JPS61195903A - Manufacture of amorphous molded body - Google Patents

Abstract

PURPOSE:To obtain a massive amorphous molded body having extremely high density and amorphism when powder of an amorphous substance is pressurized and heated to form a molded body, by specifying the temp. under an extremely high pressure. CONSTITUTION:The crystallization temp. Tx of an amorphous substance rises in dependence on pressure. Powder of the amorphous substance is pressurized to an extremely high pressure (p) and heated to a temp. between >90% of the temp. Tx under ordinary pressure and a temp. below the temp. Tx(p) under the pressure (p) to obtain a massive molded body. The preferred extremely high pressure (p) is >=0.2GPa.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing a bulk amorphous molded product, which has advantages unique to amorphous material: It has advantages such as low magnetic force, high maximum permeability, and high specific resistance, so it is effective when used as a magnetic material.

(Prior art) Amorphous materials such as metals, alloys, semiconductors, dielectrics, etc. have conventional long range order.
Because it has a disordered atomic structure that is fundamentally different from crystalline materials, it has various unique properties that cannot be obtained with crystalline materials, such as high hardness and strength, high magnetic permeability, It has properties such as high corrosion resistance, and applied research is being conducted in various fields using this property.

Generally, amorphous materials are manufactured by a liquid quenching method, which is a method in which molten metals, alloys, etc. are rapidly cooled. Typical examples of this liquid quenching method are (1
) Single roll method for producing thin strips, roll method, centrifugal quenching method, cutting) Taylor method for producing thin wire, fluidized liquid spinning method, etc.
(3) There are spray methods, cavity silane methods, etc. for producing powder.

(Problems to be Solved by the Invention) However, the amorphous materials produced by these methods are thin ribbons (at most several tens or hundreds of μm thick).
Because they are powders and thin wires with a particle size of several tens or hundreds of micrometers, they are used only in extremely limited small-scale applications.

Therefore, in recent years, research has been conducted into methods of forming amorphous materials into blocks for a wide range of applications. It is extremely difficult to produce bulk amorphous molded bodies.

For example, a method has been devised (Japanese Unexamined Patent Publication No. 7433/1983) to obtain an amorphous compact by filling a cylindrical metal container with powder of an amorphous material and pressing the container with explosives from around the container. There is. However, because the hardness of the powder is higher than that of crystalline powder, it is difficult to obtain a uniform and integral molded product unless high-energy impact pressure is applied uniformly, and if the pressure is too high, the amorphous powder It has many problems such as crystallization, cracking, cracking, and formation of cavities. Furthermore, when produced industrially by the above method, the cost becomes high.

Also, while bringing the ribbon of amorphous material into contact, a specific pressure (at least 0.006 Gpa) and crystallization temperature (T
x) Compressing at a temperature below (approximately 70 to 90% of the crystallization temperature) - a method of obtaining an amorphous block-shaped body by so-called hot press molding (JP-A-59-28501; JP-A-5
9-28502), or by placing ribbons of amorphous material in contact with each other at a specific pressure and glass transition temperature (Tg).
A method (U.S. Pat. No. 4,298,382) has been devised in which hot pressing is carried out at temperatures ranging from 25° C. above the glass transition temperature (Tg) to about 15° C. above the glass transition temperature (Tg). There is. That is, diffusion bonding and hot press molding using pressure and heating are considered to be effective for amorphous materials as well as for crystalline materials. However, the temperature (
Conventionally, there is a serious problem in that some or all of the amorphous material crystallizes during hot press molding when heated to about 90% or more of the crystallization temperature (Tx℃). Attempts have been made to obtain a molded body by heating to a temperature below the crystallization temperature (Tx). Therefore, the molded product obtained by the above-mentioned manufacturing method is
The density is 90% or less of the theoretical density, that is, 10% or more of pores are present in the molded body. Therefore, the problem is that the magnetic properties deteriorate compared to thin ribbons of amorphous materials, or that the high magnetic permeability characteristic of amorphous materials is not exhibited even when compared to conventionally used magnetic materials such as permalloy. have.

