 200, 240) (injection pressure P _N from the nozzles a to d of the high-pressure injection processing device. : The raw material mixture was subjected to high-pressure jetting treatment while changing the initial pressure when the liquid was jetted from the nozzle inlet into the nozzle. Then, when performing the high-pressure injection process, an ultrasonic wave having a frequency of 0.2 MHz or more generated in the nozzle hole is detected by the AE sensor, a signal level from the AE sensor is detected, and each injection pressure over time The change in the AE signal voltage of _PN was measured.

The results are shown in FIGS.

9 to 12 are graphs showing changes over time of the AE signal voltage V _rms using various injection pressures _PN as parameters when the nozzles a to d are used.
In the nozzle a, the Wn of the nozzle tip is short and the Dh of the nozzle holder is abruptly larger than the Dn of the nozzle tip. Therefore, even if the injection pressure _PN changes, the AE signal V _rms is about 80 mV. It did not change greatly. When the nozzle b is used and the Dh of the nozzle holder is reduced to 0.8 mm, a slight decrease in V _rms can be seen when the injection pressure _PN is 150 MPa, but at 200 MPa, the V _rms is 120 to 150 mV. It became bigger. When the nozzle tip Wn is thickened to 1.5 mm in the nozzle c, no change is observed when the _PN is as low as 50 MPa. However, when the _PN is 100 MPa or more, the V _rms is rapidly as 130 mV. Became bigger. Furthermore, when it was 240 MPa, it became large to 190 mV. In the nozzle d, when the Dn of the nozzle tip was increased to 0.2 mm, when the _PN was as small as 50 MPa, the V _rms was as large as 100 mV, but even if the _PN was increased, it did not exceed 140 mV. Moreover, it was not larger than V _rms of a nozzle having _PN of 100 MPa or more and Dn of 0.1 mm. From these results, it was shown that V _rms tends to be larger when the nozzle tip Dn is 0.1 mm and larger when the nozzle tip Wn is thicker than when the nozzle tip Dn is 0.2 mm. Further, it was found that the value of V _rms increases as the Dh of the nozzle holder is as small as 0.8 mm.

(Experimental example 2)
Experimental example 2 of single nozzle N1 (stacking nozzle)
Three nozzle chips used in the nozzle c shown in (Table 1) were stacked, and the nozzles h and i shown in (Table 2) below (FIG. 2 (d)) and ad shown in (Table 1) were subjected to high-pressure injection processing. It is attached to the apparatus and the injection pressure P _N [MPa] (P _N : 50, 100, 150, 200, 240) (injection pressure P _N : initial pressure when liquid is injected into the nozzle from the nozzle inlet) is changed. The raw material mixture was subjected to high-pressure injection treatment. The average speed v _N and the AE signal voltage V _rms (effective value of the AE signal voltage) due to the change in _PN were measured.
FIG. 13 is a graph showing a change in average velocity v _N [m / sec] due to various injection pressures P _{N at} the nozzles a to d, h and i, and FIG. 14 is a graph showing the change in P when the nozzles a to d are used. ₅ is a graph showing changes in V _rms [mV] due to _N.
In the nozzle with Dn of 0.1 mm, v _N showed the same value even when Wn was increased from 0.9 mm to 1.5 mm (Wn / Dn was 9 to 15). Nozzle tip and three stacked, in the case of the nozzle h was the Wn and 4.5 mm (Wn / Dn is 45), _{v N} was smaller. On the other hand, Dn is the case of 0.2 mm, Wn / Dn is a 7.5, _{v N} became drastically reduced.
In the laminated nozzle h (Wn / Dn is 45), by which to increase the Wn of the nozzle tip, _{v N} has become slower, exceeding the 300 meters / s is, _{P N} was from above 150 MPa. In Dn is 0.15mm nozzle i (Wn / Dn is 30), increasing the three stacked Wn nozzle tip, _{P N} is below 150 MPa, _{v N} was not become so small. v To increase the value of _N is, Dn is a 0.15mm or less, Wn is also an important parameter, for its Wn was found that there is an optimum range.

Figure 14 is a graph showing the voltage _V rms [mV] of the AE signal by the various injection pressure _{P N} at the nozzle to d.
When Dn was 0.1 mm, V _rms suddenly increased when Wn was increased from 0.9 to 1.5 mm. If a smaller Dh at this Dn, _{P N} is _{V rms} in the range of 50~150MPa decreases, at 200MPa higher than _{P N, V rms} increased. On the other hand, when Dn was increased to 0.2 mm, V _rms tended to decrease. It was found that the value of V _rms is related to the value of Wn. In Dn is 0.2mm Considering the results of FIG. 13, _v from the value of _N is rapidly _reduced, was found to be important also the magnitude of _{v N} is the value of _{V rms.}

Experimental Example 1, the results of Experimental Example 2, when using the nozzle d (nozzle tip Dn large as 0.2mm and was) a flow velocity _{v N} becomes _{slower, V rms} also becomes smaller. As a result, it was confirmed that Dn and Wn of the nozzle tip strongly depend on the magnitude of the AE signal voltage V _rms indicating the amount of high voltage cavitation.
As described above, Dn of the nozzle tip is an important parameter in the high-pressure injection processing apparatus, and in the miniaturization processing using high-pressure cavitation, Dn is small, Wn is as small as possible, and Wn / Dn is 10 or more. It was shown to be effective.
The actual through hole has a thickness dependency, but here, the minimum diameter of the nozzle tip is Dn.

(Second embodiment of the present invention)
Multi-stage nozzle (nozzle for miniaturization)
FIG. 4 is a cross-sectional view showing a multi-stage nozzle N2 according to the second embodiment of the present invention.
The nozzle N1 according to the first embodiment is a single nozzle composed of one nozzle holder and a nozzle tip. From the results of Example 1 and Example 2, it was found that the nozzle tip having a small Dn, a Wn as thick as possible, and a Wn / Dn of 10 or more is effective for the miniaturization process using high-pressure cavitation. However, it is very difficult to form a small Dn with a thick Wn in a single crystal diamond, a sintered diamond, a polycrystalline diamond or the like, which is a material of the nozzle tip.
Therefore, the nozzle N2 of the present invention includes a plurality (multi-stage) nozzle tips Nn _m (m = 1, 2,..., M) and a plurality (multi-stage) nozzle holders Nh _m (m = 1, 2,... ., M) are combined to form the nozzle N2. This enables the same effect as the nozzle N1 of the first embodiment, and the other configurations are the same as those of the first embodiment. Therefore, the same reference numerals are assigned to the same configurations. Description is omitted.

The nozzle N2 is composed of a plurality of nozzle tips Nn _m (m = 1, 2,..., M) and a plurality of nozzle holders Nh _m (m = 1, 2,..., M). _Nn 1 to the downstream _{side, Nh 1, Nn 2, Nh} 2, Nn 3, Nh 3, ···, Nn M, mounted side by side in the order of Nh _M, wherein the through hole of the nozzle tip Nn _m nozzle through hole of the holder Nh _m is formed all so as to be coaxial.
The number M of the nozzle tips Nn _m (m = 1, 2,..., M) and the nozzle holder Nh _m (m = 1, 2,..., M) is preferably 2 or more. More preferably.
A cylindrical through hole is provided at the center of the nozzle tip Nn _m (m = 1, 2,..., M). The material of the nozzle tip Nn _m is or a single crystal diamond, a sintered diamond, polycrystalline diamond or the like.
The nozzle holder Nh _m is a holder for fixing the nozzle tip Nn _m, upstream is attached to the high-pressure cylinder unit 500, the downstream side is connected to the chamber 400. Wherein in the center portion of the nozzle holder Nh _m nozzle tip _{Nn m (m = 1,2, ···} , M) similarly to cylindrical through hole. The material of the nozzle tip Nh _m is SUS-based metal such as SUS630.
The nozzle tip Nn ₁ located on the most upstream side is an inlet for flowing the pressurized raw material mixture 10 into the chamber 40, and the upstream side is connected to a pipe from the raw material tank 103, and the downstream side Is attached to the nozzle holder Nh ₁ .
The diameter Dn _m (m = 1, 2,..., M) of the nozzle chip Nn _m is preferably 0.2 mm or less in order to increase the flow velocity in the nozzle N2. Further, to reduce most the diameter Dn ₁ through hole nozzle tip Nn ₁ located most upstream side, the other nozzle tip _{Nn 2, Nn 3, ···,} Nn M diameter _Dn 2 through holes of Dn ₃ ,..., Dn _M is a value larger than the diameter Dn ₁ as shown in (Equation 5).

