JP5679555B2 - Metallic glass plastic forming method and plastic forming apparatus - Google Patents

Description

The present invention is, while retaining the metallic glass to a supercooled temperature range, to a plastic molding method and plastic molding apparatus for molding a metallic glass into a predetermined shape.

When processing metal glass, it is necessary to perform plastic forming by heating to a temperature exceeding the glass transition temperature (Tg) and not entering the crystallization region (so-called supercooling temperature region Tx). And in the supercooling temperature range, since it becomes easy to process like glasswork, it is supposed that metal glass can be shape | molded very easily.
For example, Patent Document 1 describes a metal glass molding apparatus that processes a metal glass placed between an upper mold and a lower mold with a mold while heating it with radiant heat from a heater. In the equipment, the sleeve is heated by radiant heat, and the upper mold, lower mold, and metal glass are heated by heat conduction from the sleeve, so the temperature of the metal glass is easily affected by the temperature of the peripheral processing equipment. There is a problem that it is difficult to always keep the temperature in the supercooling temperature range.

In recent years, metal glass having a relatively low melting point of 400 ° C. to 600 ° C. (hereinafter referred to as low melting point metal glass) has attracted attention. In the case of this low melting point metal glass, the glass transition temperature (Tg) is 100. to be relatively low temperatures to 200 DEG ° C., although there is an advantage that easy to handle as compared with the case of high temperature, for tractable supercooled temperature range is not so large, glass transition temperature is lower metallic glass when processing is well temperature of metallic glass, the peripheral processing devices (e.g. roll, dies, etc.) using also the temperature of, and precisely controlled at all times a supercooled temperature range during processing・ It is required to hold. Should is insufficient or the temperature control of the metallic glass during processing, metals glass temperature is influenced by the temperature of processing equipment near off the supercooled temperature range glass transition temperature (Tg if) it drops more, to become working difficult state lost the advantage of easy processing, also when the temperature of the material was heated to the crystallization region, excellent characteristics as a metallic glass It will be completely lost.

JP-A-10-249600

The present invention, plastic molding method for molding a processing equipment etc. near subjected to Ruga lath transition temperature and our low metal glass on the molding while kept at the supercooled temperature range, the metallic glass into a predetermined shape and An object is to provide a plastic forming apparatus.

Upon melting point Tg is processed metallic glass of 80 ° C. to 200 DEG ° C. at 400 ° C. to 600 ° C., since the supercooling temperature zone is not so large, it, Rukin genus Gala is subjected to plastic forming also the temperature of the processing equipment around to be used for processing not a Minara a scan of intensive studies on techniques which can be always held in the supercooled temperature range during processing. As a result, heat held in the range Tr (room temperature) of to 210 ° C., in an excellent silicone oil in oxidation resistance be processed while immersed processing equipment around and your metallic glass, only the temperature of the silicone oil It has been found that the above-described problem of the present invention, in which plastic molding is performed while maintaining in the supercooling temperature range, can be solved only by a simple operation of controlling and managing the above.

The present invention has been made based on such knowledge.
The present invention, the metallic glass of the glass transition temperature Tg of 80~200 ℃, Tg + 5 ℃ ~Tg + 30 ℃ method forming features and to Rukin genus glass to plastic forming in silicone oil in a temperature range of It is.
The present invention has a glass transition temperature Tg of 80 to 200 ° C. The metallic glass by immersing the processing means for plastic forming in a silicone oil which is stored in the tank, the temperature of the silicone oil of Tg + 5 ℃ ~Tg + 30 ℃ held within a range, before after forming the Kikin genus glass is supplied to the processing unit from outside the tank, characterized in that quickly discharged the molded metallic glass to the tank outer it is a plastic molding method of metallic glass.

In metallic glass plastic molding method of the present invention, it is preferable time before Kikin genus glass is immersed in the silicone oil is in the range of 30 to 300 seconds. Further, polarized before performing the rolling process Kikin genus glass, or inside the the mold provided with a groove of arcuate cross-sectional shape as the processing means and the groove by using a pair of rolls as said processing means using one roll being Kokoroshite disposed, it is preferable to carry out the reduced diameter of the front Kikin genus glass.

The present invention includes a tank for storing the silicone oil, and the processing means is immersed in the silicone oil in the glass transition temperature Tg is plastically molding the metallic glass of 80 to 200 ° C., the pre-Kikin genus glass a material feeding means for charging said processing means from the outside of the tank, and unloading means for discharging Kikin genus glass before molded by said processing means to said tank outside of the temperature of the silicone oil Tg + 5 ℃ ~Tg + 30 ℃ an oil temperature adjusting means for retaining within a plastic forming device features and to Rukin genus glass to have a.