Therefore, the present inventors attempted to mold a powdery amorphous material into a block-shaped compact by using diffusion bonding using pressure heating as described above, and found that the heating temperature was higher than the crystallization temperature (Tx
), part or all of the amorphous material crystallizes, making it impossible to obtain a good amorphous compact; conversely, if the temperature is sufficiently lower than the crystallization temperature CTx), the powder becomes solid and - The molded product was not bonded to the body and was brittle and easily broken.

After that, the inventors repeated various theoretical studies and experiments, and found that under ultra-high pressure (several Q p B mlQ'P
In case a), by focusing on the phenomenon that the crystallization temperature (Tx) of the amorphous substance increases and utilizing this phenomenon in the method for producing a block-shaped compact, a good block-shaped amorphous compact can be obtained. I came to the idea that it would be possible.

However, regarding the above phenomenon, there is a small report that the crystallization temperature (Tx) of an amorphous material increases by about 10°C per about 1 Gpa (Bulletin of the Japan Institute of Metals, Vol. 21, No. 9).
No., 19B2: W, ni, Wang, H, Iwasaki.
and K, Fukamlchi: J, Mata.
r, Set, 15 (1980), 2701), but those reports only mention thin strips of amorphous materials and do not study powders, and they also do not investigate bulk amorphous moldings. The bonding strength and density when manufacturing the body had not been elucidated.

Therefore, the present inventors formed the powder of an amorphous substance by heating it to a temperature higher than the crystallization temperature (Tx) at normal pressure under conditions of ultra-high pressure (about several Gpa). Conventionally, even at temperatures above the crystallization temperature (Tx) or above 90% of the crystallization temperature (Tx) at which all or part of the amorphous material crystallizes, it remains dense (at least 90% density) and remains amorphous. The present invention was achieved by discovering that it is possible to obtain a lump-like amorphous molded body that is integrally molded.

(Means for Solving the Problems) The present invention has been made in view of the above-mentioned points, and the present invention has been made in view of the above-mentioned points. The purpose is to provide a manufacturing method for manufacturing.

That is, the present invention utilizes the fact that the crystallization temperature (Tx) of an amorphous material increases depending on pressure to obtain a lump-shaped compact from a powder of an amorphous material. Ultra high pressure (p)
Below, the crystallization temperature (T
X) and below the crystallization temperature (Tx (p)) of the amorphous material at its pressure (p),
It is characterized by producing a lumpy amorphous molded body by pressurizing and heating powder of an amorphous substance.

Here, amorphous substance powder refers to amorphous substances such as metals, alloys, semiconductors, dielectrics, etc. that have been pulverized into small pieces.
The powder used is one produced by a spray method, a cavity silane method, a rotating ring water injection method, or the like, or a thin ribbon of an amorphous material produced by a roll method or the like is pulverized into small pieces. Further, although amorphous materials of any composition can be used to produce bulk molded bodies by the method of the present invention, when ferromagnetic properties are desired in the molded bodies, the compositions are Fe-based and C.

Just choose the appropriate one from the system.

In the production method of the present invention, the heating temperature is set to a temperature exceeding 90% of the crystallization temperature (Tx) of the amorphous material under normal pressure, and the crystallization temperature (Tx) of the amorphous material under ultra-high pressure (p). The reason why it is limited to less than Tx (p, )) is that there is a problem that at a temperature of 90% or less of the crystallization temperature (Tx) at normal pressure, the bonded body of the manufactured molded body becomes brittle and crumbles. In addition, the crystallization temperature of amorphous materials at ultra-high pressure (
This is because the manufactured molded body will crystallize at a temperature higher than Tx(p)).

In addition, the ultra-high pressure condition is preferably 0.2 Gpa or higher, because if the pressure is less than 0.2 Gpa, the molded product will have many pores and poor bonding properties, so it will become brittle and collapse when external stress is applied. This is because the

In addition, in order to obtain a well-bonded molded body with a density of 95% or more, the pressure must be at least 1 Gpa, and the crystallization temperature (Tx) under each pressure must be equal to or higher than the crystallization temperature (Tx) at normal pressure. ) is preferred.