The diameter Dn ₁ is preferably 0.1 mm to 0.16 mm (0.16 mm or less), and the other Dn _m (m = 2,..., M) is preferably 0.16 mm to 0.8 mm. .2 mm is more preferable.
Further, the through hole thickness Wn _m (m = 1, 2,..., M) of the nozzle chip Nn _m is equal to the diameter Dn ₁ of the through hole of the nozzle chip Nn ₁ as shown in (Equation 4). compared the nozzle tip Nn _m through hole in the thickness _Wn m to (m = 1,2, ···, M ) total sufficiently to increase the (the diameter Dn ₁ through hole of the nozzle tip Nn ₁ of the nozzle The total ratio of the through-hole thicknesses Wn _m (m = 1, 2,..., M) of the chip Nn _m is 10 or more) (Equation 6).

(5), by using a nozzle tip Nn _m, such as (6), without forming a nozzle tip with a long through-hole diameter is small and the length is shorter (E) Length (E), (F), wherein a plurality of nozzle tips having through holes are combined, (F) a nozzle having a small diameter of the through hole is arranged on the most upstream side, and the diameters of the other nozzles are increased to some extent. By realizing the above, efficient miniaturization processing becomes possible, and it becomes possible to obtain the same effect as when a nozzle chip having a long through-hole is used. Further, since it is not necessary to make a long hole in a hard and hard material such as single crystal diamond, sintered diamond, and polycrystalline diamond which are hard materials for the nozzle tip, the manufacturing is simplified.

(Third embodiment of the present invention)
Multi-stage nozzle (nozzle for defibrating treatment)
FIG. 5 is a sectional view showing a multi-stage nozzle N3 according to the third embodiment of the present invention.
The nozzle N2 according to the second embodiment is a multistage nozzle in which a nozzle tip having a small diameter is arranged on the upstream side, and enables efficient miniaturization processing. The multistage nozzle of the present invention N3 forms a nozzle for defibrating treatment by disposing a nozzle tip having a large diameter on the upstream side. Since the other configuration is the same as that of the second embodiment, the same reference numeral is assigned to the same configuration, and description thereof is omitted.

The nozzle N3 is composed of a plurality of nozzle tips Nn _m (m = 1, 2,..., M) and a plurality of nozzle holders Nh _m (m = 1, 2,..., M). in _Nn 1 from the upstream side to the downstream _{side, Nh 1, Nn 2, Nh} 2, Nn 3, Nh 3, ···, Nn M, mounted side by side in the order of Nh _M, through the nozzle tip Nn _m through hole of the a hole nozzle holder Nh _m is formed all so as to be coaxial.
The number M of the nozzle tips Nn _m (m = 1, 2,..., M) and the nozzle holder Nh _m (m = 1, 2,..., M) is preferably 2 or more. More preferably.
The nozzle tip Nn ₁ located on the most upstream side is an inlet for injecting the pressurized raw material mixture 10 into the chamber 40, and the diameter of the through hole of the nozzle tip Nn ₁ located on the most upstream side. increasing the dn _1, nozzle tip _Nn 2 disposed from the upstream side to the downstream side, ..., the diameter _dn 2 through holes of _{Nn M-1,} ..., a _{dn m-1} of the nozzle tip Nn ₁ similar or size as the diameter Dn ₁ through hole or a small value. Then, the diameter Dn _M through hole of the nozzle tip Nn _M which is located on the most downstream side, the diameter _Dn 1 other nozzle tip through _holes, Dn 2, · · ·, to a value smaller than _{Dn m-1} (Equation 7).

The diameters Dn ₁ , Dn ₂ ,..., Dn _m-1 are preferably 0.16 mm or more and 0.8 mm or less, and more preferably 0.2 mm. The most downstream Dn _M is preferably 0.1 mm to 0.16 mm (0.16 mm or less).

By using the nozzle tip Nn _M as shown in (Equation 7), the injection pressure is divided, and the fiber solution using the shear force in the laminar flow at a high pressure and the slightly low energy cavitation due to the pressure loss. It becomes possible to perform fiber processing.

Thus, by combining various nozzle tip Nn _m having different diameters, it becomes possible to control the energy in the nozzle, the nozzle and for fine processing, nozzles or the like for defibration treatment, be selected depending on the usage It becomes possible.

(Experimental example 3)
Experimental example 3 of multi-stage nozzle N2
Nozzles N2 used in Experimental Example 3 is a nozzle of the three stages (M = 3), a nozzle tip Nn _m used were as follows in Table 3.

As the nozzle e, the most upstream nozzle tip Nn _{1 having} a diameter Dn ₁ of the through hole of 0.1 mm is used, and the other nozzle tips Nn ₂ and Nn ₃ are larger than Dn ₁ . Those having a diameter Dn ₂ and Dn ₃ of ₂ mm were used.
As the nozzle f, nozzles having diameters Dn ₁ , Dn ₂ , Dn ₃ of 0.1 mm for all the nozzle tips Nn ₁ , Nn ₂ , Nn ₃ were used.
The nozzle g is a nozzle hole having a diameter Dn ₁ , Dn ₂ of 0.2 mm in the through hole of the nozzle chip Nn ₁ on the most upstream side and the nozzle chip Nn ₂ positioned adjacent thereto, and the through hole of the nozzle chip Nn ₃ is used. the diameter Dn ₃ were from smaller 0.1mm than the diameter _Dn 1, _{Dn 2.}
In all the nozzles e to g, the total of the through hole thicknesses Dn ₁ , Dn ₂ , Dn ₃ of the nozzle tips Nn ₁ , Nn ₂ , Nn ₃ was 4.5 mm.

In Experimental Example 3, in the high pressure injection processing apparatus using the nozzles e to g, an AE sensor is attached to a place where ultrasonic waves generated by the nozzles e to g of the high pressure injection processing apparatus can be detected, and the nozzle of the high pressure injection processing apparatus The raw material mixture was subjected to high-pressure injection processing while changing the injection pressure P _N ( _PN : 50, 100, 150, 200, 240) from e to g. Then, when performing the high-pressure injection process, ultrasonic waves from the nozzles were detected by the AE sensor, and the AE signal voltage V _rms when each injection pressure _PN was used as a parameter was measured. The results are shown in FIGS.

15 to 17 is a graph showing the time course change of the AE signal voltage _{V rms} of the injection pressure _{P N} at the nozzle E to G.
V _rms (FIG. 16) when a nozzle f having a multistage configuration of nozzle tips Nn ₁ , Nn ₂ , Nn ₃ having a small diameter Dn ₁ , Dn ₂ , Dn ₃ of 0.1 mm is 0.1 mm Only V _rms smaller than V _rms (FIG. 11) in the case of using the nozzle c having a single nozzle tip Nn with Dn was obtained. In addition, V _rms (FIG. 17) in the case where a multistage nozzle g in which nozzle tips Nn ₁ and Nn ₂ having diameters Dn ₁ and Dn ₂ of 0.2 mm are arranged on the upstream side is used is 0.2 mm in diameter. The value was close to V _rms (FIG. 12) when the nozzle d having a single nozzle nozzle Nn having Dn was used. When V _rms (FIG. 15) using a multi-stage nozzle e in which a nozzle tip Nn ₁ having a diameter Dn ₁ of 0.1 mm is arranged on the upstream side is used, the nozzle tip Nn having a Dn of 0.1 mm is Compared to the case where the nozzle c having a single configuration is used (FIG. 11), a large value can be obtained, and even if the injection pressure _PN is a low pressure value of 50 MPa, a large signal with V _rms of about 220 mV. It was possible to get
_Vrms was increased by disposing a nozzle tip having a smaller diameter on the upstream side and placing a nozzle tip having a larger diameter on the downstream side than the upstream side.

