JP2715861B2 - Method and apparatus for producing non-metallic amorphous by mechanochemical - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to the production of non-metallic amorphous.

[0002]

2. Description of the Related Art In recent years, attention has been paid to amorphous materials for many substances, research and development have been advanced, and they have reached the point where they are offered to the market as products. Amorphous (amorphous) refers to the solid state in which long periodic atomic arrangements, such as the crystals that make up a substance, are blocked. Oxidizing glass has been widely known for a long time. As a result, properties different from those originally possessed by the substance have been found, and have attracted attention in many industries.

[0003] The characteristics of the amorphous material are that the structure is macroscopically uniform and the composition is homogeneous. Crystals always have non-uniform regions such as grain boundaries and dislocations.
Although it is inevitable that a locally heterogeneous structure exists due to precipitation and grain boundary segregation, since amorphous has no crystal itself, the non-uniformity due to the mode of each crystal structure is wiped out, and physical This has the advantage of maintaining extremely uniform properties chemically and chemically. In recent years, pure metals such as Fe and B
Amorphous products such as i, Ni, Pd-Si, Cd-Co, etc. as alloys, Si, Ge, etc. as semiconductors, and Si-C, Li-Nb-O, etc. as ceramics are offered as commercial products. Used in

[0004] In principle, an amorphous manufacturing method is to realize a non-equilibrium process from a thermodynamically stable state. For example, metals such as alloys and ceramics are manufactured by rapid cooling from a molten state (liquid), and semiconductors are condensed from a gaseous state, such as sputtering,
Manufactured by vacuum evaporation. As a non-equilibrium process from a solid, a method of irradiating a crystal with particles and implanting ions to introduce many defects, and a recently discovered method of interdiffusion of a thin film (crystal) have been proposed. However, it has not been seen that it has reached the stage where it was economically established as a product.

[0005]

The above-mentioned amorphous materials have been used in fields having a relatively high added value, and have achieved a certain effect. For example, power transformers, magnetic heads, and superconducting materials for alloys, solar cell substrates for semiconductors,
As a phototube film, it is used as a thermistor and sensor in ceramics, so even with advanced equipment such as rapid cooling, vacuum deposition, vapor phase decomposition, and sputtering, and small-scale production, that immediately hinders commercialization. It is not an element to do. However, there are many substances that want to realize better physical properties than before by making use of the properties of amorphous. .

For example, it has been used as a conventional raw material for porcelain, refractory, etc. In recent years, rubber and plastic fillers,
Amorphous talc and kaolin, which are used in paints, chemicals, cosmetics, etc., in addition to agricultural chemical extenders, have a high dissolution rate, suppress sublimation rate, and improve magnetic performance. Can be expected to bring more excellent properties to products at the destination of use. However, general-purpose products such as kaolin, talc, barium sulfate,
It is difficult to allow small-scale production with the above-mentioned advanced equipment, judging from the economic balance, and it is extremely desirable to improve the performance of the product, but the problem is that productivity cannot be ignored.

In recent years, as a method of producing an amorphous state from a solid state, instead of the above-described method of forcing ions into a lattice structure of a crystal and forcibly forming a solid solution, a mechanical force stronger than the binding energy between lattices is used. Add energy,
A method of making a nonmetallic inorganic substance amorphous by shearing and dispersing the structure has been reported as an application of mechanochemical. With this method, the equipment cost is not so large and can be a very effective solution. However, at present, the problem is that amorphous quality and productivity have not yet reached a satisfactory level. The broken line shown in FIG. 9 is a result of supplying the kaolin powder into the batch-type vibrating mill, operating the device, collecting the kaolin after 240 hours, and performing X-ray analysis. When the crystal remains, a specific direction unique to the crystal appears. That is, as a result of X-rays being scattered and interfered with regularly arranged atoms, only a unique direction that satisfies a certain condition is strengthened, and a certain angle (horizontal axis 2θ in the figure = formed by incident wave and scattered wave) Angle)), which appear as several peaks, which are referred to as Bragg
It is called reflection and is applied as a conventional means for confirming the degree of amorphization. As shown in the figure, the fact that an apparent peak does not disappear and remains as it is even after being operated for 240 hours clearly indicates that amorphousization by mechanical energy is hardly performed.

FIG. 10 shows a conventional technique aiming at amorphization by another mechanochemical. The inorganic material to be treated is talc, and the applied mechanical energy is generated by a batch type planetary ball mill. In this experiment, the talc material was sealed in a batch type planetary ball mill and operated by applying mechanical action such as pulverization and shearing. And the X-ray analysis was performed.
As a result, the torque-specific peak disappeared by the processing for 3600 seconds or more, and it was confirmed that almost satisfactory amorphous was obtained. However, although this report has shown in the laboratory that the use of a planetary ball mill enables the amorphous material to be amorphous, it still requires one hour of operation to obtain satisfactory quality. It is hard to say that the process has reached the stage where it can be applied to actual production in combination with the inefficient small-volume processing called the formula.