In addition, in order to obtain a molded product with higher density and better bondability, the higher the pressure (p), the better the crystallization temperature (p) under that pressure (p). Tx
(p)) increases, making it possible to heat the material to a higher temperature.

However, in practice, a device that generates a pressure of 10 Gpa or more would be large, so a pressure of less than 10 Gpa would be preferable. Furthermore, if the density of the shape is 95% or more and it is to be produced industrially, , the lower the pressure, the better, so the pressure should be several Gpa, that is, 1 Gpa or more and 3 Gpa.
It is believed that pressures of less than or equal to

(Example) Before explaining the examples of the manufacturing method of the present invention, (1) crystallization temperature (Tx (p)) (al crystallization temperature (Tx) under ultra-high pressure (p), (b) High temperature and high pressure generator,
(C) Measurement pressure cell and (d) Measurement results will be explained.

■, crystallization temperature (Tx(p) under ultra-high pressure (p>
) (a) Crystallization Temperature (Tx) For amorphous materials, the crystallization temperature (Tx) is generally defined as the temperature at which the onset of crystallization occurs and is measured by differential scanning calorimetry using the heat capacity versus temperature curve wA (differential thermal The crystallization temperature (Tx) described in I in the specification is the point at which the electrical resistance suddenly changes when an amorphous substance starts crystallizing. The temperature at which the electrical resistance value starts to decrease in the electrical resistance vs. temperature curve is the temperature at which the crystallized part It(Tx)
shall be.

False) High temperature and high pressure generator The high pressure generator has a pressure chamber 9 of 15 x 15 x 15 mm3.
It is a cubic type pressurizing device (CIA-15), the structure of which is shown in Figure 1. The six anvils 1 forming a cube are:
- Square top surface with sides of 15 mm and height of 60 rn m
s Made of tungsten carbide (Igetalloy D-1) with a bottom diameter of 60 mm, which is made of II with an outer diameter of IQ 2 mm.
It is held by a ring of (SNCM-11). A high speed II (SKI-3) pressure plate is applied. The upper and lower surfaces of the six anvils L are fixed to guide blocks 5 and 6 in the figure, respectively, and the four sides of the guide blocks 5 and 6 are provided with sliding surfaces with an inclination angle of 45 degrees. is provided. The remaining four side anvils 1 are also fixed to side anvil supports 2 each having a sliding slope with an inclination angle of 45 degrees. The "wedge" effect using this sliding slope allows the uniaxial load in the vertical direction to be applied to the side surface 4.
A total of six anvils L, two on the upper and lower surfaces, all move synchronously toward the center of the pressure chamber 9.

The sliding parts of the side anvil support 2 and the guide block 5.6 are kept lubricated by molybdenum disulfide and Teflon sheets. Upper and lower guide blocks 5°°6 have a diameter of 65mm
The center positions are aligned using four guide pins 7. This pressurizing device is driven by a pressure tester equipped with a constant load device with a maximum load of 12 MN.

The sample heating method uses a constant power control method with a maximum output of 3KW using a Hall element and a thyristor.
This is resistance heat generated by a cylindrical carbon heater built into the 0. The heating current is applied from the current terminal plate 3 shown in FIG. 1 through the upper and lower anvils 1. In order to avoid an increase in the anvil temperature during heating, cooling water is circulated through the passageways 4 of the upper and lower guide blocks 5 and 6, and the upper and lower anvils 1
Cool the bottom of the.

(C) Measurement Pressure Cell (10) The pressure cell (10), which is housed in the pressure chamber 9 of the high-temperature, high-pressure generator (a) and heats and pressurizes an amorphous substance, will be described with reference to FIG.