(Experimental example 4)
Experimental example 4 of multi-stage nozzle N2
Using the nozzles d to g used in Experimental Example 1 and Experimental Example 3, the average speed v _N due to the change of P _N (P _N : 50, 100, 150, 200, 240) and the AE signal voltage V _rms (AE The effective value of the signal voltage was measured. The results are shown in FIGS.

Figure 18 is a graph showing the average speed _v changes in N [m / sec] by various injection pressure _{P N} in the nozzle D-G, Figure 19, the nozzle c, AE by various injection pressure _{P N} at e~g It is a graph showing voltage _Vrms [mV] change of a signal.
When a multi-stage nozzle g having nozzle chips Nn ₁ and Nn ₂ having 0.2 mm Dn ₁ and Dn ₂ on the upstream side is used, or a nozzle chip Nn ₁ having 0.1 mm Dn ₁ on the upstream side is used. The v _N (FIG. 18) of the arranged multi-stage nozzle e was the same as v _N when the nozzles a, b, c having a single nozzle tip Nn having a Dn of 0.1 mm were used. However, when using the nozzle f having a multi-stage nozzle tip Nn ₁ , Nn ₂ , Nn ₃ having 0.1 mm Dn ₁ , Dn ₂ , Dn ₃ , v _N is 80% of the theoretical value v _NJ . Decreased to.

Consideration of the results of Experiments 1 to 4 V _rms increased when the nozzle tip became thick (in the case of a single configuration) and when a nozzle tip with a small diameter was placed on the upstream side and the downstream side thereafter This is the case where a nozzle tip having a large diameter is arranged (in the case of a multi-stage configuration). With respect to v _N, in the case of sole structure depends on the diameter of the nozzle tip, as v _N diameter is smaller is larger. For multi-stage configuration, the nozzle tip of the same diameter only when placed in multiple stages v _N slowed. In this case, a phenomenon of clogging often occurred during the experiment, and this configuration was found to be inferior in practicality.
V _N when diameter is arranged different nozzle tips in multiple was the same as v _N in the case of using the nozzle tip having a minimum diameter of the arranged nozzle tip alone.

Consideration of relationship between injection pressure and solution speed Here, in order to consider the speed of _PN and the speed of the solution in the nozzle, v _{NJ with} respect to _PN when nozzles c (S01L15) and d (S02L15) in Table 1 are used. (occurs cavitation at half the injection pressure P _N, the speed in the case of the process when passing through the nozzle at that rate: theory) performs calculation of were compared with the measured value (measured). In FIG. 41, a theoretical value assumed to form a jet flow at half the above-described injection pressure and pass through the nozzle at that speed is indicated by a broken line with v _NJ , and a measured value v _N is indicated by a solid line.

(A) shows the nozzles c, (b) the nozzle d, the measured value _{v N} and _{v NJ} (c), the nozzle i. Wn / Dn is 15 of (a) _{v N was} very good agreement to _{v NJ.} In Wn / Dn is 30 (c), _{v N} has been reduced by about 10% in the high pressure _{P N} is 200 MPa, it becomes the same value in the low pressure 100 MPa. On the other hand, it becomes greater as the Wn / Dn is 45 (b), resistance increases, _{v N} was reduced from _{v NJ.} If Wn / Dn is less than 45, the injection pressure _{P N} is at least 100 MPa, _{v N} were able to more 300 meters / s.
Further, when the nozzle multi-stage configuration, since the Dn have the same v _N minimum diameter of the nozzle tip, in place after the jet stream is generated, indicated and that the fluid resistance is small, It was confirmed that there was no problem with this model. It was shown that in order to achieve high-efficiency miniaturization, a nozzle configuration in which v _N in the nozzle is close to v _NJ is necessary.

(Experimental example 5)
Consideration on the state of fluid in the nozzle when the nozzle hole diameter is changed (Experimental Example 5)
Next, the nozzles c (Dn: 0.1 mm, Wn: 1.5 mm), nozzles d (Dn: 0.2 mm, Wn: 1. The flow rate in the nozzle (5 mm) was calculated from the processing time. The results are shown in Table 4.
Table 4 shows the state of fluid in the nozzle when the nozzle c (Dn: 0.1 mm, Wn: 1.5 mm) and the nozzle d (Dn: 0.2 mm, Wn: 1.5 mm) are used. is there.
Here, it is assumed that the velocity of the laminar flow region in the nozzle is much smaller than the velocity of the jet flow region, and the average in the nozzle when _PN is changed by 50, 100, 150, 200, 240. from the speed v _N, it was carried out an estimate of the diameter of the jet flow in the nozzle. At this time, the jet flow velocity was calculated as a pressure half of the injection pressure. v _N a cylinder capacity, that is, by dividing the one processing capacity by the product of the nozzle diameter and the processing time can be easily calculated.
The 0.1mm nozzles, but of course the diameter of the jet flow is almost the same as 0.099mm in the range of 240MPa from _{P N} is 50, the 0.2mm nozzles, in the range of 200MPa from _{P N} 50 0. It was calculated as 167 to 0.170 mm.

From this result, it is considered that a nozzle having a diameter larger than the maximum diameter of the jet flow is not suitable for strong miniaturization because a large shear force cannot be obtained because a laminar flow of liquid is caused on the side wall. This is the diameter of v _N is large nozzle tip through hole is equal to or less than 0.16 mm, shows that the high atomization efficiency.

Consideration on the state of the fluid in the nozzle From these results, the results of considering the state of the flow in the nozzle are shown in FIGS. Here, a schematic view showing the flow state of the fluid generated in the nozzle tip Nn_sample of the nozzle is shown, FIG. 6 is a cross-sectional view cut along a plane parallel to the axis of the through hole, and FIG. It is sectional drawing cut | disconnected by the perpendicular plane.
In the nozzle tip Nn_sample of the nozzle, the following two fluid flows are mainly generated (G) and (H).
(G) Jet flow: “Jet flow” is a fast flow region generated at the axial center when the flow direction is the axis in the raw material mixture. A jet stream is defined as one that includes bubbles due to cavitation at the boundary of the region around the slow side surface (laminar flow). The flow of the raw material mixture injected at a high pressure changes from laminar flow to turbulent flow and jet flow. Although the speed change (unevenness) in the generated jet flow is small, the speed difference at the boundary of the jet flow is large, and here, a large shearing force works and a fine phenomenon occurs in this peripheral portion. An AE signal is also generated. In this part, the fluid resistance is low because gas is passed through the boundary.
(H) Laminar flow: “Laminar flow” is a steady continuous flow that is generated in the peripheral region of the side surface of the nozzle through-hole when the nozzle diameter is large, and is generated around the jet flow region. Resistance is high.
In the vicinity of the inlet of the raw material mixture of the nozzle tip Nn_sample of the nozzle, the pressure of the solution pressurized to high pressure is converted to kinetic energy (energy conservation law), and the solution is depressurized in the process. When the solution exceeds a certain speed, cavitation occurs, and a jet flow region and a laminar flow region are generated in the vicinity of the nozzle tip Nn_sample (FIG. 6).
It is considered that there is a large speed difference at the boundary between the jet flow region and the laminar flow region, and a strong refining action occurs. In order to improve the atomization efficiency, expanding the jet flow area without causing a bubble state due to super cavitation, that is, using a nozzle tip with a high speed and a thick through-hole improves the atomization characteristics. validate.
On the other hand, an early laminar flow portion at high pressure can be used for soft defibration treatment due to a large velocity gradient in the laminar flow.

