JP2008025020A - Manufacturing method of amorphous alloy bulk or composite alloy bulk composed of amorphous alloy and conventional crystal metal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a large size bulk exceeding the current small size amorphous alloy bulk (a metallic glass bulk or a nanocrystalline alloy or a quasicrystalline alloy bulk). <P>SOLUTION: A manufacturing method comprises the steps of: melting one of the amorphous alloy selected from among the metallic glass alloy, the nanocrystalline alloy, and the quasicrystalline alloy; pouring molten amorphous alloy from at least two inlets (2) into a mold (1), while bonding the amorphous alloy (4) in a molten state each other in a cavity (3) provided in the mold (1); and then cooling it at a cooling rate of at least a critical cooling velocity of the amorphous alloy (4). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a metal glass, nanocrystal or quasicrystalline alloy bulk which is a large amorphous alloy in the form of a line, plate or block (including deformed members), and further to these amorphous alloys and iron, copper, aluminum and stainless steel. The present invention relates to a production method for efficiently producing a composite alloy bulk with a general metal material such as.

  Amorphous metals, metallic glasses, nanocrystals or quasicrystalline alloys, which are amorphous alloys, have high strength, low Young's modulus, high corrosion resistance, and excellent magnetic properties compared to general crystalline metal materials. And is expected to be applied to a wide range of fields.

Half a century after the discovery of amorphous metal, basic theoretical research in this field has been carried out in great detail and numerous results have been announced. The development of the alloy system requires a very fast cooling rate of 10 ⁶ K / s (= Kelvin / second), and from the early stage amorphous metal that can only be foil, 0.033 K / s (= Kelvin / second) to date ), Which can be produced even at the critical cooling rate (in this case, bulk production is possible), and the cooling rate has actually advanced by 8 digits (100 million times).

  And metal glass member production technology from metal glass liquid (molten metal) is single roll method, twin roll method, direct casting method, liquid forging method, quenching in water, and supercooled viscous flow (like glass when stress is applied) Have been developed such as secondary processing utilizing the viscous flow. Processing techniques for nanocrystals or quasicrystalline alloys have also been developed in accordance with the above.

  In metallic glass alloys, atoms are arranged in a disorderly manner over a wide range, but in order to make such a disordered arrangement, it is necessary to cool the molten metal at a constant cooling rate that is equal to or higher than the critical cooling rate. It is known that the critical glass metal production rate of many alloy systems developed so far is 102 to 3 K / s (= Kelvin / second). It should be noted that a quasi-crystalline structure that cannot be said to be a very fine nanocrystal structure or crystal (= a state that should be called a third solid material different from a crystal or an amorphous material, but has no translational symmetry that defines a crystal, It is necessary for the same cooling conditions to be satisfied even if the atomic arrangement has high order.

  Currently, casting and liquid forging are the mainstream methods for producing metallic glass members as described above. However, in the rapid solidification process employed in these manufacturing methods, when a large-sized metallic glass bulk is to be produced, the molten metal must be poured into a cavity formed in a bar shape or a wide area in a wide area over a long distance. The molten metal was cooled little by little while flowing through this cavity, and the critical cooling rate could not be satisfied.

Then, in order to form a large-sized metal glass bulk, the friction welding, the joining by a laser, etc. are tried (patent documents 1-3). According to such a method, a desired metallic glass composition was obtained at the joint surface and the vicinity thereof, but at a portion slightly deviated from that portion, the cooling rate was insufficient and a crystal structure was formed, so-called “2” in welding. No. "(part where the structure of the base material changed due to the heat effect) was formed, and it was impossible to overcome the fatal defect of being easily damaged from this part.
JP 2002-283067 A JP-A-9-323174 JP 2003-285170 A

  In other words, the conventional metallic glass forming technique has a volume limit as described above even if a small one is possible in the bulk production of amorphous alloys including metallic glass. For this reason, it is necessary to open the way to the production of larger-capacity amorphous alloys (metal glass, etc.) for further development in the future, and to meet the demand for amorphous metals as structural materials and functional materials unless otherwise. Currently, it is difficult to respond widely.