For the pressure medium 11, a cubic pyrophyllite with a side of 20 mm was used, and the pyrophyllite was fired at 500° C. for 1 hour. Inside this pressure medium 11, a cylindrical carbon heater 12 (outer diameter 8 mm, inner diameter ? mm, length 10
mm), and upper and lower copper rings 13 (outer diameter 7 mm, inner diameter 5 mm, length 4.
7mm) and disc cane stainless steel plate 14 (diameter 8mm,
jj: 0.3 mm) is fitted. Inside the carbon heater 12, there are cylindrical boron nitride 15 (BN) (outer diameter 7 mm, inner diameter 5 mm, length 10 mm) and three cylindrical boron nitride 16, 17, and 18 (outer diameter 5 mm s) at the top, middle, and bottom.
Each length 5.0 mm, 2.5 mm, 2.5 mm) are fitted. A sample 19 is inserted between the cylindrical boron nitride (BN) 16 and 17 and pressurized. Carbon heater 12, boron nitride 15, 16, used here.
Items 17 and 18 were previously fired at 1000° C. for 5 hours in a vacuum furnace to remove impurities and gases therein.

This is to prevent electrical insulation from deteriorating due to leakage of impurities and gases inside during the heating and pressurizing process.

4 leads & 1I2G are pure AI, %I (Jone
refining, made by Japan Vacuum, diameter 0.35mm)
The sample 19 is wired in a four-terminal configuration so that the electrical resistance of the sample 19 can be measured. These leads 20 are connected as voltage and current leads to the four side anvils 1 shown in FIG. As the thermocouple 21, a PR thermocouple (pt-pt13%Rh) inserted between boron nitride 17 and 18 is used. Note that the lead wire 20 and thermocouple 21 are connected to the carbon heater 1.
2 and 1IIA&t, it is led out through the similarly calcined boron nitride capillary 21 described above. Furthermore, in order to improve reproducibility in the above experiment, the machining accuracy of each component of the pressure cell was maintained at 0.02 mm. Further, in order to increase the friction between the pressure cell 10 and the anvil 1 and to improve pressure generation efficiency and reproducibility, a thin layer of red iron (hematite) was applied to the surface of the pressure cell 10.

ld) Measurement results as described above (al) In the pressure chamber 9 of the high temperature and high pressure generator ('b)
Electrical resistance vs. temperature (temperature rise rate 2
℃/m1n) and the crystallization temperature (Tx (p)) at pressure (p) are shown in FIG. 3 as Q marks. sB+ts
l+* amorphous metal thin body (thickness 20 μm, length 5 m
m, width 3 mm) was used. The measurement error range of the thermocouple under high pressure is also listed.

As can be seen from Figure 3, the crystallization temperature (T
x) increases depending on the pressure (p), and the rate ΔTx/
Δp” is approximately 110° C./Gpa.

That is, the crystallization temperature (TX) under normal pressure is approximately 5
For example, under a pressure of 2 Gpa, it is about 530°C.
℃, the pressure under the pressure of 5.4 Gpa is about 560℃. Therefore, an amorphous substance under ultra-high pressure (p) does not crystallize and maintains an amorphous state even at a temperature higher than the crystallization temperature (Tx) under normal pressure. Using this phenomenon, under high pressure (p), the crystallization temperature (T
It becomes possible to bond an amorphous material without crystallizing it even at a temperature near x) (90% of the crystallization temperature (Tx)) or above the crystallization temperature (Tx).

■Method for manufacturing an amorphous molded body (a) Production pressure cell 30 Pressure cell 30 used to mold and manufacture an amorphous molded body
will be explained based on FIG. Pressure cell 30 has basically the same construction as pressure cell 10 shown in FIG.

A carbon heater 12 (outer diameter 9 mm, wall thickness 0.5 mm) is placed inside the pressure medium 11 (cube with a side of 29 mm).