FIG. 8 is a conceptual diagram showing the difference between the jet flow and laminar flow in the through-hole when using nozzle tips with different through-hole diameters, and (a) uses a nozzle tip with a large through-hole diameter Dn. (B) shows the jet flow and laminar flow in the through hole when a nozzle tip having a small diameter Dn is used.
Summarizing the above, it can be seen that the laminar flow portion becomes larger when the diameter of the nozzle hole is increased.
(I) Since the nozzle c of 0.1 mm with a small Dn generates almost a jet flow in the entire through hole, it is used for miniaturization processing using a high-pressure cavitation region generated at the boundary between the jet flow region and the laminar flow region. (FIG. 8B).
(J) Since a jet flow is generated only in the central portion of the nozzle d having a large Dn of 0.2 mm, it is used for defibrating treatment by using a laminar flow having a low velocity around the nozzle d (FIG. 8 ( a)).
In this way, by changing the diameter of the through hole, it is possible to switch between the use for fine processing and the use for defibrating processing.

FIG. 20 is a schematic diagram showing a flow of a solution generated in a multistage nozzle f (a combination of a plurality of nozzle tips having the same diameter) when a multistage nozzle is used . It is sectional drawing cut | disconnected by the plane parallel to the axis | shaft of a through-hole. FIG. 21 is a schematic view showing a flow of a solution generated in a multi-stage nozzle e (a nozzle tip having a small diameter arranged upstream), and is a cross-sectional view cut along a plane parallel to the axis of the through hole. is there. FIG. 22 is a schematic view showing a flow of a solution generated in a multistage nozzle g (with a nozzle tip having a large diameter on the upstream side), and is a cross-sectional view cut along a plane parallel to the axis of the through hole. is there.
Regarding the state of the fluid in the nozzle when a multi-stage nozzle is used, the diameters Dn ₁ , Dn ₂ , Dn ₃ of all the nozzle tips Nn ₁ , Nn ₂ , Nn ₃ are set as in the nozzle f. When the same one is used, the flow velocity is reduced (FIG. 18) and the effect of miniaturization is reduced (FIG. 16) due to collision loss between the jet flow generated upstream and the downstream nozzle (FIG. 20). It is thought that. Specifically, by the time the jet flow generated at the first nozzle tip reaches the next nozzle tip, the surrounding laminar flow is entrained and the diameter of the high-speed flow increases, and a collision occurs at the nozzle tip. This is probably because The same phenomenon occurs due to the deviation of the nozzle tip axis. Therefore, it is understood that it is important to increase the diameter of the nozzle tip on the downstream side in consideration of the expansion of the jet flow diameter when performing efficient miniaturization processing.
On the other hand, in the nozzle tip Nn ₁ on the most upstream side like the multi-stage nozzle e, _one having a small diameter Dn ₁ of the through hole is used, and the other nozzle tips Nn ₂ and Nn ₃ on the downstream side have a diameter Dn _1. When the larger diameters Dn ₂ and Dn ₃ are used, the speed reduction due to the collision with the jet flow does not occur, so there is no speed reduction (FIG. 21), and the miniaturization efficiency is expected to increase (FIG. 15). .
Further, the most downstream nozzle tip, such as the multi-stage nozzle g, having the largest diameter Dn ₁ , Dn ₂ of the nozzle tip Nn ₁ on the most upstream side and the nozzle tip Nn ₂ located adjacent thereto is used. limiting diameter Dn ₃ through hole of nn _3, when using smaller than the diameter _Dn 1, Dn _2, greater nozzle tip _nn 1 of the upstream side diameter, the nn within _2, the flow rate in the nozzle of a small diameter In the nozzle tips Nn ₁ and Nn ₂ , there is little jet flow and most of them are laminar flow regions. At this time, a jet flow is generated in the nozzle tip Nn ₃ , but part of the energy is converted into a velocity in the nozzle tips Nn ₁ and Nn ₂ , and the laminar flow region has a large resistance and a pressure loss, so that the diameter is small. In the nozzle tip Nn ₃ , the pressure is reduced by the pressure loss of the nozzle in the high pressure portion. The magnitude of the AE signal decreases (FIG. 17).

Nozzle evaluation of high-pressure injection processing apparatus using AE monitoring apparatus (monitoring method of the present invention)
The high-pressure injection processing apparatus of the present invention can evaluate the performance of apparatuses such as nozzles and high-pressure cylinders from AE signals by cavitation using an AE monitoring apparatus.
FIG. 23 is a flowchart showing a work procedure of the monitoring method of the high-pressure injection processing apparatus according to the embodiment to which the present invention is applied. In the present embodiment, first, the AE sensor is attached to a place where ultrasonic waves generated by the nozzles of the high-pressure injection processing apparatus can be detected (step S1). When the high frequency ultrasonic wave generated by the nozzle passes through the suspension and can be propagated by the high pressure cylinder, the nozzle and the chamber member, it may be attached to any of them. Next, the raw material mixture is subjected to high-pressure injection processing at a predetermined pressure from the nozzle of the high-pressure injection processing device (step S2). Then, an ultrasonic wave having a frequency of 0.2 MHz or more generated in the nozzle when performing the high-pressure injection process is detected by the AE sensor, and the signal level from the AE sensor is evaluated (step S3). Then, it is determined whether or not the high-pressure injection process is repeated (step S4).
Signal level from the AE sensor to be measured, and the fluid cavitation signal AE _s generated from the high-speed solution, the sum of the particle cavitation signal AE _p generated from the particles in the nozzle, ultrasonic propagation characteristic (attenuation ratio) It will reflect Att _u . Therefore, the measured signal strength AE _m is represented by the following equation: AE _m = (AE _s + AE _p ) × Att _u .
In this equation, when the material concentration in the suspension is high, the AE _p increases and the change in particle size can be accurately captured. On the other hand, when the suspension concentration is low, AE _s increases, and thus AE _p having particle size information is buried. Therefore it can not be the exact evaluation of the particle, the AE _s indicates the phenomenon of peripheral nozzles is believed that the efficiency of the device is increased by it greatly. That is, the magnitude of the AE signal can be used for nozzle evaluation. This measurement can be evaluated once with only the solution.

Monitoring Device of the Present Invention FIG. 24 is a conceptual diagram showing signals generated by cavitation detected by the monitoring device of the high pressure injection processing apparatus of the embodiment to which the present invention is applied. A cavitation signal AE _s generated from the liquid in the signal, the cavitation signal AE p generated from the _particles, further, their ultrasonic propagation characteristics (attenuation ratio) Att _u is described. The present embodiment is a monitoring device 1 of a high-pressure injection processing device that atomizes particles by high-pressure injection of a raw material mixture 10 from a nozzle 400 at a predetermined pressure, and includes an AE sensor 9 attached to the high-pressure injection processing device and the AE sensor 9 includes a signal processing determination unit 8 that processes and determines the AE signal detected from 9. The AE sensor 9 is a resonant AE sensor having a resonant frequency of 0.5 MHz. Examples of the signal processing determination means 8 include an AE tester, an FFT analyzer, a spectrum analyzer, a digital oscilloscope, and other effective value calculation recording / displaying devices. The AE signal is processed to improve the performance of a nozzle, a high pressure cylinder, and the like. A program for judging is also included.
In FIG. 24, reference numeral 500 denotes a high-pressure cylinder portion, and reference numeral 400 denotes a nozzle.

  In FIG. 24, the flow rate of the liquid in the nozzle 400 can be obtained from the nozzle diameter D1 and the signal generation time of the AE sensor 9. First, consider the case where the propellant is only a solution such as water. Assuming the cavitation state of the fluid from the cavitation number σ, if σ is smaller than 1, cavitation occurs. In the vicinity of the outlet of the nozzle 400, the pressure is reduced in a low-pressure chamber having a large diameter, and σ is 0.6 or less, where there is a super cavitation state, that is, there are many bubbles on the side of the nozzle, and a strong stirring effect is obtained. It is in a state that can be. In this reduced-pressure atmosphere, the shrinkage rate decreases and the decay energy also decreases rapidly. In this region, the effect of atomization due to strong cavitation collapse cannot be obtained.

