JP3484360B2 - Manufacturing method of amorphous alloy hollow molded article - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molded article having an amorphous phase, and more specifically, a hollow molded article having an amorphous phase obtained by pouring a molten alloy into a mold. Regarding manufacturing.

[0002]

2. Description of the Related Art Conventionally, as a manufacturing method of this type, a technology described in Japanese Patent Laid-Open No. 3-253525 is known. This publication discloses that a molten metal is injected into a mold to produce a solidified material having an amorphous phase. By controlling the conditions of the molten metal at the time of pouring, the cooling conditions of the molten metal, etc. It is disclosed that it is possible to produce a solidified material having a substance phase. However, the technique described in the above publication is an effective method for producing a solid intermediate material (plate-shaped, columnar, rod-shaped, etc.) or a cast material having a simple shape. It is difficult to manufacture a complex or hollow product.

In order to improve these points, a technique disclosed in, for example, Japanese Patent Laid-Open No. 5-309427 is already known. The technique of this publication is disclosed in the above-mentioned Japanese Patent Laid-Open No. 25352/1993.
First, an intermediate material is produced by using the method described in Japanese Patent Publication No. 5, and the intermediate material is placed in a mold for imparting the shape of the final molded product, and the final shape is imparted in the mold to form the molded product. It is what However, in this technique, in order to give the final shape once the intermediate material is manufactured, it has to be set again in a different mold and reheated to perform molding, and the process is complicated and There is a problem that it is difficult to maintain the amorphous phase because it is thermally affected by heating.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and a molded product is manufactured by a relatively simple method and the thermal effect is reduced to form an amorphous phase. The object of the present invention is to provide a method for producing an amorphous alloy hollow molded product, which can easily manufacture a hollow molded product, and can be easily applied to a hollow molded product having a complicated surface shape. It is an object of the present invention to provide a method for producing an amorphous hollow molded article having good dimensional accuracy.

[0005]

According to a first aspect of the present invention, a molten alloy having a composition having a glass transition region is filled in a molding die, cooled to a temperature in the glass transition region, and then cooled. Hold the alloy at the temperature in the area, and then hold it in the alloy by using a gas nozzle placed in the mold.
It is a method for producing an amorphous alloy hollow molded article, in which a hollow molded article having an amorphous phase is produced by performing pressure molding with pressure and cooling.

In a second aspect of the present invention, a molten alloy having a composition having a glass transition region is filled in a mold and cooled to a temperature not higher than the melting point but not lower than the crystallization temperature, and after cooling, the melting point and the crystallization temperature are changed. Hold at a temperature within the temperature range between, then to the held alloy, to the gas nozzle placed in the mold
The method for producing an amorphous alloy hollow molded article is characterized in that a hollow molded article having an amorphous phase is produced by performing pressure molding with a gas pressure according to the above and cooling.

According to a third aspect of the present invention, a molten alloy having a composition having a glass transition region is filled in a mold and cooled to a temperature not higher than the melting point and not lower than the crystallization temperature, and after cooling, the melting point and the crystallization temperature are set. Hold at a temperature within the temperature range between, then to the held alloy, to the gas nozzle placed in the mold
By applying pressure forming by gas pressure according to the above, further cooling to the temperature in the glass transition region, after cooling, holding at the temperature in the glass transition region, and then applying pressure forming to the held alloy and cooling it A method for producing an amorphous alloy hollow molded article, which comprises producing a hollow molded article having a crystalline phase.

The component composition of the molten alloy which can be applied to the present invention is required to have a glass transition region, and for easier molding, a component composition having a glass transition region of 40K or more. Is preferred.
Specifically, the component composition described in JP-B-7-122120 and JP-B-7-122119, that is, the component composition of the molten alloy is the following general formula I) or II).
Shown are those _{I) X a M b Al c} II) Al100-de T d Ln e ( where a, X: 1 one or two elements selected from Zr and Hf, M: Ni, Cu, Fe, Co, At least one element selected from Ti and Mn, T: Ti, V, Cr,
Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, H
at least one element selected from f, Ta and W, L
n: Y, La, Ce, Nd, Sm, Gd, Tb, Dy,
At least one element selected from Ho, Yb and Mm (Misch metal which is an aggregate of rare earth elements), a,
b, c, d, and e are atomic percentages of 25 ≦ a ≦ 85, 5
≦ b ≦ 70, 0 <c ≦ 35, 0 <d ≦ 55, 30 ≦ e ≦
90. ) Is effective, and especially the above general formula I) is effective. The alloy described in the above general formula has a glass transition region, has a glass transition region of 40K or more in most component compositions, and has a glass transition region of 60K or even more than 80K in a specific component composition. Things exist. Incidentally, the component composition of the above general formula is a preferred example, if the component composition having a glass transition region,
It goes without saying that the present invention can be applied.