  As can be seen from the above, it is possible to create a large amorphous alloy bulk by removing the current small amorphous alloy bulk (metal glass bulk or nanocrystalline alloy or quasicrystalline alloy bulk). Is the technical problem of the present invention.

  Claim 1 relates to a method for producing a large amorphous alloy bulk using a homogeneous amorphous alloy material such as a metallic glass alloy, a nanocrystalline alloy, or a quasicrystalline alloy, wherein “a metallic glass alloy or nanocrystalline alloy which is an amorphous alloy (4) or Any one of the quasicrystalline alloys is melted, and a melt of the amorphous alloy (4) is injected into the mold (1) from two or more injection ports (2), and the cavity (3) formed in the mold (1) ), The amorphous alloys (4) are joined together in a molten state and cooled at a cooling rate equal to or higher than the critical cooling rate of the amorphous alloy (4).

  The alloys injected here are of the same kind, those of metallic glass alloys are metallic glass alloys, in the case of nanocrystalline alloys, nanocrystalline alloys, in the case of quasicrystalline alloys, quasicrystalline alloys, This is the case when the composition is the same.

  Conventionally, there is only one molten metal injection port in the casting of a crystal alloy. When a large-sized cast product is manufactured, a large amount of molten metal is injected at a time from the single injection port or injected first. This was performed by sequentially injecting the next molten metal after the molten metal was cooled and solidified. However, when a large-sized metallic glass bulk is cast by injecting a large amount of molten metal at a time, a portion that cannot be cooled at a cooling rate higher than the critical cooling rate is generated, and crystals may be generated in a part of the bulk. In addition, when the molten metal is sequentially injected, the preceding and following metallic glass alloys may not be sufficiently bonded, or the cooling rate may be reduced at the interface between the preceding and succeeding metallic glass alloys, resulting in crystals.

  In the present invention, an amorphous alloy of the same type is injected into a cavity “from two or more inlets”, and the amorphous alloys are “joined in a molten state” in the cavity and “critical cooling of the amorphous alloy” A large amorphous alloy bulk is manufactured by “cooling at a cooling rate higher than the speed”.

  This shortens the distance for flowing the molten amorphous alloy injected from one injection port, and in contact with the molten amorphous alloy injected from the other injection port in a state still above the melting temperature, Since the cooling can be performed at a cooling rate higher than the critical cooling rate, it is possible to join the amorphous metal without generating crystals.

  Claim 2 relates to a method for producing a large amorphous alloy bulk using a heterogeneous amorphous alloy material such as a metallic glass alloy, a nanocrystalline alloy, or a quasicrystalline alloy, wherein “a metallic glass alloy or nanocrystalline alloy that is an amorphous alloy (4)”. Alternatively, two or more of the quasicrystalline alloys are melted, and the melt of the different amorphous alloy (4) is injected into the mold (1) from the two or more inlets (2), and formed in the mold (1). In the cavity (3), the different amorphous alloys (4) are joined in a molten state and cooled at a cooling rate equal to or higher than the critical cooling rate of the amorphous alloy (4).

  In this case, since it is a heterogeneous alloy to be joined, the metallic glass alloys, nanocrystalline alloys, quasicrystalline alloys have different compositions, as well as metallic glass alloys-nanocrystalline alloys, nanocrystalline alloys-quasicrystals. A combination of an alloy, a quasicrystalline alloy-metallic glass alloy, or a metallic glass alloy-nanocrystalline alloy-quasicrystalline alloy is conceivable.