Next, in the case of a suspension in which large particles having a particle size of several microns are present in the nozzle 400, a signal AE _p due to cavitation is generated from the particles. This shows different sizes depending on the number and particle form. Since cavitation occurs when a fluid flows on the surface of a solid, a negative pressure occurs, and when it falls below the vapor pressure of the fluid, the negative pressure that becomes the basis of bubbles increases as the particle size increases. Therefore, the energy, that is, the signal level of the high-frequency AE signal is considered to increase. From this signal level, the particle size in the suspension can be estimated. This is more likely to cause cavitation than with fluid alone.

In actual measurement, as shown in FIG. 24, an ultrasonic AE signal propagating from the low pressure chamber 40 direction and an ultrasonic AE signal propagating through the liquid in the suspension 10 in the high pressure cylinder direction can be considered. .
Here, signal generation and propagation paths will be described. As shown in FIG. 24, due to the change in the number of cavitations, cavitation occurs in the middle of the nozzle and then becomes super cavitation. In the second half of the nozzle, in addition to the presence of many cavitations in the direction of the chamber 40, there is a further difference in acoustic impedance between the solution and this part because of the super cavitation state. As a result, it is difficult for an ultrasonic wave having a large reflection to propagate in the direction of the chamber 40. Therefore, it is considered that the ultrasonic wave propagates in the liquid in the direction opposite to the traveling direction of the nozzle 400 and not causing cavitation. When the propagation velocity of the ultrasonic wave in the solution is calculated, the propagation velocity of the ultrasonic wave is 1500 m / s, which is larger than the flow velocity of 400 m / s. Therefore, propagation in this direction is possible.

In the nozzle 400, there are AE _p and AE _s generation sources in the AE signal. When the AE sensor 9 is attached as shown in FIG. 24, many signals propagated in the liquid of the suspension 10 are detected. This naturally shows that it is influenced by the propagation characteristic (attenuation rate). According to Non-Patent Document 1 (a paper on ultrasonic spectroscopy), propagation characteristics (attenuation characteristics) are said to depend largely on the particle diameter. Non-Patent Document 1 shows that a suspension containing particles of 1 micron or more has a large ultrasonic attenuation even at a frequency of 1 MHz or less. This is because the signal to be measured is affected by these frequency characteristics.

As described above, the measured AE signal AE _m is the sum of the fluid cavitation signal AE _s generated from the solvent and the particle cavitation signal AE _p generated from the particles in the nozzle. ) Att _u is reflected. Therefore, the measured signal strength AE _m is represented by the following equation: AE _m = (AE _s + AE _p ) × Att _u .
In this equation, when the material concentration of the suspension is high, AE _p increases and the change in particle size can be accurately captured. On the other hand, when the material concentration of the suspension is low, the AE _s increases, so the AE _p having the particle size information is buried, but the AE _s indicates a phenomenon around the nozzle. It is believed that the efficiency of the device will increase, and this information can be used as an evaluation of the atomization characteristics of the nozzle including the high pressure generator that drives it, such as a high pressure cylinder.

FIG. 25 is a diagram schematically showing cavitation that occurs in the high-pressure jetted raw material mixture 10 and atomization caused thereby. In FIG. 25, reference numeral 1a represents raw material particles immediately before atomization, reference numeral 1b represents particles in the middle of atomization, and reference numeral 1c represents atomized particles.
When considering the flow of particles in a solution, the way of cavitation depends greatly on the particle morphology. For example, as shown in FIG. 25 (a), in the case where the particles 1a in the raw material mixture 10 are in a distorted form such as an aggregate, negative pressure is likely to occur at a portion where the curvature suddenly decreases. Cavitation 700 is generated starting from, and its collapse occurs. In this contraction process, the pressure that draws the particles in contact and the impact due to the collapse are applied to the part. That is, a more effective atomization process can be performed with particles having a distorted particle shape such as necking.
On the other hand, as shown in FIG. 25 (b), when the particle 1b has a spherical shape such as a sintered body, the portion that tends to be negative pressure decreases. That is, the size of the cavitation 700 is also reduced, and its decay energy is also reduced. As shown in FIG. 25 (c), when the particle 1c is in a minute spherical shape, the size of the cavitation becomes smaller and its decay energy also decreases. As a result, it is considered that the impact due to the collapse does not exceed the stress necessary to destroy the particles 1c, and the atomization does not proceed. This state means the end of the atomization process. Due to this effect, the high-pressure spray treatment can produce a monodispersed suspension with a uniform particle size.

  This is because the cavitation in the high pressure part occurring in the high pressure injection process is naturally not larger than the particle size, and the smaller the particle size, the less the atomization phenomenon occurs. It means that only the effect of strong agitation by energy cavitation and super cavitation can be used. Due to this destructive force—the limit of atomization, there is no change in the particle size or morphology in the suspension. At that time, the end of the atomization process by high-pressure injection is shown (FIG. 25C). In addition, although it does not lead to direct atomization, the impact on this particle surface is much stronger than ultrasonic cleaning, etc., and expects effects such as particle surface contamination removal and shape sphere formation. Can do. These phenomena are the features of high-pressure injection processing.

  FIG. 26A is a diagram showing the frequency characteristics of the AE sensor according to the present invention and the frequency spectrum of the measured signal. The vertical axis of the graph is the signal level (dB), and the horizontal axis of the graph is the frequency (MHz). FIG. 26B is a diagram showing a frequency spectrum of the AE signal when only water is ejected from the nozzle 400 as a control reference. Reference numeral 91 denotes a resonance type AE sensor. Reference numeral 92 denotes a broadband AE sensor. The resonance type AE sensor 91 used in the experiment is generated in the nozzle 400 because the resonance frequency is in the vicinity of 0.5 MHz and the reception sensitivity is −20 dB or less in the low frequency region where the frequency is less than 0.2 MHz. This is suitable for selectively detecting the high-frequency AE signal 700 (FIGS. 24 and 26). The wideband AE sensor 92 has a wide frequency band that can be detected, and may detect a low-frequency cavitation signal having a frequency of less than 0.2 MHz (FIG. 26). Therefore, when using the broadband AE sensor 92, it is necessary to perform sharp filtering of the frequency using a circuit such as a band-pass filter circuit. However, the amplification amplifier may be saturated with a large low-frequency signal, which is not suitable for highly sensitive measurement.

(Experimental example 6)
Changes in the refinement state of cellulose due to the difference in the diameter of the nozzle chip through-holes The nozzles c (S01L15) and d (S02L15) in Table 1 are used as the nozzles of the high-pressure jet processing apparatus of the present invention. Then, the raw material mixed solution 10 containing cellulose powder having a concentration of 2% with respect to water was repeatedly subjected to high pressure injection treatment under the condition that _PN was 200 MPa. The particle size distribution was measured by using Zetasizer Nano ZS manufactured by Malvern, Inc. of dynamic light scattering method. The particle size distribution of the cellulose fibers when the the N _P representative N _P 5, is present in suspension 20 in the case of 20 shown in FIG. 27. The fiber particle size distribution is described on a number basis.

FIG. 27 is a graph showing the percentage (%) of the cellulose fiber diameter (nm) present in the suspension 20 at the nozzles c and d. (A) is the case where _NP is 5. Yes, (b) is the case where _NP is 20.
When Dn of the nozzle tip is 0.1mm nozzle c and (S01L15) Dn of the nozzle tip is to compare the nozzle d (S02L15) of 0.2 mm, if when _{N P} is 5 and _{N P} is either in the case of 20 However, the ratio of the suspension 20 that has been subjected to the high-pressure spraying process using the nozzle c (S01L15) increased in the presence of cellulose having a small fiber diameter. This indicates that the use of a nozzle chip with a small Dn increases the effect of miniaturization.