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, an object of the present invention is to provide a method for producing non-metallic amorphous by mechanochemical and an apparatus therefor, which can be applied to actual production activities because of high productivity and large mass production effect. And

[0010]

According to the present invention, there is provided a method for producing a non-metallic amorphous material by a mechanochemical method, wherein an inorganic material as a raw material is supplied to a raw material feeder of a dry continuous planetary ball mill and revolves in a mill pot which revolves in the same direction while revolving. Into the mill pot with the air sucked into the mill pot,

(Equation 5) While maintaining the centrifugal acceleration ratio G applied to the inside of the mill pot represented by Equation 5 to at least 30 or more,

(Equation 6) Numerical values related to revolution and rotation expressed by Equation 6 are 0.40 to
The above-mentioned problem is caused by applying compression, shearing, and / or impact pulverizing action within a range of 1.50, and then introducing the treated powder into a powder recovery device by placing it in an air stream from a mill pot to separate and recover the powder. Was solved.

In this case, the treated powder separated and recovered in the powder recovery device is returned to the raw material feeder via the branch valve and supplied again into the mill pot of the dry continuous planetary ball mill under the same conditions as the previous time. Alternatively, the circulation may be repeated in the closed system until the desired amorphization progresses.

At this time, a method may be employed in which the processed powder separated and recovered by the powder recovery device is returned to the storage tank provided in the system path instead of the raw material feeder via the branch valve.

As an apparatus used for this amorphous manufacturing method, a dry continuous planetary ball mill provided with a mill pot in which crushed balls and raw materials are charged and revolved in the same direction while revolving,

(Equation 7) The centrifugal acceleration ratio G applied to the inside of the mill pot represented by the formula 7 has a structure and strength that can be freely selected from a range of 30 to 150,

(Equation 8) Numerical values related to rotation and revolution represented by Equation 8 are 0.4 to
1.50 The raw material feeder is connected to the front and the powder recovery device is connected to the rear, respectively, and the separated and recovered amount in the powder recovery device is collected and the product is recovered. It is a requirement that a branch valve that can be arbitrarily selected from any of a return path to the storage tank is interposed.

[0014]

According to the present invention, as a means for applying mechanochemicals,
A dry continuous planetary ball mill was identified. The feature of this mill is that the grinding body is charged, and the treated body is transported in the air flow in a mill pot that revolves while rotating and revolves, while intense grinding, shearing, impact that is not required for other types of grinding machines It is in giving mechanical energy such as. That is, for example, in a normal rolling ball mill, a grinding medium and a material to be crushed cause a cascade motion in a single rolling cylinder, and the crushing and abrasion due to the gravitational drop advance the crushing action. In a planetary ball mill, the centrifugal force and the Coriolis force due to high-speed revolution and rotation work synergistically to provide excellent mechanical energy to the raw material. This intense transfer of energy inevitably raises the temperature of the raw material and should have a considerable effect on the quality of the inorganic substances.However, the inorganic substances move along the airflow and are discharged, or are returned to the mill pot along the airflow. Because of the mechanism of returning, it moves while receiving a cooling action, so that a change in quality and mutual aggregation are prevented, and mechanical energy is efficiently consumed for shear dispersion of the crystal structure.

As a result of the experiment, in order to achieve a mechanochemical action that satisfies productivity as a condition to be provided for the dry continuous planetary ball mill, the centrifugal acceleration ratio G applied to the mill pot must be at least 30; Depending on the material of the equipment, there is a high probability that a maximum of 150 is required, and a high-capacity driving force that can realize this G
It is a requirement of the device to have a structure made of a robust member capable of withstanding this operation and a combination thereof.