In the plastic molding apparatus metals glass of the present invention, that the processing means comprises a pair of rolls, or the processing means, and the mold having a groove of arcuate cross-sectional shape, the inside of the groove It is preferable to have one roll arranged eccentrically.

According to the present invention, the processing equipment and the like around the Tg is called contact metal having a low glass to be subjected to machining while maintaining the supercooled temperature range, it is possible to plastically molding the metallic glass into a predetermined shape.

It is a perspective view which shows typically the example of the plastic forming apparatus of this invention. It is sectional drawing which shows typically the other example of the plastic forming apparatus of this invention. It is a state diagram from a molten state of the metallic glass to solidify. An example of a device for injection molding a metallic glass is a perspective view schematically showing.

Figure 1 is an example of a plastic forming device of metallic glass of the present invention is a perspective view schematically showing. The present invention is subject and to Rukin genus glass (melting point Tm: 400 to 600 ° C., a glass transition temperature Tg: 80 to 200 ° C.) are, Au-Cu-Si-based, Au-Cu-Ag-Si-based, Ca -Li-Mg-Zn, Ce-Cu-Al, Yb-Zn-Mg-Cu, Au-Cu-Ag-Pd-Si, Pt-Ni-Cu-P, Mg-Cu-Au- Ga-based metallic glass.

  Silicone oil 2 is stored in the tank 1, and an oil temperature adjuster 3 that adjusts the temperature of the silicone oil 2 is attached to the tank 1. The oil temperature controller 3 has a built-in heater and thermometer, and PID control is performed based on the measured value obtained by the thermometer and the target temperature of heating by the heater, so that the temperature of the silicone oil 2 is adjusted. The target temperature can be maintained within a range of ± 0.5 ° C. The oil temperature regulator 3 is provided with a pump for circulating the silicone oil 2. After the silicone oil 2 in the tank 1 is taken into the oil temperature regulator 3 through the inflow pipe 12 and heated to a predetermined temperature. The silicone oil 2 is returned to the tank 1 through the outflow pipe 13. In this way, the temperature of the silicone oil 2 in the tank 1 can be kept constant. In addition, since the silicone oil 2 circulates through the tank 1 and the oil temperature regulator 3, the silicone oil 2 in the tank 1 is agitated, and the effect of making the temperature of the silicone oil 2 uniform is also obtained.

The metallic glass 5 processing equipment for plastic molding is arranged immersed in silicone oil 2. FIG. 1 is a perspective view showing an example in which a pair of rolls 6 is used as a processing device. The arrows in FIG. 1 indicate the rotation direction of the roll 6. Further, the inclined surface 7 for supplying metallic glass 5 from 1 outer tank disposed, from the lower end of the inclined surface 7 to the entry side of the roll 6 processing equipment (i.e. a pair of rolls 6), entry side A conveyor roller 10 is provided . Metallic glass 5 is heated by the silicone oil 2 while being supplied from the inclined surface 7 on the roll 6, the same temperature and the silicone oil 2. The example FIG. 1 (a) rolling a metallic glass 5 massive, 1 (b) is an example of rolling a metallic glass 5 of a round bar, and by the rolling metallic glass 5 the resulting metallic glass 5a is shown as a perspective view.

Further, since the processing equipment (that is, the pair of rolls 6) is also immersed in the silicone oil 2, the temperature is the same as that of the silicone oil 2. Accordingly, the temperature of the metallic glass 5 does not change during the plastic forming.
Temperature of metallic glass 5 (i.e. the temperature of the silicone oil 2) is a its glass transition temperature of the metallic glass 5 (Tg) than, yet does not enter the crystallized region (Tx) temperature (i.e. supercooled temperature Region, region A) of FIG. As already described, it is possible to control the temperature of the silicone oil 2 in the range of the target temperature ± 0.5 ° C. by the PID control, by setting the target temperature in the range of Tg + 5 ℃ ~Tg + 30 ℃ , the temperature of the metallic glass 5 Is retained without falling below Tg or rising to the crystallization region.

Also, exit plastic molding before entering the crystallization region, in order to maintain the characteristics of the metallic glass, the time required for molding in the range of 30 to 300 seconds.
Since the present invention the Tg of the target and to Rukin genus glass 5 is 80 to 200 ° C., it is not necessary to use a high-frequency induction heating apparatus as a heater 15, which generates heat by electrical resistance due to the normal current, for example, liquid A sheath heater or the like can be used.