  The third aspect of the present invention relates to a method for producing an amorphous / crystalline alloy bulk by combining an amorphous alloy material and a general crystal melting alloy, which is “a metallic glass alloy (4) which is an amorphous alloy, nanocrystalline alloy or quasicrystalline alloy”. Any one or two or more and one or two or more crystalline metals (5) are melted individually, and the melt of the amorphous alloy (4) is individually fed into the mold (1) from one or more inlets (2). The molten metal of the crystalline metal (5) is individually injected into the mold (1) from the remaining injection port (2), and the amorphous alloy (4) is formed in the cavity (3) formed in the mold (1). And the crystalline metal (5) are joined in a molten state and cooled at a cooling rate equal to or higher than the critical cooling rate of the amorphous alloy (4).

in this case,
(a) Metallic glass alloy-crystalline metal, nanocrystalline alloy-crystalline metal, quasicrystalline alloy-a combination of crystalline metal or a composite material of these and crystalline metal,
(b) Metallic glass alloy-, crystalline metal-, nanocrystalline alloy-combination of composite materials with crystalline metal,
(c) Two or more metal glass alloys (different in composition or alloy system) —one or more crystalline metals, two or more nanocrystalline alloys (different in composition or alloy system) —one or more A combination of crystalline metal, two or more quasicrystalline alloys (different in composition or alloy system) -1 or a composite material of two or more crystalline metals,
(d) Metallic glass alloy—nanocrystalline alloy—one or more crystalline metals, nanocrystalline alloy—quasicrystalline alloy—one or more crystalline metals, quasicrystalline alloy—metallic glass alloy—one or more crystalline metals Composite material combination,
(e) A composite material of a combination of metallic glass alloy-nanocrystalline alloy-quasicrystalline alloy-1 or two or more crystalline metals, and the advantages of each of the combined crystal alloys are further manifested, and the disadvantages are hidden or reduced. As a result, the application of the alloy material can be greatly expanded.

  For example, crystalline alloys generally have plasticity, while amorphous alloys have high strength, low Young's modulus, and high corrosion resistance. Therefore, a composite material in which a crystalline alloy and an amorphous alloy are combined has plasticity and high strength, low Young's modulus, and high corrosion resistance.

  A fourth aspect of the present invention relates to a method for producing an amorphous alloy bulk or a composite alloy bulk according to any one of the first to third aspects, wherein “a molten metal of the amorphous alloy (4) is pressurized to form a mold (1 ). ”

  According to the present invention, the molten metal of the amorphous alloy (4) is pressurized and injected into the mold (1) from the injection port (2), so the flow rate in the cavity of the molten metal is increased, and the molten metal of the molten metal is wider. Can be extended to range.

  Claim 5 relates to a method for producing an amorphous alloy bulk or a composite alloy bulk according to any one of claims 1 to 4, wherein “the cavity (3) is rod-shaped, plate-shaped, or massive, and the injection port (2) is a cavity. The length between the inlets (2) and (2) is in the molten state holding range of the cast metal (4) (4) or (4) (5) ". As a result, the molten metal that has come into contact with each other in the cavity (3) comes into contact with each other in a molten state, and is completely joined and completely integrated at the interface (K). In other words, the amorphous alloy can be joined only by this method.

  Claim 6 is a modification of the method for producing an amorphous alloy bulk or a composite alloy bulk, “the communication ports of the inlets (2a), (2b)... To the bulk forming cavity (3) are formed at the same location”. As a result, a plurality of alloys are mixed together in one bulk via an interface, and the advantages of the amorphous alloy and the crystalline metal (including the alloy) combined as described above are further developed. However, the drawbacks are hidden or reduced, and the application of the block or massive alloy material can be greatly expanded.

  As described above, in the method of the present invention, in the molten state, the same kind or different kinds of amorphous alloys are joined in the mold at a temperature equal to or higher than the melting temperature, and then cooled at a cooling rate equal to or higher than the critical cooling rate. It is possible to prevent the occurrence of “No. 2” close to the joining interface of the amorphous alloy and the vicinity thereof, which could not be avoided by the conventional joining method. This allowed the formation of a fully integrated large bulk that was considered impossible with amorphous alloys. In addition, bonding with a crystalline metal can alleviate defects of an amorphous alloy, such as brittle fracture. Conversely, it is possible to make up for defects of crystalline metal, such as insufficient strength and insufficient hardness.