Glass transition region (supercooled liquid region: ΔT =
Tx-Tg) is a temperature range between the crystallization temperature (Tx) and the glass transition temperature (Tg) of the alloy having an amorphous phase. The glass transition temperature (Tg) is a value at a portion where an endothermic reaction occurs on the obtained differential scanning calorimetric curve or differential thermal analysis curve when the alloy having an amorphous phase is subjected to differential scanning calorimetric analysis or differential thermal analysis. The temperature at the point where the rising portion of the curve intersects with the extrapolation of the base line, on the contrary, the crystallization temperature (Tx) is the temperature obtained in the same manner as above at the portion where the exothermic reaction occurs.

Due to the existence of the glass transition region and the wideness of the region, it is possible to easily and indefinitely plastically deform at a low pressure, and to control the temperature during molding (processing) and the control of molding (processing) time. Can be relaxed. In addition, because of its characteristics as so-called glass (amorphous), the molding (deformation) surface has extremely high smoothness, and steps such as slip bands appearing on the surface, such as when deforming a crystalline alloy, do not substantially occur. There are features. Further, an alloy having a glass transition region and having a wider region has a high amorphous forming ability, and the formed amorphous phase is also stable.

In the manufacturing method of the present invention, when the molten alloy is filled in the mold and cooled to a temperature in the glass transition region or to a temperature between the melting point and the crystallization temperature, the final molded product is not cooled. In order to have a crystalline phase, it is necessary to set the cooling rate such that it does not enter the crystallization region of the continuous cooling transformation curve (CCT curve) or enters it to some extent. In particular, in order to make the final molded product an amorphous single phase, the cooling rate must be such that it does not enter the crystallization region.
It should be noted that since the above-mentioned region differs depending on the component composition, it is necessary to obtain such knowledge in advance, but as a concrete guideline, it is preferable to set it to 10 K / s or more, and further 10 ² K / s It is more preferable to set it as above.

Further, the manufacturing method of the present invention is characterized in that molding (processing) is performed in the process of filling the molten alloy in a molding die and cooling it, and this molding (processing) is performed in the glass transition region. It is applied to an alloy (molten metal) held at a temperature inside or a temperature between the melting point and the crystallization temperature, and pressure is applied to the alloy filled in the forming die (pressure forming). Specific pressure molding is performed by injecting gas into the molding die and using gas pressure . This approach, hollow molded article and / addition is effective in producing a molded article subjected to complicated pattern or the like on the surface.

The cooling rate after molding (processing) is preferably 10 K / s or more, more preferably 10 ² K, as a concrete guide, similar to the cooling rate at the time of pouring the mold before the above-mentioned molding. / S or more is preferable. Hereinafter, a specific example of the manufacturing method of the present invention will be described with reference to the drawings.

FIG. 1 shows a method of injecting gas into a molding die and performing it by gas pressure. As shown in FIG. 1a), the molding die comprises two molds, an upper mold 1 and a lower mold 2. A molding part 3 of a molded product is formed therein, and a heating means (heating heater) 4 and a temperature detecting means (thermocouple) 5 are provided in the molding die in order to maintain or control the temperature inside the die. ing. Immediately above the sprue 6 of the mold A, a molten metal supply means (quartz crucible) 8 having a heating means (high frequency heating coil) 7 different from the above is arranged. The molten metal supply means 8 is slidable with respect to the sprue 6 of the mold A. Figure 1b) c)
d) is a drawing showing the action of pressure molding. As shown in the figure, the apparatus is constructed such that a gas pressure means (air nozzle) 9 is slidably arranged on the sprue 6 directly above the sprue of the molding die. Has been done. The configuration other than this is the same as that of FIG. Next, the operation will be described with reference to FIG. As shown in FIG. 1a), the master alloy having its components adjusted is supplied to the molten metal supply means 8 and heated by the heating means 7 to melt the master alloy. Next, the molten metal S is supplied from the gate 6 of the molding die A to the molding part 3 in the molding die, and the molten metal S is cooled in the mold to obtain a temperature in the glass transition region or between the melting point and the crystallization temperature. Hold at temperature.