In the example shown in FIG. 1 Thus, metallic glass rolling can be subjected to, rolling the resulting metallic glass 5a (walking Sunawa chicken genus glass plate metallic glass foil that ) Is quickly discharged out of the tank 1 through the takeout conveyor roller 11 via the takeout conveyor 4. Note in Figure 1, it showed metallic glass 5 massive and round bar, even with metallic glass 5 of square bar or plate-like, to obtain a metallic glass plate or gold genus glass foil it can.

FIG. 2 is a cross-sectional view showing an example in which a mold 9 provided with a groove 8 having an arcuate cross-sectional shape and one roll 6 disposed eccentrically inside the groove 8 are used as processing means . is there. In FIG. 2, the oil temperature regulator is not shown. The mold 9 is fixed in the tank 1, and the roll 6 rotates in the direction of the arrow in FIG. Metallic glass 5 of the supplied tubular along the inclined surface 7 is supplied from a wide gap side of the groove 8 and the roll 6 of the mold 9, the diameter during rolling into a narrow gap side contracted (hereinafter, The diameter is reduced) and is discharged from the groove 8 via the takeout conveyor 4. Note in Figure 2, an example of reduced diameter of the metallic glass 5 of the tubular, it is also possible to shrink the metallic glass 5 of a round bar.

In the example shown in FIG. 2, metallic glass 5, because it is heated by the silicone oil 2 while being supplied to the roll 6 along the inclined surface 7, the same temperature and the silicone oil 2. Further, the mold 9, the roll 6 may have been immersed in a silicone oil 2, because they become the same temperature as the silicone oil 2, the temperature of the metallic glass 5 is not changed to the reduced-diameter . Therefore, by setting the target temperature of the silicone oil 2 in the range of Tg + 5 ℃ ~Tg + 30 ℃ , the temperature of the metallic glass 5 is held without being raised to the crystallization region or below the Tg. The metallic glass 5 is within the range time is immersed in a silicone oil of 30 to 300 seconds, it is possible to maintain the characteristics of the metallic glass even after diameter.

In the example shown in FIG. 2 this way, the metallic glass 5 of the tubular or rod-shaped can be reduced in diameter.
Further, as the processing unit, by making a withdrawal with withdrawal dies, it can also be stretched metallic glass 5 into a linear shape.
Alternatively, by using the punch as a processing unit, it can be subjected to stamping to metallic glass 5.

Here, the technique of manufacturing by injection molding a Rukin genus glass used in the present invention will be described with reference to FIG.
Figure 4 is a perspective view schematically showing an example of an apparatus for injection molding a Rukin genus glass Kyosu the molding of the present invention. An inert gas supply device 18 for supplying a high-pressure inert gas is detachably attached to the upper end of the stainless steel circular tube 14. When loading a small piece of metallic glass was preconditioned component in a circular tube 14, remove the inert gas supply unit 18 from the circular tube 14, top or et metals glass of circular tube 14 It is charged with small pieces. The circular tube 14 plays a role as a container for heating a small piece of metallic glass as described later, by using an inexpensive stainless steel, contributing to a reduction in cost of an injection molding device .

After charging a small piece of metallic glass to a circular pipe 14, attaching the upper end to the inert gas supply apparatus 18 of the circular tube 14.
A heater 15 is attached to the lower part of the circular tube 14. The heater 15 is for heating and melting small pieces of metallic glass which has been charged into the circular pipe 14 above the melting point, it is not necessary to use a high-frequency induction heating apparatus, the electrical resistance due to the normal energization A device that generates heat (for example, a cartridge heater) is used. Since such a heater is inexpensive, contributes to reduce the cost of the injection molding apparatus, Hiite can reduce the manufacturing cost of the metallic glass.

Further, a thermometer 16 is attached to the outer surface of the circular tube 14 at a site heated by the heater 15. Then soars temperature of the outer surface of the circular tube 14, it is determined that the metallic glass in the circular tube 14 reaches the target temperature is melted and held at that temperature until the injection molding is completed. By performing PID control based on the heating by measurement and heater 15 obtained in this thermometer 16 in the target temperature to maintain the temperature of the molten metallic glass in the range of the target temperature ± 0.5 ° C. It becomes possible. As the thermometer 15, a conventionally known one such as a thermocouple is used.