10 mm in length) and upper and lower copper rings 13 (outer diameter 8 mm, wall thickness 0.5 mm, length 4.
5mm) and copper plate 14 (diameter 9mm, thickness 0.5mm)
, a pyrophyllite cylinder 11° (outer diameter 7 mm, length 4.5 mm) as a heat insulating material is fitted. Inside the carbon heater 12, there is a cylindrical boron nitride 15 (outer diameter 3 mm, wall thickness 1 mm, length 10 mm), and within this cylindrical boron nitride 15, three cylindrical boron nitrides 31, 32.
33 (outer diameter 6mm, each length 2.5mm 51.5m
m, 2.5 mm) is inserted. And boron nitride 31
The space between and 32 is filled with powder 34 (thickness: 3.5 mm) having the composition shown in Tables 1 to 3. Moreover, between boron nitride 32 and 33,! A thermocouple 21 identical to that shown in FIG. 2 is provided. In addition, each of the above-mentioned components is
It is made of the same material, work precision, heat treatment, etc. as the pressure cell 10 already described.

The above-mentioned powder 34 is in the form of flakes (density 7.
18, Thickness 10~50μ, Length 50~200μ, Width IO
-50μ) and granular particles (particle size 5 to 200μ) prepared by a rotating liquid injection method were used.

佽）Manufacturing method Powder with the composition and shape shown in Tables 1 to 3 was placed in a press cassette 3.
Fill it evenly within 0. Here, filling was performed by applying appropriate vibrations from the outside. Thereafter, the pressure cell 30 is inserted into the pressure chamber 9 of the high temperature and high pressure generator, and while pressurized to a predetermined pressure, the pressure cell 30 is heated at 20 °C/m to a temperature 100 °C below the predetermined temperature.
It was heated at a rate of i n, and then heated instantaneously (in a few seconds) to a predetermined temperature. The pressurizing time after reaching this predetermined temperature was defined as the molding time. After molding, the molded product was rapidly cooled by turning off the heating current (average cooling temperature was approximately 140°C/5ec). After the rapid cooling, the pressure was lowered and the molded product was taken out and subjected to XvA diffraction, electron beam diffraction, and high-resolution 78M observation. Amorphousness was confirmed, and those for which the presence of amorphous was recognized by any test were determined to be amorphous and marked with an ○ mark in the table. In addition, the density was measured based on the Archimedes method, and the density of the powder was compared with that of an amorphous ribbon having the same composition, and the ratio was shown. The hardness is the average value of Vickers hardness measured at several locations on the surface of the molded body. The zygosity is
When the above-mentioned measurement experiment was carried out, it was determined whether the surface of the molded body was crushed when it was polished, and the m-weave was observed using an optical microscope.

Incidentally, the surface of the molded body was polished using emery paper.

(C) Amorphous molded object When an amorphous material is heated, crystallization begins at a specific temperature, but this crystallization process is extremely complex, and the crystallization temperature (Tx) depends on the temperature and its maintenance. related to time. Generally, the crystallization temperature (Tx) of an amorphous material is determined by the MS-1 layer (
This is the temperature at which a metastable phase (a metastable phase in which a minute crystal layer (approximately 30 to 50 people in diameter) with uniform nuclei generated in an amorphous material precipitates) appears, and the temperature (TX) changes depending on the holding time. As the length increases, the crystallization temperature (Tx) decreases,
In the time-temperature-transformation diagram (hereinafter referred to as TTT diagram),
It is known that the crystallization temperature (Tx) shows a downward slope.

On the other hand, 1. Crystallization temperature (Tx) under ultra-high pressure (p)
As already explained in (p)), ultra-high pressure (
At p), the crystallization temperature (T
It was confirmed that x) increased. In addition, based on this, an amorphous molded body was manufactured by the method already explained in Section (1), Manufacturing method of an amorphous molded body, and the results shown in Tables 1 to 3 were obtained. The results are plotted in Figures 7 to 9, and the crystallization temperature (Tx) at each pressure (p) is determined by determining the presence or absence of amorphous property.
．． The crystallization temperature (T
x) is 55 to 60°C, and the crystallization temperature (Tx) is increased by about lθ°C under an ultra-high pressure of 1 Gpa. That is, although the crystallization temperature (TX) depends on the holding time, it is confirmed that the crystallization temperature (TX) increases at a rate of 10° C./Gpa at a predetermined holding/molding time.