  Hereinafter, the present invention will be described in detail according to illustrated embodiments. As shown in FIGS. 1-4, the metal mold | die (1) as a casting_mold | template uses the metal material excellent in thermal conductivity, for example, copper, and the cavity (3) of a required shape is formed inside. The shape of the cavity (3) is a circular cross section large diameter linear hole, cross section deformed large diameter linear hole, rectangular or circular or deformed flat plate, sphere, spheroid, deformed block, and other shapes according to needs. It is formed. In the present specification, all compositions are shown in atomic percent.

  In the cavity (3), a plurality of inlets (2) [= pouring gates] communicating with the cavity (3) are formed, and the intervals between the inlets (2) are the melts injected from the respective inlets. [Fused metal glass (4), molten nanocrystalline alloy (4), molten quasicrystalline alloy (4), general crystalline metal (5) (eg, iron, copper, aluminum and its alloys) or alloys (eg, stainless steel alloys) ] Are formed within a range where they meet each other in a liquid state. In addition, it is suitable for the temperature of the molten metal at the time of injection | pouring that it is melting | fusing point + 100-300 degreeC, such as the alloy.

  This embodiment is a circular hole with a circular cross section or a cross-shaped or massive cavity (3), and the number of injection ports (2) is “2” at both ends, but naturally, as shown in FIG. “5” or more may be formed. In addition, since the molten metal (4a) (4b) is in contact with the interface (K) and needs to be cooled at a critical cooling rate, the pouring is performed almost simultaneously. If necessary, the molten metal is pressurized up to several hundred tons at the time of pouring. The speed at which the molten metal flows through the cavity is 1 m / s or more.

  The cooling means (6) may be any means as long as the mold (1) is cooled and the molten amorphous glass such as a molten metal glass can be cooled at a rate higher than the critical cooling rate. However, in this embodiment, a method of flowing 10 to 20 L / min of cooling water through a cooling water hole (not shown) drilled in the mold (1) is adopted.

  As a method of injecting the molten alloy of the amorphous alloy such as metal glass into the injection port (2), injection by mere self-weight or a pressure injection method in which pressure is applied to the molten metal as described above may be used. In the case of the pressure injection method, since the inflow speed is high, the interval between the injection ports (2a) (2b)... (2n) can be widened.

The metal glass applied to the present invention is
(1) generating a single-phase solid solution consisting of a multicomponent system of three or more components belonging to adjacent group numbers in the periodic table of elements;
(2) The ratio of atomic dimensions of at least two constituent elements is 3% or more,
(3) Satisfies the “3 metallic glass generation conditions” such that the heat of mixing of the constituent elements has a positive value, zero or a slightly negative value, and the bonds between atoms are repelling each other. The combination is not limited to the same type (same composition), but different types (metal glass alloys, nanocrystalline alloys, quasicrystalline alloys having different compositions, metallic glass alloys-nanocrystalline alloys, Nanocrystalline alloy-quasicrystalline alloy, quasicrystalline alloy-metallic glass alloy, metallic glass alloy-nanocrystalline alloy-quasicrystalline alloy, etc.) may be used. Furthermore, the crystalline metal may be cast into these simultaneously. In the case of different types, the molten metal enters and mixes with each other but forms an interface (K), and the composition does not change in the interface (K) without mixing with each other. This is because the cooling rate is sufficiently high so that the molten metal (4) (4), (4a) (4b) or (4) (5) is solidified before being completely mixed. As a result, the joining of dissimilar metals (4a) (4b) or (4) (5) at the interface (K), as described above, between the amorphous alloys (4) (4) or (4a) (4b) or non- The advantages of the crystalline alloy (4) and the crystalline metal (5) (including the alloy) are further developed, and the disadvantages are hidden or reduced, and the application of the alloy material can be greatly expanded.