(Experimental example 7)
Change in refinement state of cellulose due to difference in nozzle tip thickness Nozzles b (S01L09) and c (S01L15) of (No. 1) (Table 1), which is a single nozzle N1 as a nozzle of the high-pressure injection processing apparatus of the present invention, (No. 2) No. h (S010101L45) was used, and the raw material mixed solution 10 containing cellulose was repeatedly subjected to high pressure injection treatment under the condition of _PN of 200 MPa. Representative N _P is the case of 5 and N _P was measured particle size distribution of the cellulose fibers present in the suspension 20 in the case of 20. The results are shown in FIGS.
Here, the nozzle h is formed by continuously connecting nozzle tips having the diameters Dn ₁ , Dn ₂ , and Dn ₃ of the through holes without gaps.

Figure 28 is a graph showing the percentage of the cellulosic fiber diameter (nm) (Frequency percentage) ( %) present in the suspension 20 in the nozzle b, c, h, is (a) the number of injections _{N P} 5 is the case of, (b) shows the case of injection number _{N P} is 20. Figure 29 is a graph showing the nozzle b, c, a N _P dependence of the average diameter D of the cellulose in the suspension 20 of the high-pressure injection process in h.
A nozzle b (S01L09) having a nozzle tip Wn of 0.9 mm, a nozzle c (S01L15) having a nozzle tip Wn of 1.5 mm, and a nozzle h (S010101L45) having a total nozzle hole thickness of 4.5 mm. the suspension By comparison, subjected to high-pressure injection process in the order of even if _{N P} is 5 and _{N P} is either in the case of 20, the nozzle h (S010101L45), nozzle c (S01L15), nozzle b (S01L09) It was shown that the ratio of cellulose having a small fiber diameter increases. The effect of miniaturization became higher when a nozzle tip having a large Wn was used.

(Experimental example 8)
Change in refinement state of cellulose due to difference in diameter of nozzle holder through-hole Nozzle a (S01L09D10-30) (nozzle holder through-hole) as single nozzle N1 (Table 1) as a nozzle of the high-pressure jet treatment apparatus of the present invention The raw material mixed solution 10 containing cellulose was repeatedly subjected to high pressure injection treatment under the condition of _PN of 200 MPa using a nozzle c (S01L15D08) (Dh of 0.8 mm). FIG. 30 shows the particle size distribution of cellulose fibers present in each suspension 20 when _NP is 20.

FIG. 30 is a graph showing the percentage (%) of the cellulose fiber diameter (nm) present in the suspension 20 in the difference in the diameter of the nozzle holder through-hole, and FIG. It is a conceptual diagram showing the phenomenon in a nozzle by the difference in the diameter of the through-hole of (a), (a) is a case where the diameter of the through-hole of a nozzle holder is small (0.8 mm), (b) is the through-hole of a nozzle holder This is when the diameter is large (10 mm-30 mm).
Comparing the nozzle c (S01L15D08) with a nozzle holder Dh of 0.8 mm and the nozzle i (S01L09D10-30) with a Dh of 10 mm-30 mm, the suspension subjected to the high-pressure injection process using the nozzle c (S01L15D08) No. 20, but the proportion of cellulose having a small fiber diameter in the liquid increased. Therefore, the effect of miniaturization was greater when a nozzle holder having a small diameter of the through hole was used. This indicates that the use of the nozzle holder having a small Dh shows that the high pressure region is expanded because the pressure drop is small when the raw material mixture 10 flows from the nozzle tip region to the nozzle holder region. It is considered that the same effect as in the nozzle tip also occurs in the nozzle holder. On the other hand, when a nozzle holder with a large Dh is used, when the raw material mixture 10 flows from the nozzle tip region to the nozzle holder region, a sudden pressure decrease occurs, and the state immediately shifts to the super cavitation state, and only the stirring action occurs. It is thought that it will become.

(Experimental example 9)
Changes in cellulose defibration due to the difference between the multistage nozzles N2 and N3 As nozzles of the high-pressure injection processing apparatus of the present invention, the nozzles e (M010202), f (M010101) and g (Table 3) are the multistage nozzles N2 and N3. M020201) and the nozzle c (S01L15) of Table 1 as a single nozzle N1 as a comparative example were used, and the raw material mixed solution 10 containing cellulose was repeatedly subjected to high-pressure injection treatment under the condition of _PN of 200 MPa. And for a typical N _P 5, the particle size distribution of the cellulose fibers N _P is present in the suspension 20 in the case of 20 shown in FIGS. 32 and 33.

Figure 32 is a nozzle c, e, is a graph showing f, the percentage of the cellulose fiber diameter (nm) present in the suspension 20 in g a (Frequency percentage) (%), is (a) the _{N P} This is the case of 5, and (b) is the case of NP ₌ 20. Figure 33 is a graph showing nozzle c, e, f, the N _P dependence of the average fiber diameter D of the cellulose in the case of using g.
Even when N _P is the case of 5 and N _P is either in the case of 20, the suspension 20 subjected to high-pressure injection process using the nozzle e (M010202) is, there is less cellulose having fiber diameters in the liquid The percentage to do became high. On the other hand, the nozzle Dn of all of the nozzle tip are of the same size (0.1mm) f (M010101), even if _{N P} is in either cases of 5 and 20, among other nozzle, submerged The ratio of the cellulose having the largest diameter in the case was high. Therefore, the most upstream side to the smallest diameter Dn ₁ through hole nozzle tip Nn ₁ located (0.1 mm), the diameter _Dn 2 other nozzle tip _Nn 2, Nn of holes, Dn ₃ it can be seen that the nozzle N2 which was the nozzle tip Nn ₁ through hole larger than the diameter Dn ₁ (0.2 mm) is best suited to fine processing. The nozzles having the same diameter (0.1 mm) of the through holes of all the nozzle tips deteriorated the miniaturization characteristics due to the decrease in the flow rate.

(Experimental example 10)
Change in viscosity of cellulose due to differences in various nozzles N1, N2, and N3 Nozzles b (S01L09), c (S01L15), and d (S02L15) of Table 1 are the single nozzle N1 of the high-pressure jet processing apparatus of the present invention. Using three types of nozzles, the raw material mixed solution 10 containing _PN at 200 MPa and cellulose powder at a concentration of 2% was repeatedly subjected to high pressure injection treatment under the conditions of _PN of 200 MPa.
Further, the nozzles e (M010202), f (M010101), and g (M020201) of the multistage nozzle N2 (Table 3) of the high-pressure injection processing apparatus of the present invention, and a single nozzle N1 as a comparative example (Table 1) the nozzle c (S01L15) of) the same _{P N} alone nozzle N1, the raw material mixture 10, _{P N} is high-pressure injection process repeated under conditions of 200 MPa. The viscosity of the cellulose in the suspension 20 in the case where the N _P is changed when η shown in FIG. 34.

Consideration view of change in viscosity η due alone nozzles N1 34 is a graph showing various nozzle N1, N2, N3 _{N P} dependence of η of cellulose in the suspension 20 in, (a) represents a single nozzle N1 (B) is a case where multistage nozzles are used.
For a single nozzle N1, eta rises with a small N _P as Wn of the nozzle tip is large. This means that the high-pressure cavitation region is enlarged depending on the size of Wn of the nozzle tip. As a result, the nozzle c (S01L15) has twice the processing capacity of the nozzle b (S01L09).
On the other hand, the nozzle h (S010101L45) is when _{N P} is small η is not increased, it was confirmed that the gradual η increases with increasing _{N P.} This is considered to be because the shearing force is reduced because the speed is low, but the high-pressure region having the effect of miniaturization is maintained to some extent.
Looking at changes in eta cellulose, eta is initially about the same 1 mPa · sec and water and _{N P} is 10, becomes very large and 270 MPa · sec. This means that the processing time did not change even when the change in η was large. That is, it shows that the speed of the jet flow in the nozzle hardly changes. This result shows that the inside of the nozzle is not a laminar flow but a jet flow that does not depend on viscosity.
Nozzle d (S02L15), which is thought to be slow in flow and partially including laminar flow, had the smallest increase in η. In other words, the performance required for the nozzle is considered to be excellent in efficiency because it has a structure in which the entire nozzle is in a jet flow with little fluid resistance and the side surface in contact with the nozzle tip side wall is enlarged.
In the case of a multistage configuration, it is considered that when the diameter of the nozzle holder through hole is as small as possible, the pressure after the nozzle tip is less likely to decrease, the high-pressure cavitation region effective for atomization increases, and the efficiency increases.
Considering that the diameter of the jet flow is about 0.16 mm when a nozzle having a nozzle tip Dn of 0.2 mm is used and the injection pressure _PN is high pressure treatment at 200 MPa, the optimum nozzle tip Dn is 0. When the thickness is .16 mm or less and the thickness is Wn, a nozzle having a Wn / Dn of 15 to 45 or less is considered to have the highest atomization efficiency. The magnitude of the measured AE signal voltage V _rms also coincides with the increasing tendency of η, and this value of V _rms can be used as a quantitative guide for nozzle miniaturization performance.