As is clear from Table 1, the molded bodies molded according to the manufacturing method of the present invention -1 to 10 all have a density of 90% or more, no lattice image is observed in high-resolution 78M observation, and In X-ray diffraction and electron diffraction, only halo patterns and halo rings characteristic of amorphous materials were observed.It is a good amorphous material, and its bondability is also good, with a hardness of 830 on the Vickers scale.
It had a high hardness of ~91O.

That is, this composition has a crystallization temperature (TX) of 510°C at normal pressure.
(holding time is several minutes), but the temperature is higher than 5.
Molded at 50°C, pressure 5.4 Gpa, and molding time 1 minute (Example 11th3.5), or at 460°C and pressure 0 at a temperature of 90% or more of the crystallization temperature (Tx).
．． 2. The molded products under the conditions of 1 minute molding time (execution side part 10) remained amorphous without crystallization, were bonded with a density of 95% or more, and had a Vickers hardness similar to that of crystalline. It was relatively high. In addition, the crystallization temperature (Tx) at normal pressure and holding time of 10 minutes is 465°C, but at a higher temperature of 500°C, pressure of 5.4 Gpa, and molding time of 1
0 minutes (Example-2), or the same temperature (Tx) as 460°C, pressure 1°0 Gpa,
Even when molded under the conditions of molding time of 10 minutes (Example No. 8), good products were obtained which were amorphous and had a density of 93% or more. In addition, the crystallization temperature (T
X) is 407℃, but the higher temperature is 450℃,
Pressure 5.40pa, molding time 126 minutes (Example-1, 4
), or crystallization temperature (Tx)
Same temperature as 407℃, pressure I Gp a, molding time 12
Molded under the conditions of 0 minutes (Example Arashi 7), 90% of the crystallization temperature (Tx) at 367°C, pressure 0, 20 p
a, and those molded under the conditions of molding time 120 minutes (Example 11h9) were all good amorphous and had a density of 90.
% or more was obtained.

From the above, the crystallization temperature (Tx (p)) is 10℃/Gp at each pressure of 0.2 Gpa or higher.
Even if the temperature is higher than the crystallization temperature (Tx) at normal pressure for the above composition, if it is lower than the crystallization temperature (Tx (p)) at each pressure p, the molded body will be crystallized. It can be seen that it is in an amorphous state without becoming oxidized. Further, if the temperature is higher than 90% of the normal pressure crystallization temperature (Tx (p)), a well-joined molded body with a density of 90% or more can be obtained.

In addition, in order to obtain a well-joined molded body with a density of 95% or more, the pressure must be at least 1 Gpa, and the crystallization temperature (Tx (p It turns out that temperatures below )) are preferred.

Furthermore, the time required for molding depends on its working time, workability,
It is possible to change the time as appropriate depending on the cost, but considering the preservation due to thermal expansion when raising the temperature of the high pressure generator pressure cell etc. to the specified temperature, the time required is about several tens of seconds to one minute. (Both are necessary and considering industrial productivity, ioo.

It would be preferable to set the molding time to less than 2 hours.However, if we consider productivity, it would be more advantageous in terms of cost if the molding time is within 2 hours.As can be seen from Figures 7 to 9, Needless to say, when molding for a short time, it is necessary to mold at a higher temperature than when molding for a long time.

On the other hand, in comparative examples in which the temperature and pressure in the manufacturing method are outside the range of the present invention, it can be seen that the amorphous is crystallized or the bonding is poor (it becomes brittle and collapses, causing practical problems). .

That is, the crystallization temperature (Tx
(p)) Higher temperature (Example &11 to I'&L16)
Although the molded products under the above conditions had a density of 90% or more, none of them were amorphous, and all or a portion thereof was crystallized. In addition, the temperature is 90% or less of the crystallization temperature at normal pressure, and the pressure is lower than 0.2 Gpa (Example 1).
In all of the powders produced in 7 to 20), the powder was not bonded at all, or the bonding properties were poor and the particles were brittle and crumbled.