The inner diameter of the circular tube 14 is more than 15 mm, the distance of the central portion and the heater 15 of the circular tube 14 becomes longer, the heating capacity of the heater 15 is also coupled, it is kept uniform temperature of the molten metallic glass It becomes difficult. If it is less than 5 mm, it becomes difficult charged a small piece of metallic glass. Therefore, the inner diameter of the circular tube 14 is preferably in the range of 5 to 15 mm. Capacity Rukin genus glass to dissolve in the circular pipe within 14 is 1～25Cc.

A stainless steel injection nozzle 17 is fitted into the lower end of the circular tube 14 and fixed. Since the injection nozzle 17 is manufactured by machining a conical stainless steel, a small-diameter injection port as described later can be processed with high accuracy.
The stainless steel injection nozzle 17 is not only inexpensive, but can accurately process the injection nozzle into various shapes. Moreover, since it is difficult to break, a number of injection moldings can be continuously performed. In addition, when the injection port is clogged with foreign matter, the foreign matter can be removed without damaging or deforming the injection nozzle 17.

Then, after the metallic glass of the circular tube 14 is melted, the circular tube 14, the inert gas supply unit 18, and integrally lowers the heater 15, the thermometer 16 and the injection nozzle 17, the injection nozzle 17 copper after close to受湯hole 20 of the injection mold 19, and supplied from the upper end of the inert gas supply apparatus 18 of the circular tube 14 a high-pressure inert gas into a circular pipe 14, metals melted the glass from the injection nozzle 17 to受湯hole 20, is injected at a pressure of inert gas. The pressure of the inert gas at the time of injection is less than 0.02 MPa, since no sufficient ejection speed can be obtained, not amorphous metallic glass can be obtained. On the other hand, when it exceeds 0.2 MPa, defects such as air bubbles are generated inside of the metallic glass. Therefore, the pressure of the inert gas is preferably in the range of 0.02 to 0.2 MPa. The inert gas used is preferably N ₂ or Ar.

Injection time is less than 0.01 seconds, can not inject a sufficient amount of metallic glass. On the other hand, when it exceeds 0.5 seconds, sufficient cooling rate is obtained to obtain an amorphous metallic glass. Therefore, the injection time is preferably in the range of 0.01 to 0.5 seconds.
When injecting the metallic glass is an injection nozzle 17 since the closer to受湯hole 20 may be injected into reliably受湯hole 20 of molten metallic glass. At that time, it is preferable to provide a gap without contacting the outer surface of the injection nozzle 17 and the opening of the hot water receiving hole 20. By providing the gap, it is possible to easily discharge the air in受湯hole 20 with the injection of the molten metallic glass.

The copper injection mold 19 is fixed on a moving table 21 that is movable in the horizontal direction. The injection mold 19 is provided with a受湯holes 20, is cooled to solidify the metallic glass was injected into受湯hole 20 from the injection nozzle 17. In the present invention, as described below, since the ejection from the injection port of the area 0.2 to 2.5 mm ^2, in Rukin genus glass such the subject of the present invention described above, as shown in FIG. 3, the crystal from the molten state cooled without reduction, a sufficient cooling rate is obtained to obtain an amorphous metallic glass.

The injection mold 19 is preferably provided with a plurality of hot water receiving holes 20 in one row. In this case, after injecting a metallic glass which is melted from the injection nozzle 17 to受湯hole 20, to stop the supply of inert gas, further circular tube 14, the inert gas supply unit 18, a heater 15, a thermometer After the 16 and the injection nozzle 17 are raised integrally, the moving table 21 is moved, the second hot water receiving hole 20 is arranged vertically below the injection nozzle 17 and the moving table 21 is stopped. Then, the second to受湯hole 20 is brought closer to the injection nozzle 17 injects the molten metallic glass. By repeating this procedure, a plurality of injection moldings can be performed continuously. That can be achieved to improve the efficiency of the injection molding of metallic glass. FIG. 4 shows an example in which five hot water receiving holes 20 are provided in one row in the injection mold 19, but the present invention is not limited to this.

Next, remove the injection mold 19 from the moving table 21, taking out the solidified metallic glass from受湯hole 20. If the injection mold 19 divided into two parts can be constructed along the columns of受湯hole 20, since the metallic glass that easily taken out preferred.
The shape of the hot water receiving hole 20 is a round bar, and the inner diameter is preferably in the range of 2 to 5 mm. The inner diameter is less than 2mm of受湯hole 20, the molten metallic glass is hardly filled in受湯hole 8. On the other hand, when it exceeds 5 mm, since the cooling of the central portion is delayed, not homogeneous metallic glass can be obtained.