Another requirement of the dry-type continuous planetary ball mill is the relationship between rotation and revolution, as shown in FIGS. 4 (A) and 4 (B).
A description will be given based on (C). Each of these figures shows the relationship between the motion state of the crushed ball B in the mill pot and the relative ratio of the revolution and rotation of the mill. The revolution angle is ω ₁ , the relative angular velocity of the revolution is ω ₂ , Ratio R = ω ₂ / ω ₁
An explanation in which the value of R is added with the elements of the revolving diameter and the inner diameter of the mill pot used in the embodiment of the present invention, and r calculated by the equation presented earlier is compared with the behavior of the ball in the mill pot. FIG. FIG. (A) shows r = 0.70.
In this state, the balls are integrally and collectively surging along the inner wall of the mill pot, and a strong shearing force and impact force are applied to the non-metal powder inserted between the inner peripheral surface and the balls and the balls. Giving them all effective mechanochemical effects and energy transfer is progressing. FIG. (B) shows r = 1.00,
FIG. 9C shows the behavior of the ball when r = 1.50. As the rotation angular velocity becomes a relatively large ratio, a part of the ball moves away from the inner peripheral surface of the mill pot and moves inside the mill pot. In the space between the two, the collision between the balls causes a part of the energy to be wasted and the phenomenon of receding from mechanochemical purposes begins to appear. This tendency accelerates as R increases, and if it exceeds a certain limit, it becomes difficult to amorphize no matter how much G is increased. Therefore, it depends on the other configuration of the dry continuous planetary ball mill. The calculated r must remain in the range 0.4 to 1.50.

[0017]

FIG. 1 is a flowchart showing an embodiment of the present invention. In the figure, a raw material feeder 2 is connected in front of a dry continuous planetary ball mill 1 to supply an inorganic raw material A by a fixed amount. A powder recovery device 3 is connected to the rear of the dry continuous planetary ball mill, and a fan 4 at the rear further sucks air to form an airflow that travels in one direction, and receives a predetermined mechanical action in the dry continuous planetary ball mill. The raw material is discharged from the mill pot by this air flow, separated into air and powder in a bag filter, and the air is purified and released into the atmosphere.
The separated product is recovered by opening the discharge valve 31.

If the desired amorphization has not yet been achieved even after receiving only one mechanical action, the supply of the raw material A to the raw material feeder 2 is stopped, and the branch valve 32 is switched to the return side to perform processing. The powder is returned to the raw material feeder, charged again into the dry continuous planetary ball mill, and subjected to the same mechanical action as the first time. Since such conditions can be known in advance empirically, it is also possible to determine working standards for each inorganic material, such as the operating time and the number of circulations at which a high degree of amorphousness can be obtained.

FIG. 2 is a flow chart of another embodiment of the present invention. Assuming a case where the circulation is repeated, a treatment tank 5 is interposed in addition to the raw material feeder 2 and separated by the powder recovery device 3. The powder is returned to the storage tank, weighed by a fixed amount by the load cell 51, and the cut-out feeder 52 is opened to supply the powder to the dry continuous planetary ball mill 1 to give a mechanical action again. obtain. In this case, since the processed powder does not pass through the raw material feeder, it does not mix with the raw material and is often advantageous in quality. FIG. 3 is a flow chart showing still another embodiment, in which the second raw material feeder 21 is used in combination. The present invention is not limited to the flow illustrated here, but is a continuous mill. Various combinations are possible as a configuration in which the processed product circulates and repeatedly receives processing in a closed system for a predetermined time, and if a system that is continuous but substantially satisfies the function of a batch system is constructed, It is not a question of the difference between the combinations.

FIG. 5 is a vertical sectional front view showing an example of a dry continuous planetary ball mill 1 which is desirable for carrying out the present invention. In the figure, a plurality of mill pots 13 that revolve in response to rotation of a main shaft 12 driven by an electric motor 11 are arranged uniformly around the main shaft, and the mill pot 13 itself also rotates around its own rotation axis. That is, a planetary gear 14 is provided around the outer periphery of a mill pot that rotates together with the main shaft 12, and the sun gear 15 meshing with the planetary gear 14 is separately rotated or stopped, and the mill pot is rotated while revolving. The sun gear is fitted around the main shaft. A grinding ball B is inserted into the inside of the mill pot, and performs a unique movement with the rotation of the mill pot. A raw material supplied from a raw material feeder (not shown) is supplied from a supply hole 16 to a center hole 1 formed in a shaft center of a main shaft.
7 and into the mill pot through a supply pipe 18 co-rotating with the main shaft, and is discharged from a rear outlet 19.

FIG. 6 illustrates the operating conditions of a dry continuous planetary ball mill showing one embodiment of the present invention, and is also a motion diagram of a mill pot. Table 1 gives specific numerical values for this figure, and shows the operating conditions in the example. The revolving direction is the same as the revolving direction, the revolving angular velocity is ω ₁ , the relative angular velocity of the revolving to the revolving is ω ₂ , the ratio of the two is R, and the relation of the revolving calculated by substituting the revolving diameter K and the mill pot inner diameter. The value is represented by r, and the centrifugal acceleration ratio is represented by G.