  FIG. 1 shows the schematic internal structure of the molten metal joining apparatus (A) used in the present invention, and FIGS. 2 to 4 show the mold (1) used. The mold (1) is provided with a circular cross section large diameter straight rod hole or a cross section circular large diameter cross-shaped rod hole or a bulky cavity as a cavity (3), and both ends thereof or an injection port (2) communicating therewith. . In the figure, (21) is a vent hole, and when molten metal is injected, the molten metal enters to form a cylinder (L). This part is removed after casting. The molten metal joining apparatus (A) is provided with two high-frequency heating coils (8) and (9) corresponding to the injection port (2), and the high-frequency heating coils (8) and (9) are used to provide a crucible (10). (10) The alloys in (10) are melted, and the melted alloys are simultaneously injected into the mold (1) to form a predetermined bulk (B).

  A sample for measuring the mechanical properties was prepared using a linear cavity (3) shown in FIG. On the other hand, a sample for seeing the flow of the molten metal at the interface (K) (see FIG. 12) was produced using the intersecting cavity (3) of the mold (1) shown in FIG. 2 (b). 3 is used to form a bulky bulk, and FIG. 4A is used to produce a long thick bar bulk. FIG. (b) A mold (1) as shown in (c) of FIG.

Alloys with a composition of Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ , Cu ₄₂ Zr ₄₂ Al ₈ Ag ₈ and Ti _41.5 Cu _42.5 Ni _7.5 Hf ₅ Zr _2.5 Si ₁ with large metal glass forming ability are selected and arc An ingot is produced in argon gas using a melting furnace, melted by the molten metal joining device (A), and simultaneously cast into the two inlets (2) and (2) in the mold (1). It is. In this example, simultaneously with casting, the molten metal was pressurized by blowing nitrogen gas into the two inlets (2) and (2). Of course, it is possible to cast by its own weight.

  The phase of the prepared sample (large-diameter bar-shaped bulk) was identified by the X-ray diffraction method (FIG. 6). The thermal properties were examined using a differential thermal analyzer (DSC) (FIG. 7 (a)). The mechanical properties were measured with an Instron type testing machine (FIG. 7 (b)), and the hardness was investigated using micro Vickers (Hv) (FIG. 8 (a)). The fracture surface was observed using a scanning electron microscope (SEM) (FIG. 8 (b)). The structure evaluation was performed by observing a sample corroded with 0.5% HF acid using an optical microscope (FIG. 9).

  Using the mold (1) set in the molten metal joining device (A) as described above, the same kind of molten metal glass (4) (4), dissimilar metal glass melt (4a) from the two inlets (2) (2) ) (4b) was cast to prepare each sample, and the structure, mechanical properties and fracture surface characteristics of the joint were investigated.

(1) Molten metal joining of the same kind of metal Using a Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ alloy sample having the ability to form a metallic glass from two inlets (2), a bulk sample having a diameter of 3 × 150 mm was prepared.
(a) Identification of each phase of the interface (K) of the bulk sample was analyzed by XRD (X-ray diffractometer) (FIG. 6). Identification samples Nos. 1 to 14 were obtained by cutting out a portion within the range of the leader line in the diagram shown in FIG. 5A into 14 pieces, and phase identification was performed on these samples. As a result of the identification, since no sharp peak is observed in the X-ray diffraction graph, it can be determined that these samples have no crystal portion and all the samples 1 to 14 have produced a metallic glass phase.
(b) The result of thermal analysis of the joint part alloy using DSC (differential thermal analyzer) is shown in FIG. 7 (a). Tg and Tx of all the samples (5 # to 10 #) are the same as shown in FIG. 7 (a), so that it can be determined that they are completely joined.
(c) The result of measuring the compressive strength of the joined large rod-shaped bulk metallic glass sample with an Instron device is shown in FIG. 7 (b). Most of them were 1600 to 1700 MPa, and it was found that they had the same mechanical properties as the bulk metallic glass material produced by the conventional direct casting method. Further, as a result of measuring the hardness of the cut surface, as shown in FIG. 8A, it was confirmed that the cut surface had a uniform hardness of Hv500 to 515 over the entire sectional view. From this result, it can be inferred that they are completely joined.