Consideration of change in viscosity η by multi-stage nozzles N2 and N3 Only nozzle e (M010202) exceeded the characteristics of nozzle c (S01L15). This is because the mass of cellulose of several μm was completely defibrated and the density of fiber-like particles increased due to the effect of stirring the solution in the periphery of the jet flow along with the expansion of the high pressure region downstream of the nozzle. Therefore, the transparency of the suspension treated with nozzle e (M010202) was the highest.
On the other hand, in the configuration in which the nozzle tip having a small Dn is arranged on the downstream side of the nozzle like the nozzle g (M020201), the jet flow is generated after the laminar flow portion pressure is lost on the upstream side of the nozzle. The atomization efficiency decreased.

(Experimental example 11)
Nozzle c of (Table 1) which is nozzle N1, N2, N3 of the high-pressure injection processing apparatus of the present invention regarding the structural change of cellulose in the suspension 20 subjected to high-pressure injection processing using the nozzles N1, N2, N3 Using (S01L15) and nozzles e (M010202) and g (M020201) shown in (Table 3), a high-pressure jet treatment was performed 20 times under the condition of _PN of 200 MPa, and a dried cellulose membrane was produced. X-ray diffraction pattern analysis of the film and electron microscope observation of the dried sample were performed. The observation magnification was 300 times and 5000 times, and the fine structure was observed. The results are shown in FIG. 35, FIG. 36, and FIG.

FIG. 35 is a diagram showing a diffraction pattern of a cellulose film subjected to high pressure injection processing using nozzles N1, N2, and N3, and FIG. 36 shows high pressure injection processing performed using nozzle e (M010202). It is an electron microscope image of a cellulose, (a) is a 300 times magnified image, (b) is a 5000 times magnified image. FIG. 37 is an electron microscopic image of cellulose that has been subjected to high-pressure spraying using the nozzle g (M020201), (a) is a 300-fold magnified image, and (b) is a 5000-fold magnified image.
Cellulose subjected to high-pressure spraying with a defibrating nozzle g (M020201) has the highest (200) peak, indicating that it could be defibrated without destroying the structure.
Further, when the electron microscopic images of cellulose subjected to the high-pressure jet treatment with the defibrating nozzle g (M020201) and the nozzle e (M010202) were compared, a state in which fibers were entangled was observed in the defibrating nozzle g (M020201). . In the image magnified at high magnification, the fiber diameter was narrower. Therefore, it was found that the defibration type nozzle g (M020201) defibrated cellulose softly and did not damage the fibrous structure.
From the above results, this configuration showed less damage to the crystal and a longer fiber length. Therefore, when manufacturing a long fiber, this nozzle configuration is suitable, and a miniaturization process with little damage using a high-speed and high-speed laminar flow is suitable. Rather than simply reducing the injection pressure _PN , the efficiency of the entire processing process can be structured by adjusting the nozzle configuration and using the injection pressure according to its role.

(Experimental example 12)
A suspension of approximately 30 wt% of the particle size distribution PZT powder PZT powder by single nozzle N1 as the raw material mixture 10, using a nozzle (Table 1) b (S01L09), c (S01L15), P N twice processing _{(N P} is 2) was carried out under the conditions of 200MPa. The particle size distribution of the PZT powder present in the suspension 20 after the treatment is shown in FIG. The particle size distribution of the fine particles is described on a volume basis.

FIG. 38 is a graph showing the percentage (%) of the diameter (nm) of the PZT powder existing in the suspension 20 at the nozzles b and c.
The higher the thickness Wn of the nozzle chip through hole, the higher the atomization performance.

(Experimental example 13)
Change in diameter of nano-sized alumina fine particles by single nozzle N1 Using nano-sized alumina fine particles as a raw material of the raw material mixture 10, nozzles b (S01L09) and c (S01L15) in (Table 1) are used, and _PN is 200 MPa. Processing was performed under conditions. And the percentage of the representative _{N P} is the diameter of the nano-sized alumina particles present in the suspension 20 in the case of 5,10,20 (nm) (Frequency percentage) (%), the average diameter D of the fine alumina particles It was to evaluate the N _P dependence. The results are shown in FIGS. 39 and 40. The particle size distribution of the fine particles is described on a volume basis.

Figure 39 is a graph showing the diameter of the nano-sized alumina particles present in the suspension 20 in the nozzle b, c percentage of the (nm) a (Frequency percentage) (%), is (a) the _{N P} 5 (B) is the case where _NP is 10, and (c) is the case where _NP is 20. FIG 40 is a graph showing the N _P dependence of the average diameter D of the fine alumina particles.
In any _{N P,} nozzle c (S01L15) rather than the nozzle b (S01L09), it can be seen that has a small diameter. If the average diameter D of the alumina particles to compare _{N P} to become 150nm nozzle c (S01L15) had four times the performance compared to the nozzle b (S01L09). Regarding the zeta potential V _ζ , there was not much difference between the two. As a result, it was confirmed that even when the particle size is 100 nm, the atomization efficiency is increased by increasing the thickness of the nozzle tip.

(Experimental example 14)
Using the nozzle a in (Table 1), was measured the change in AE signal voltage _{V rms} of _{N P} when treated cellulose 2% concentration. Here, _PN is 200 MPa.
The result is shown in FIG. Figure 43 is a graph showing the time course change of the AE signal voltage at each injection number N _P. Viscosity η from about the initial 1 mPa · sec, at _{N P} is 10, even though also risen to 140 mPa · sec, the processing time and 2.25 seconds, was hardly changed. This indicates that the average speed in the nozzle is almost constant. On the other _{hand, V rms} is _{N P} up to 10, rises in proportion to _{N P,} increase thereafter was less. This change corresponds well with the change of η, and it can be seen that the state of refinement of cellulose can be monitored well.

In summary, it is very effective to use the magnitude of the AE signal voltage V _rms for quantitative performance evaluation of the miniaturization characteristics of high-pressure injection processing devices such as nozzles and high-pressure cylinders. The conversion effect was high. It was also found that V _rms has a large speed dependency. That is, even if the high pressure region is lengthened, a high refining effect cannot be obtained unless the speed related to the shearing force of atomization is large. The boundary speed was around 300 m / s. That is, a high atomization performance can be realized by achieving a speed of 300 m / s or more together with the nozzle structure.
The following (a), (b), and (c) can be derived.
(A) When the diameter was the same, a larger AE signal voltage was obtained with a thicker nozzle tip.
(A) The speed reduction was less when the nozzle chips were divided than when the nozzle chips were stacked, and a large AE signal voltage was obtained.
(C) A large AE signal voltage was obtained by placing a nozzle tip having a small diameter on the high voltage side even at a low voltage.