In addition, the injection port of the injection nozzle 5 has an area in the range of 0.2 to 2.5 mm ² . The area of less than 0.2 mm ^2, it becomes difficult to inject the molten metallic glass, it is possible that metallic glass is not amorphized to not be injected immediately. On the other hand, when it exceeds 2.5 mm ^2, droplets of molten metallic glass is dropped from the injection port by its own weight.
Metallic glass injection molded by the procedure as described above, the present invention can be molded without hindrance, yet metallic glass after molding, the organization is not crystallized, the amorphous it is a metallic glass material of quality.

It was performed forming of metals glass of Au-Cu-Ag-Pd- Si system using plastic molding apparatus shown in FIG. The procedure will be described below.
First it was prepared a metallic glass by using an injection molding apparatus shown in FIG. To As a metallic glass, using a plastic forming device of FIG. 1, it was subjected to molding (i.e., rolling) by the following procedure.

  An oil temperature regulator 3 was attached to the tank 1 storing the silicone oil 2 and heated while circulating the silicone oil 2. The heater built in the oil temperature controller 3 was a cartridge heater. The target temperature was 100 ° C., which is the temperature in region A in FIG. 3 (ie, Tg + 5 ° C. to Tg + 30 ° C.). In the oil temperature controller 3, the temperature of the silicone oil 2 was measured using a thermocouple as a thermometer, and the temperature of the silicone oil 2 was maintained within the target temperature range of ± 0.5 ° C. by performing PID control.

Next, round bars (diameter 4 mm, length 40 mm) of the metallic glass 5 is supplied to the roll 6 from the inclined surface 7 pair performs rolling, resulting metallic glass plate (thickness 0.5 mm) The product was taken out of the tank 1 through the take-out conveyor 4. At that time, the time metallic glass 5 is immersed in a silicone oil 2 was 30 seconds.
Examination of its a metallic glass sheet tissues, whole has become an amorphous structure was a plate of metallic glass.

While maintaining the machining equipment such Rukin genus peripheral and glass Contact Kyosu machining supercooled temperature range, since the metallic glass can be plastically molded into a predetermined shape, it exhibits the remarkable effect industrially.

First tank 2 Silicone oil 3 oil temperature controller 4 taking out conveyor 5 Metal glass
6 Roll 7 Inclined surface 8 Groove 9 Mold
10 Inlet conveyor roller
11 Outlet conveyor roller
12 Inflow pipe
13 Outflow pipe
14 round pipe
15 heater
16 Thermometer
17 Injection nozzle
18 Inert gas supply device
19 Injection mold
20 Receiving hole
21 Moving table

Claims (8)

The metallic glass of the glass transition temperature Tg of 80~200 ℃, Tg + 5 ℃ ~Tg + 30 ℃ characteristics and be Rukin genus glass plastic molding method to molding in silicone oil in the temperature range. Processing means for the glass transition temperature Tg is molded metallic glass of 80 to 200 ° C. is immersed in the reservoir silicone oil in the tank, maintaining the temperature of the silicone oil in the range of Tg + 5 ℃ ~Tg + 30 ℃ , before after Kikin genus plastic and glass is supplied to the processing unit from outside the tank molding, features and be Rukin genus glass to quickly discharged the molded metallic glass to the tank outer Plastic forming method. Plastic molding method of metallic glass according to claim 1 or 2, characterized in that the time before Kikin genus glass is immersed in the silicone oil is in the range of 30 to 300 seconds. Metallic glass plastic forming method according to any one of claims 1 to 3, characterized by performing rolling before Kikin genus glass with a pair of rolls as the processing means. Characterized in that using a single roll which is disposed eccentrically inside the mold having a groove of arcuate cross-sectional shape as the processing means and the groove, it performs diameter before Kikin genus glass metallic glass plastic forming method according to any one of claims 1 to 3. A tank for storing the silicone oil, the a processing unit for the glass transition temperature Tg is plastically molding the metallic glass of 80 to 200 ° C. is immersed in the silicone oil, the pre Kikin genus glass from outside the tank The raw material supply means to be charged into the processing means, the take-out means for discharging the low Tg metallic glass plastic-formed by the processing means to the outside of the tank, and the temperature of the silicone oil are kept in the range of Tg + 5 ° C. to Tg + 30 ° plastic forming device features and to Rukin genus glass that has a fluid temperature adjustment means, the for. It said processing means is plastic forming device of the metallic glass according to claim 6, characterized in that it comprises a pair of rolls. Gold according to claim 6, wherein the processing means is a die having a groove of arcuate cross-sectional shape, and one roll disposed eccentrically inside the groove, characterized in that it has a plastic molding apparatus of the genus glass.

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