Incidentally, FIG. 5 is a photomicrograph of a good molded product molded by Example 11kL1, and FIG. 6 is a photo of a molded product molded by Comparative Example Arashi 18 with poor bondability.

Similarly, when Go -B-S tSN i -B-5i was also tested, the results shown in Tables 2, 3, 4, and 5 were obtained.

Therefore, in the above experiment, Fe B 5i-Co-B-
3i and N 1-B-3i system compositions, but those skilled in the art will be able to calculate the
It would be easy to obtain dense and amorphous molded bodies of other compositions by conducting experiments and producing them.

Table 1-1 Fe-based amorphous alloy (FetsB+zS
f 16) Table 1-2 Fe-based amorphous alloy (pew'
B193 i,,) Table 2 CO-based amorphous alloy (C
OysStsB+. ) Table 3 Ni-based amorphous alloys (
N'raS i +78s) (0 Effect of the invention) The present invention utilizes the fact that the crystallization temperature (Tx) of an amorphous material increases under ultra-high pressure (p), and at a specific pressure, temperature, and molding time. By molding, it was possible to obtain an amorphous molded body with extremely high density and good bondability. Such amorphous compacts have a large volume compared to amorphous ribbons, powders, etc., so their industrial value is high as they are expected to have a wider range of uses. be. In particular, since the amorphous molded body molded according to the manufacturing method of the present invention has extremely high density, it can be used as a magnetic material for various purposes.

[Brief explanation of the drawing]

Figure 1 is a schematic view of the high-temperature and high-pressure generator from the top and side views, Figure 2 is a schematic perspective view showing the components of a pressure cell for measuring crystallization temperature (Tx), and Figure 3 is a diagram showing pressure (p) and A diagram showing the relationship between crystallization temperature (Tx (p)), FIG. 4 is a schematic perspective view showing the components of the molding pressure cell used in the examples, and FIG. 5 is the example part 1 of Table 1. FIG. 6 is a microscopic photograph of the molded product molded in Comparative Example No. 18 of Table 1. FIG. 7 shows the results of Table 1, f,
Knee T T T Figure 8 shows the results in Table 2.
TT diagram, Figure 9 is a TTT graph showing the results of Table 3.
It is a diagram. Representative Patent Attorney Takashi Okabe 1i1 Figure 4FIII Pa', ゛, ), 415, f, 1''<, y,, W'''゛〼'ku1y,・Pa・'+-'t'. ~ fH7 figure time (intermediate) Haru autopsy P -・Ren P

Claims (7)

[Claims] (1) In a method of manufacturing an amorphous molded body by pressurizing and heating powder of an amorphous substance, the crystallization temperature (Tx) of the amorphous substance at normal pressure under ultra-high pressure (p) at least 90 of
% and below the crystallization temperature of the amorphous material (T A method for producing a characterized amorphous molded body. (2) The ultra-high pressure (p) is at least 0.2 Gpa
The method for producing an amorphous molded body according to claim 1, wherein the pressure is . (3) The ultra-high pressure (p) is 1 Gpa or more and 10 Gpa
The method for producing an amorphous molded body according to claim 1, wherein the pressure is less than or equal to (4) The method for producing an amorphous molded body according to claim 1, wherein the high pressure (p) is a pressure of 1 Gpa or more and less than 3 Gpa. (5) Crystallization temperature (Tx(p)) at the pressure (p)
) is the temperature obtained by adding a temperature increased at a predetermined rate according to the pressure (p) to the crystallization temperature (Tx) at normal pressure. Claims 1, 2, 3, or 4. The method for producing an amorphous molded body according to item 4. (6) The predetermined ratio is such that the temperature is 10 Gpa per pressure.
6. The method for producing an amorphous molded article according to claim 5, wherein the rate of increase in temperature is .degree. (7) The method for producing an amorphous molded body according to claim 3 or 4, wherein the temperature is equal to or higher than the crystallization temperature (Tx) at normal pressure.