  In addition, in order to observe the bonding state of the interface (K), the bulk metallic glass sample is corroded with 0.5% HF acid, and the part of the hot water (= interface (K) of both metallic glass alloys) is removed using an optical microscope. investigated. As a result, as shown in FIG. 9, the structure is uniformly and thinly discolored, and a hot water boundary (however, both are not mixed at the atomic level. This point is clarified by the joining of dissimilar alloys) appears. In other words, it was observed that they were completely joined. The fracture surface of the compressed sample was observed by SEM (scanning electron microscope). As shown in FIG. 8 (b), the interface (K) has a typical metallic glass vein-like fracture pattern.

  As a result of this, if the molten metal has a temperature higher than the melting point when the amorphous metal injected from a plurality of inlets contacts and mixes and can maintain fluidity even at the moment of contact mixing, sufficient atomic diffusion energy can be obtained. It can be seen that they merge together like water. However, the interface (K) is not formed and mixed at the atomic level. This is the same even in the case of dissimilar composite alloys.

  Next, it is the interval of the inlet (2), but when the molten metal flows in the cavity (3) of the mold (1), a temperature change (that is, the temperature rapidly decreases) appears depending on the distance the molten metal travels, The temperature of the interface (K) is a very important factor for joining amorphous alloys such as metallic glass. Further, when the molten metal is solidified by running a long distance and reaching the interface (K), it can no longer be joined. In addition, even if the tip of the liquid metal flowing through the mold (1) is in a semi-molten state, the bonding surface cannot sufficiently bond atoms, and a clear hot water boundary such as a cavity or a gap is generated. The mechanical properties of the part are significantly reduced. Therefore, it is necessary to maintain a temperature equal to or higher than the melting point (preferably a melting point + 150 ° C.) at the joining surface, and the liquid metal pouring temperature, casting speed, molten metal travel distance, mold (1) It is necessary to control the temperature of the machine. In other words, if these are appropriately controlled, the width between the injection ports (2) is set to an appropriate width (a molten state is maintained at the interface (K)). This is the same even in the case of dissimilar composite alloys.

  Based on the above results, a number of inlets (2) are prepared and cast simultaneously from a manufacturing method in which only a single amorphous alloy bulk such as a metallic glass bulk with a certain area and volume can be produced with a single inlet (2). By adopting the molten metal joining method, it has become possible to produce a bulk metal glass product of the same type that is theoretically unlimited in size. In other words, using this method, a large number of bulk metal glass rods of several meters can be obtained by providing a large number of inlets (2a), (2b)... (2n) as shown in FIG. It can be easily manufactured. Similarly, a plate material as shown in FIG. 3B, a product having a complicated shape as shown in FIG. 3C, and a bulk as shown in FIG. 3 can all be easily produced.

(2) Molten metal joining of dissimilar metals Next, joining of dissimilar metal glasses will be described. The composition of the alloy used for joining dissimilar metallic glass to each other is _{Zr 55 Cu 30 Al 10 Ni 5} , Cu 42 Zr 42 Al 8 Ag 8, and _{Ti 41.5 Cu 42.5 Ni 7.5 Hf 5} Zr 2.5 Si 1. It was confirmed in appearance that it seemed to be completely joined (see the top three in FIG. 10; the bottom three are the same type of metal).