The temperature control at this time is performed by the temperature detecting means 5 and the heating means 7. As shown in FIGS. 1b) to 1c), the gas pressure means 9 is supplied to the molten metal (alloy) S whose temperature is maintained as described above, and the inert gas such as He or Ar is supplied from the gas pressure means 9. By supplying at a predetermined pressure, a hollow molded product P matching the shape of the molding portion 3 is manufactured as shown in FIG. 1d). Various conditions are based on the above.

Further, a specific manufacturing method will be described with reference to the drawings.

[0017] Figure 2 is a view showing a method of manufacturing a hollow float for fishing or fish net (molded article), the process is as shown in FIG. 2 a) b) c).

[0018] As shown in FIG. 2 a), is in the mold of the mold A will be formed molding part 3, also for temperature maintenance or control in the mold is a mold A, the heating means ( (Heater heater) 4, cooling means (cooling water or cooling gas passage) 11
Further, a temperature detecting means (thermocouple) not shown is provided. Immediately above the sprue 6 of the mold A, a molten metal supply means (quartz crucible) 8 having a heating means (high frequency heating coil) 7 different from the above is arranged. The molten metal supply means 8 is slidable with respect to the sprue 6 of the mold A. Further, a gas pressure means (air nozzle) 9 is arranged immediately below the molding portion 3 of the molding die A so as to be slidable toward the opening of the molding portion 3. Furthermore, the apparatus described above is housed in a container, and the container is provided with a cooling gas inlet 12 for supplying a cooling gas. Next will be described the effect on the basis of FIG.
As shown in FIG. 2 a), the master alloy, the components of which have been adjusted, is supplied to the molten metal supply means 8 and heated by the heating means 7 to melt the master alloy. Then fed to the molding portion 3 of the sprue in the mold than 6 of the mold A molten metal S as shown in FIG. 2 b), the melt S was cooled in the mold, the temperature or the melting point of the glass transition region Hold at a temperature between the crystallization temperature. The temperature control at this time is performed by the temperature detecting means 5, the heating means 7, and the cooling means 11. Thus the molten metal temperature is held (alloy) figure S 2 b), as shown in Figure 2 c),
Gas pressure means 9 is supplied, and for example He,
By supplying Ar inert gas such as at a predetermined pressure, to produce a hollow molded article P as shown in FIG. 2 c). The molded product P manufactured in this way is cooled by the cooling means 11
Finally, the cooling gas from the cooling gas inlet 12 is used for cooling.

In FIG. 3 , the molding die A of FIG. 2 is used as the lower die 2, and the lower die 2 and the upper die 1 constitute the molding die A. The lower surface of the upper die 1 has a convex shape. The molding part 3 is formed. 4 has the same basic device structure as FIG. 3 ,
The difference is that a concave shaped portion 3 is formed on the lower surface of the upper mold 1. 3, convex mirror or a concave mirror comprising a hollow by using the apparatus shown in Figure 4 (molded article) P can be produced, respectively.

The operation of the manufacturing method shown in FIGS. 3 and 4 is as follows.
First, FIG. 2 a) b) the melt S is supplied to the lower mold 2 as shown in, then 3, together with arranging the upper mold 1 as shown in FIG. 4, to supply gas pressure means 9 production Is to do. Other points are the same as in FIG.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on Examples. First, prior to the experiment, Zr ₅₅ Al ₁₀ N
The i ₅ Cu ₃₀ amorphous single phase alloy was subjected to thermal analysis by DTA (differential thermal analysis). The measurement was performed by heating at a temperature rising rate of 10 ° C./min. The results are shown in FIG.
According to FIG. 5 , the glass transition temperature (Tg) was 391 ° C. (6
64K), crystallization temperature (Tx) is 479 ° C (752K)
And the glass transition region (temperature range: ΔT) is 88 ° C.
(88K). Further, regarding the above alloy, a continuous cooling transformation curve (CCT curve) and an isothermal transformation curve (T
TT curve) was examined. The examined results are shown in FIGS. 6 and 7 , respectively. FIG. 6 shows how to control the cooling rate during manufacturing, and FIG. 7 shows the time during which the mold can be maintained at a constant temperature. Specifically, as shown in FIG. 6 , in order to prevent the crystallization of the molded product (in particular, to maintain the structure of the amorphous single phase), the cooling rate is set so as not to enter the crystallization region. Then, the glass must be cooled to the temperature of the glass transition region, and in the case of entering the crystallization region as described above, at least a part is crystallized and an amorphous single-phase molded product cannot be obtained. In the case of 1, the molded product is a mixed phase of an amorphous phase and a crystalline phase or a crystalline phase having no amorphous material at all. Which structure is formed is determined by the time of entering the crystallization region. According to FIG. 7 , in the case of 750 K (477 ° C.), it can be held in the molding die for 100 seconds (including the molding time), and 700 K (4
It can be seen that it can be held for 10 4 seconds in the case of 27 ° C. On the other hand, when forming is carried out at a temperature between the melting point and crystallization temperature must be carried out in a region that does not enter the crystallized region as shown in FIG. 8 (eg fold line portion). Also, the figure
As shown in FIG. 8 , the first stage molding may be performed at a temperature between the melting point and the crystallization temperature, and the second stage molding may be performed at a temperature in the glass transition region. In this regard, this kind of two-stage method is useful.