(Experimental example 15)
(Table 1) (Table 2) Nozzles b, c, d, e, f, g, h, i shown in (Table 3) are attached to a high-pressure injection processing apparatus, the raw material mixture is subjected to high-pressure injection processing, and an AE signal is output. Measured. The result of _obtaining V _rms with respect to the average speed v _N from the analysis is shown in FIG. This is a graph summarizing the relationship between V _N and V _rms carried out so far, (a) shows the results of nozzles with the diameter and thickness of the nozzle tip through-hole changed, (b) shows the stacking nozzle and The result of a multistage nozzle is shown, (c) The result of a multistage nozzle is shown.
Dn is at 0.1mm, Wn is a case 0.9mm and a thin, _{v N} is _{V rms} is large becomes greater than 400m / s. When the thickness Wn was 1.5 mm, the size changed to about twice that. At high alone nozzles of Wn / Dn, rapidly _{v N} is greater when more than 300 meters / s. That is, it can be seen that an average speed of 300 m / s or more and a nozzle structure that makes use of it are necessary. There was a tendency for V _rms to increase in proportion to v _N in the case of multiple _stages . This indicates that the AE signal increases as the thickness increases.
If the D _N to 0.2 mm, _{v N} is _{V rms} at 300 meters / s or more it is sharply increased. This indicates that when _DN is increased, the surface area of the jet flow boundary in the nozzle increases, and thus the amount of AE signal measured increases.
Also, better to the nozzle tip in multiple stages from the lamination, v is less AE signal decrease of _N is increased. This indicates that the high-pressure region can be further expanded by using a multi-stage nozzle and utilizing these nozzle holder portions because the AE signal becomes large. In the multi-stage configuration, a nozzle tip having a 0.1 mm through hole diameter with a small Dn is arranged on the upstream side, and thereafter, a nozzle that does not cause a decrease in the jet flow velocity and that maintains a high pressure. However, the AE signal was the largest. That is, the nozzle having the configuration has the best atomization characteristics. These tendencies corresponded well to changes in the particle size of ceramic and cellulose treatment when various nozzles were actually used. That is, it was shown that the atomization performance of the nozzle can be quantitatively evaluated by the magnitude of the AE signal.

On the other hand, the largest shearing force acts at the boundary of the jet flow, and the miniaturization process proceeds in the vicinity. Since the AE signal is generated from the high-pressure cavitation portion, it is considered that increasing Dn increases the strong miniaturization region near the surface and increases the AE signal, but the center of the jet flow is the flow velocity. Since there is not much difference, the effect of miniaturization as large as the boundary region cannot be expected. Therefore, with a single nozzle, the size of AE due to Dn may not always match the processing efficiency. In that case, what is necessary is just to normalize with the surface area.
In some cases, the pressure cannot be rapidly increased to several hundred MPa due to the pumping capacity of the cylinder portion that pressurizes to a high pressure or the expansion of piping. In this case, the pressure rises slowly, and a time during which the solution speed does not reach the specified value occurs. The suspension treated here passes through the nozzle in a state where there is almost no miniaturization effect, the untreated portion increases, and the processing efficiency as a whole deteriorates. It is considered that the change of the AE signal is effective as monitoring of the miniaturization effect, and the performance evaluation regarding the miniaturization of the nozzle and the apparatus can be performed with the average value.

  As described above, in this embodiment, the ball collision chamber is disposed. However, the present invention is not limited to the ball collision chamber, and a single nozzle chamber, an oblique collision chamber, and the like can be applied. As described above, the present invention is not limited to the present embodiment, and can be widely applied to wet microfabrication apparatuses.

N1, N2, N3 Nozzle of the high-pressure jet processing apparatus of the present invention,
Nn, Nn1, Nn2, Nn3 nozzle tip,
Nh, Nh1, Nh2, Nh3 nozzle holder,
1 monitoring equipment,
8 Signal processing judgment means (FFT analyzer),
9 AE sensor (resonant AE sensor),
10 Raw material mixture,
20 dispersion (suspension),
1a Agglomerates of fine particles,
1c fine particles,
40 chambers,
400 Nozzle of the high-pressure jet processing apparatus of the present invention,
402 Exit,
500 high pressure cylinder part,
600 AE signal main propagation path,
AE _m intensity of AE signal measured,
AE _p- particle cavitation signal,
Signal due to cavitation of AE _s solution,
Att _u ultrasonic propagation characteristic (attenuation ratio),
The number of injections of N _P high-pressure injection,
V _rms AE signal voltage

Claims (9)

  In a nozzle of a high-pressure injection processing apparatus that finely squeezes a raw material mixture by high-pressure injection so that the average velocity in the nozzle is 300 m / s or more, the nozzle is composed of a nozzle tip having a through hole and a nozzle holder, and the nozzle The diameter Dn of the through hole of the tip is 0.16 mm or less, and the ratio (Wn / Dn) of the through hole thickness Wn of the nozzle tip to the diameter Dn is 10 or more and less than 45, Equipment nozzle. In a nozzle of a high-pressure injection processing apparatus that finely squeezes the raw material mixture by high-pressure injection so that the average velocity in the nozzle becomes 300 m / s or more, the nozzle is passed through in order to divide the thickness of the nozzle tip made of diamond. It is composed of a plurality of nozzle chips and a plurality of nozzle holder having a bore, at least one of the following 0.16mm diameter Dn _m through hole of the nozzle tip, and of diameter Dn _m through hole of the nozzle tip A nozzle of a high-pressure injection processing apparatus, wherein a ratio of a total thickness of through holes of the plurality of nozzle tips to a smallest diameter is 10 or more and less than 45. The nozzle nozzle for high-pressure injection apparatus according to claim 2, wherein the size of the diameter Dn _m is composed of a plurality of different nozzle tips and a plurality of nozzle holder.   The plurality of nozzle chips are composed of a first nozzle chip and a second nozzle chip, the second nozzle chip is arranged on the downstream side of the first nozzle chip, and the second nozzle chip The diameter of the through hole of the first nozzle tip is larger than the diameter of the through hole of the first nozzle tip and is in the range of 0.16 mm or more and 0.8 mm or less, thereby increasing the high pressure region without lowering the average speed in the nozzle. The nozzle of the high-pressure jet processing apparatus according to claim 2, wherein an efficient miniaturization process is enabled.   The plurality of nozzle chips is composed of a third nozzle chip and a fourth nozzle chip arranged on the most upstream side, and the fourth nozzle chip is arranged on the downstream side of the third nozzle chip, And the diameter of the through hole of the third nozzle tip is larger than the diameter of the through hole of the fourth nozzle tip and is in the range of 0.16 mm or more and 0.8 mm or less, thereby reducing the average speed in the nozzle. The nozzle of the high-pressure jet processing apparatus according to claim 2 or 3, wherein a suitable defibrating process such as a fiber using a shearing force in a laminar flow at a high speed is possible.   The nozzle of the high-pressure injection processing apparatus according to any one of claims 1 to 5, wherein a diameter of the through hole of the nozzle holder is 0.8 mm or less in order to maintain a high-pressure region around the nozzle tip. .   An evaluation method of a high pressure injection processing apparatus that finely injects a raw material mixture at a predetermined pressure to generate cavitation, and an AE sensor is attached to the high pressure injection processing apparatus to detect an AE signal, A method for evaluating a high-pressure jet processing apparatus, wherein performance evaluation of atomization characteristics is performed based on size.   The high-pressure injection processing apparatus including the nozzle according to any one of claims 1 to 6, wherein the raw material mixture is finely pulverized or defibrated by high-pressure injection so that the average velocity in the nozzle is 300 m / s or more. A high-pressure pump that pressurizes the raw material mixture, a drive control unit that pressurizes the raw material mixture to 100 MPa or more by driving and controlling the high-pressure pump, and a high-pressure cylinder, and the raw material mixture that is pressurized to 100 MPa or more A high-pressure injection processing apparatus characterized in that a liquid is injected into the nozzle connected to the high-pressure cylinder, thereby miniaturizing or defibrating.   The high-pressure injection processing method using a nozzle according to any one of claims 1 to 6, wherein the raw material mixture is finely pulverized or defibrated by high-pressure injection so that the average velocity in the nozzle is 300 m / s or more. A high-pressure pump that pressurizes the raw material mixture; a drive control unit that pressurizes the raw material mixture to 100 MPa or more by driving and controlling the high-pressure pump; and a high-pressure cylinder. A high-pressure injection processing method, comprising pressurizing a mixed liquid to 100 MPa or more and spraying the mixed liquid to a nozzle connected to the high-pressure cylinder to refine or defibrate the raw material mixed liquid.