_{(a) Zr 55 Cu 30 Al} 10 Ni 5, and Cu ₄₂ Zr ₄₂ Al cut 6 pieces of the sample of the joint portion of the produced thick径棒shaped bulk like above using ₈ different alloy such as Ag _8, the XRD Phase identification. The result is shown in FIG. Sample A is Cu ₄₂ Zr ₄₂ Al ₈ Ag ₈ metallic glass, and Sample B is Zr ₅₅ Al ₁₀ Ni ₅ Cu ₃₀ metallic glass. The peak center of the X-ray of the sample B1 (No. 6: the graph described at the top of FIG. 11 (a)) is about 2θ = 42 °, and the single Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ metallic glass It matches the peak position. In addition, the A1 sample on the opposite side (No. 1: the graph described in the bottom of FIG. 11A) has an X-ray peak center of about 2θ = 40 °, and Cu ₄₂ Zr ₄₂ Al ₈ Ag ₈ metal It almost coincides with the peak position of the glass. Samples AB1, AB11, BA1 in the middle part are all made of metallic glass, and the peak center of the X-ray changes monotonically between the A1 sample and the B1 sample.

  The DSC shown in FIG. 11 (b) is the result of thermal analysis of the sample corresponding to X-rays. The changes in Tg, Tx, and ΔTx of the samples joined in the middle are in good agreement with the results of changes in the position of the X-ray peak, and it was confirmed that even a dissimilar metal glass could be completely melted.

Also, using the difference in the corrosion rate of Zr ₅₅ Al ₁₀ Ni ₅ Cu ₃₀ , Zr ₄₂ Cu ₄₂ Al ₈ Ag ₈ and Ti _41.5 Cu _42.5 Ni _7.5 Hf ₅ Zr _2.5 Si ₁ metallic glass after molten metal bonding, I investigated. Fig. 12 shows Zr ₅₅ Al ₁₀ Ni ₅ Cu ₃₀ and Zr ₄₂ Cu ₄₂ Al ₈ Ag ₈ cross-type bulk metallic glass corroded in 0.5% HF acid, and the flow of molten metal by optical microstructure. It is the etching photograph of the longitudinal cross-section of the sample produced by the cross type | mold cavity (3) which shows what is called a joining condition. In the photograph, A alloy Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ flows into the first step, and B alloy Cu ₄₂ Zr ₄₂ Al ₈ Ag ₈ enters the A alloy in an unsolidified (= molten state) and collides at the junction. It is observed that a vortex-like pattern is formed. Because of this pattern, the A and B bulk metallic glass alloys are simply mixed together to form an interface, and it can be said that all of them are in an amorphous state according to the result of the X-ray diffraction described above. It was observed that no mixing was performed, that is, no mixing at the atomic level.

Further, the results of observing the pattern of the joint portion of the B alloy _{(Cu 42 Zr 42 Al 8 Ag} 8) and C alloys _{(Ti 41.5 Cu 42.5 Ni 7.5 Hf} 5 Zr 2.5 Si 1) in FIG. 13. Since this is a large-diameter bar-shaped sample produced with a linear mold, the pattern of the joint portion usually exhibits a simple needle shape. Because the physical properties such as mechanical properties change depending on the joint pattern, that is, the mixed state of different alloys, control of factors such as tapping temperature of different alloys, injection pressure, and melt flow speed affecting the joining pattern Is very important. This state is the same even in the case of the same kind of amorphous metal.

Although the results of the compression test are not shown, the strength on the A alloy side is 1500 to 1700 MPa or more and the strength on the B alloy side is 1700 to 1900 MPa, as in the case of the same kind of amorphous metal. These are the same level as single-alloy bulk metal glasses. Moreover, the strength of the joint was 1500 MPa or more and the plastic deformation was 2% or more. This is increased by about 1% from the Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ single compressive plastic deformation. This suggests a synergistic effect of A and B metallic glasses.