Based on these findings, a molten metal having the above alloy composition was cast into a mold at a cooling rate of about 10 K / s.
C. (673K), 460.degree. C. (733K) at each temperature, once held (holding the amorphous time shown in the TTT curve of FIG. 7 within a time that can be held), diameter 2.5 mm length 40
A round bar material of mm was prepared. The round bar material thus obtained was subjected to X-ray diffraction in order to examine its structure. Figure this result 9
Shown in. According to FIG. 9 , it can be seen that the round rods produced under the respective temperature conditions are in the amorphous single phase. Figure 1
The following experiment was conducted using the apparatus shown in FIG.

A master alloy of Zr ₅₅ Al ₁₀ Ni ₅ Cu ₃₀ is shown in FIG.
It was set in the quartz crucible 8 of a) and heated by the high frequency heating coil 7 to melt the mother alloy. Next, the molten metal thus melted was supplied to the forming part of the mold A, and the molten metal was cooled in the forming part. The cooling rate at this time was based on the above. In the forming part 3, the molten metal (alloy) is 400 ° C.
It was held by a heater between 460 ° C. (673K to 733K), and then molded by an air nozzle 9 as shown in FIGS. 1b) to d). He gas was used for molding, and the gas pressure was 3 kgf / cm ² . As described above, a hollow and balloon-shaped molded product P whose cross-sectional view is shown in FIG. 1d) was produced.

FIG. 10 shows the result of X-ray diffraction of the above molded product, and it can be seen that this molded product is composed of an amorphous single phase. In addition, the thickness and surface roughness of the molded product were examined. The thickness was 40 to 50 μm, which was extremely thin, and the thickness corresponding to the molding portion was uniform. Further, the surface roughness was about 0.1 μm in Rmax value, and the surface roughness was very small. The surface is a mirror surface with the naked eye.

In the molding part 3 described above, a temperature between the melting point and the crystallization temperature, specifically 600 ° C. to 800 ° C.
The same results as above were obtained when the temperature was held between (873K to 1073K). Furthermore, various molded products shown in FIGS. 2 to 4 were obtained in the same manner as above.

[0026]

EFFECTS OF THE INVENTION According to the method for producing an amorphous molded article of the present invention, a molded article can be produced by a relatively simple method and the thermal effect is reduced, and the molded article has an amorphous phase. Can be easily manufactured with high dimensional accuracy. further,
A molded product having a complicated surface shape or a hollow molded product can be easily manufactured.

[Brief description of drawings]

1A to 1D are explanatory views of a manufacturing process of the present invention.

2A, 2B, and 2C are explanatory views of a method for manufacturing a hollow float (molded product).

FIG. 3 is an explanatory diagram of a method for manufacturing a hollow concave mirror mold (molded product).

FIG. 4 is an explanatory diagram of a method for manufacturing a hollow convex mirror mold (molded product).

FIG. 5 is a graph showing a DTA curve of a Zr ₅₅ Al ₁₀ Ni ₅ Cu ₃₀ alloy.

FIG. 6 also shows a CCT curve diagram.

FIG. 7 also shows a TTT diagram.

FIG. 8 is a graph showing a molding region in a region between a melting point and a crystallization temperature.

FIG. 9 is an X-ray diffraction diagram of the same alloy obtained by casting in a mold held at 400 ° C. and 460 ° C. and then cooling.