[0022]

[Table 1]

FIG. 7 is an X-ray analysis diagram showing the result of charging kaolin into a mill pot and performing a mechanochemical action under the above-mentioned operating conditions. The horizontal axis is the angle formed by the incident wave and the scattered wave as in the description of the related art. The top line is the unprocessed kaolin, which is the raw material, and the raw material supply to the continuous planetary ball mill was temporarily stopped to reduce the processing time in the mill by one.
It is a diagram of the sample changed into three types of 0, 15, and 20 minutes.
What is clear in this figure proves that the batching process for about 15 minutes eliminates all the characteristic peaks that initially protrude, and has reached a state where the amorphization is almost completed. FIG. 8 shows data obtained by examining the number of circulations (the number of passes) and the transition of the amorphization. One pass is about 1.5 minutes. From this data, it is proved that under the operating conditions of this embodiment, it is possible to obtain a level of amorphous which can be commercialized by the circulation treatment for about 15 minutes.

[0024]

According to the present invention, as described above, an amorphous nonmetallic inorganic substance having high productivity can be obtained by the action of mechanochemical. Despite the fact that the equipment itself does not impose a very large burden, it can provide excellent perfect amorphous materials that are comparable to the advanced and inefficient amorphization of the prior art. However, it is considered to be economically sufficient. as a result,
It is expected to make a significant contribution to the development of functional materials that have reached a higher standard, and that the provision of new materials will contribute to the development of new products in various industries.

[Brief description of the drawings]

FIG. 1 is a flowchart of an embodiment of the present invention.

FIG. 2 is a flowchart of another embodiment.

FIG. 3 is a flowchart of still another embodiment.

FIG. 4 is a partial vertical sectional front view showing a relationship between fluctuations of R and r and a state change in a mill pot by (A), (B) and (C).

FIG. 5 is a vertical sectional front view of a dry continuous planetary ball mill applied to the embodiment of the present invention.

FIG. 6 is a schematic diagram showing a relation of a mill pot portion of the same example.

FIG. 7 is an X-ray analysis diagram showing an example of the effect of the embodiment (batch use).

FIG. 8 is an X-ray analysis diagram showing an example of the effect of another embodiment (circular use).

FIG. 9 is an X-ray analysis diagram of the related art.

FIG. 10 is an X-ray analysis diagram of another related art.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 Dry continuous planetary ball mill 2 Raw material feeder 3 Powder recovery device 4 Fan 5 Storage tank 11 Motor 12 Main shaft 13 Mill pot 14 Planetary gear 15 Sun gear 16 Supply port 17 Center hole 18 Supply pipe 19 Outlet 21 Second material feeder 31 Discharge Valve 32 Branch valve 51 Load cell 52 Cut-out feeder

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-18939 (JP, A) JP-A-4-94748 (JP, A) JP-A 62-126257 (JP, U) JP-A 45- 23275 (JP, Y1)

Claims (4)

(57) [Claims] 1. An inorganic material, which is a raw material, is supplied to a raw material feeder of a dry continuous planetary ball mill, and enters along with air sucked into a mill pot which rotates in the same direction while revolving, and is pulverized in advance in the mill pot. With the ball, While maintaining the centrifugal acceleration ratio G applied to the inside of the mill pot represented by the equation 1 to at least 30 or more, Numerical values related to revolution and rotation expressed by Equation 2 are 0.40 to
After applying compression, shearing, and / or impact pulverizing action to a range of 1.50, the treated powder is introduced into an air stream from a mill pot and guided to a powder recovery device to be separated and recovered. Nonmetallic amorphous manufacturing method by mechanochemical. 2. The process powder according to claim 1, wherein the processed powder separated and recovered in the powder recovery device is returned to a raw material feeder through a branch valve and supplied again into the mill pot of the dry continuous planetary ball mill under the same conditions as the previous time. A non-metallic amorphous manufacturing method using mechanochemicals, wherein the circulation is repeated in a closed system until the desired amorphization progresses. 3. The non-metallic amorphous by mechanochemical according to claim 2, wherein the processed powder separated and recovered by the powder recovery device is returned to a storage tank interposed in a system via a branch valve. Manufacturing method. 4. A dry continuous planetary ball mill provided with a mill pot in which crushed balls and raw materials are charged and revolved in the same direction while revolving, The centrifugal acceleration ratio G applied to the inside of the mill pot represented by the equation (3) has a structure and strength that can be freely selected from a range of 30 to 150. The numerical value related to rotation and revolution represented by Equation 4 is 0.4 to
1.A material feeder is connected to the front and a powder recovery device is connected to the rear, and the separated and recovered amount in the powder recovery device is collected and product recovered, and the front raw material feeder or An apparatus for producing non-metallic amorphous material by mechanochemical, wherein a branch valve which can be arbitrarily selected from any of a return path to a storage tank is interposed.