  Moreover, the photograph of the torn surface of a junction part is shown in FIG. From the figure, it can be seen that a typical vein-shaped fracture surface of metallic glass is exhibited. Further, due to the two dissimilar metals, it was found that the fracture direction of the fracture surface was fractured at 45 degrees with respect to the central axis of each. Presumably, this mechanism contributes to a 2% increase in compression plasticity.

  In addition, since nanocrystals and quasicrystals have the same properties as metallic glass, they can be produced in bulk under the same conditions.

Schematic front view of a casting apparatus used in the present invention Front view showing the internal structure of the linear mold (a) or cross mold (b) of the present invention The front view which shows the internal structure of the block mold of this invention The front view which shows the internal structure of the long linear type | mold (a) of this invention, a flat plate type | mold (b), or a deformed type metal mold | die (c). Front view of bulk metallic glass created with the mold shown in FIG. X-ray diffraction pattern of joints of homogeneous bulk metallic glass Figure of differential thermal analysis result (a) and Instron type tester measurement result (b) Micro Vickers hardness distribution state (a) and fracture surface scanning electron microscope drawing substitute photograph (b) Substitute photo for optical microstructural evaluation drawing of amorphous amorphous bulk Substitute photo for large-diameter members of the same and different types of metallic glass X-ray diffraction diagram (a) of the joint part of different types of bulk metallic glass and diagram showing the result of differential thermal analysis (b) Substitute drawing for the cross section of the joint between different types of metallic glass (A alloy and B alloy) Substituting photograph of cross section of joint part of dissimilar metallic glass Fracture surface scanning electron microscope drawing substitute photograph of joint part of dissimilar metal glass bonded large diameter member

Explanation of symbols

(1) Mold (mold)
(2) Inlet
(3) Cavity
(4) Amorphous alloy
(5) Crystal alloy

Claims (6)

  A cavity formed in a mold by melting any one of a metallic glass alloy, a nanocrystalline alloy, or a quasicrystalline alloy, which is an amorphous alloy, and injecting the molten metal of the amorphous alloy into the mold from two or more injection ports. A method for producing an amorphous alloy bulk, wherein the amorphous alloys are joined together in a molten state and cooled at a cooling rate equal to or higher than a critical cooling rate of the amorphous alloy.   Two or more of a metallic glass alloy, nanocrystalline alloy or quasicrystalline alloy, which is an amorphous alloy, are melted, and the molten metal of the different amorphous alloy is injected into the mold from two or more inlets, and formed in the mold. A method for producing an amorphous alloy bulk, characterized in that the dissimilar amorphous alloys are joined in a melted state in a formed cavity and cooled at a cooling rate equal to or higher than a critical cooling rate of the amorphous alloy.   Any one or more of a metallic glass alloy, a nanocrystalline alloy or a quasicrystalline alloy which is an amorphous alloy, and one or more crystalline metals are individually melted and individually injected into a mold from one or more inlets. Injecting the melt of the amorphous alloy and individually injecting the melt of the crystal alloy into the mold from the remaining inlet, and joining the amorphous alloy and the crystal metal in a molten state in a cavity formed in the mold And a method of producing a composite alloy bulk, characterized by cooling at a cooling rate equal to or higher than a critical cooling rate of the amorphous alloy.   The method for producing an amorphous alloy bulk or a composite bulk according to any one of claims 1 to 3, wherein the melt of the amorphous alloy is pressurized and injected into the mold from an injection port.   5. The cavity according to any one of claims 1 to 4, wherein the cavity is in the shape of a rod, a plate, or a lump, the injection port communicates with the cavity, and the length between the injection ports is in a molten state holding range of the cast metal. A method for producing an amorphous alloy bulk or a composite bulk according to claim 1.   The method for producing an amorphous alloy bulk or a composite alloy bulk according to any one of claims 1 to 5, wherein a communication port of the injection port with respect to the bulk forming cavity is formed at the same location.