FIG. 10 is an X-ray diffraction diagram of a molded product.

[Explanation of symbols]

A mold S molten metal 1 Upper mold 2 Lower mold 3 molding section 4 heating heater 5 thermocouple 6 gate 7 High frequency heating coil 8 quartz crucible 9 Air nozzle 11 Cooling means 12 Cooling gas inlet

Front Page Continuation (72) Inventor Masashi Yamaguchi 1-16-23 Izumizaki, Taichiro-ku, Sendai City, Miyagi Prefecture (72) Inventor Takeshi Taniguchi 2-30-26 Yamanoji Temple, Izumi-ku, Sendai City, Miyagi Prefecture (56) References Special Kaihei 10-186176 (JP, A) JP 3-204160 (JP, A) JP 10-296424 (JP, A) JP 10-311923 (JP, A) JP 5-309427 ( JP, A) Zhang et al., Making Amorphous Alloy Balloons, Boundary, September 15, 1991, Vol. 7 No. 9, P.I. 39-43 (58) Fields surveyed (Int.Cl. ⁷ , DB name) B22D 27/00-27/13 C22C 1 / 00,45 / 00-45/10

Claims (9)

(57) [Claims] 1. A molten alloy having a component composition having a glass transition region is filled in a mold, cooled to a temperature in the glass transition region, kept at a temperature in the glass transition region after cooling, and then retained. Gas in the mold, placed in the alloy
A method for producing an amorphous alloy hollow molded article, comprising producing a hollow molded article having an amorphous phase by performing pressure molding with a gas pressure from a nozzle and cooling. 2. A molten alloy having a component composition having a glass transition region is filled in a molding die, cooled to a temperature not higher than the melting point and not lower than the crystallization temperature, and after cooling, within a temperature range between the melting point and the crystallization temperature. and held at the temperature, then the retained alloys, in having an amorphous phase by cooling applying <br/> pressure molding by a gas pressure due disposed in a mold nozzle
A method for producing an amorphous alloy hollow molded article, which comprises manufacturing an empty molded article. 3. A molten alloy having a component composition having a glass transition region is filled in a mold and cooled to a temperature not higher than the melting point and not lower than the crystallization temperature, and after cooling, within a temperature range between the melting point and the crystallization temperature. The temperature of the alloy is maintained, and then the retained alloy is subjected to pressure molding by a gas pressure by a gas nozzle arranged in a molding die , further cooled to a temperature in a glass transition region, and after cooling, the glass is cooled. and held at a temperature in the transition region, the production of amorphous alloy hollow shaped article, characterized by producing a hollow molded article having an amorphous phase by subjecting the subsequently retained alloy pressure molding cooling Method. 4. The method for producing an amorphous alloy hollow molded article according to claim 1, wherein the molten alloy has a component composition having a glass transition region of 40K or more. 5. The amorphous alloy hollow according to claim 1, wherein the cooling in the forming die is performed at a cooling rate which does not enter the crystallization region of the continuous cooling transformation curve of the alloy having the above-mentioned composition. <br/> A method for manufacturing a molded article. 6. The method for producing an amorphous alloy hollow molded article according to claim 5, wherein the cooling rate is 10 K / s or more. 7. The amorphous alloy according to claim 1, wherein the pressure molding is carried out by a pressing means provided on the molding die.
A method for manufacturing a hollow molded article. 8. The cooling rate after the pressure molding is 10 K / s.
The method for producing an amorphous alloy hollow molded article according to claim 1, which is performed as described above. 9. The method for producing an amorphous alloy hollow molded article according to any one of claims 1 to 4, wherein the composition of the molten alloy is represented by the following general formula I) or II). I) X _a M _b Al _c II) Al _100-de T _d Ln _e However, from X: Zr and one or two elements selected from Hf, M: Ni, Cu, Fe, Co, Ti and Mn At least one selected element, T: Ti, V, Cr, M
n, Fe, Co, Ni, Cu, Zr, Nb, Mo, H
at least one element selected from f, Ta and W, L
n: Y, La, Ce, Nd, Sm, Gd, Tb, Dy,
At least one element selected from Ho, Yb and Mm (Misch metal which is an aggregate of rare earth elements), a,
b, c, d, and e are atomic percentages of 25 ≦ a ≦ 85, 5
≦ b ≦ 70, 0 <c ≦ 35, 0 <d ≦ 55, 30 ≦ e ≦
90.