JP2012214826A - Method for producing metallic glass molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a metallic glass molded body, which can easily produce a metallic glass molded body having desired dimensions and shape, and can produce a metallic glass molded body at a low cost and also with high efficiency.SOLUTION: The method includes: a powder layer forming step of laying material powders obtained by mixing a plurality of kinds of element powders or alloy powders composing the metallic glass to form a material powder layer 3; and a block body molding step of irradiating the prescribed part of the material powder layer 3 with a laser beam, and heating the material powders of the irradiated part to be melted and solidified, thus molding a block body 10 composed of the metallic glass while producing the metallic glass 11 from the material powders. The metallic glass molded body 1, in which the plurality of block bodies 10 are laminated and integrated, is produced by repeating the formation of the material powder layer 3 by the powder layer forming step and the production of the metallic glass 11 and the molding of the block body 10 by the block body molding step.

Description

  The present invention relates to a method for producing a metal glass molded body, in which a metal glass molded body is produced using a plurality of kinds of element powders or alloy powders constituting the metal glass.

  Metallic glass, which is a kind of amorphous metal, is a metal with a random structure of atomic arrangement, and due to its unique atomic arrangement, it has excellent mechanical properties such as low Young's modulus, high strength, and ultra-high corrosion resistance. Excellent magnetic properties such as magnetic permeability and low coercivity. Therefore, for example, it can be used for magnetic core materials used for magnetic heads and motor cores, ultra-precision members and precision machine parts for micromachines, Coriolis flowmeters, pressure sensors, linear actuators, gears, golf club faces, etc. It is also highly expected as a lightweight and high-strength structural material for, for example, airplanes and automobiles.

  As described above, metallic glass has been applied to various articles by taking advantage of its excellent characteristics. However, in order to produce a metallic glass molded body, a molten metal or alloy must be melted at a certain cooling rate or higher. It is indispensable to rapidly cool the film, and various methods have been proposed. For example, Patent Document 1 proposes a method of manufacturing a metal glass molded body having a predetermined shape by injecting molten metal into a mold or the like by a casting method, rapidly cooling it and solidifying it. However, metal glass is highly dependent on the cooling rate, and even if the cooling rate of the molten metal changes slightly, it does not become metal glass but becomes a metal crystal, as described in Patent Document 1. With a simple casting method, since the cooling rate is different between the molten metal near the mold and the central part, when attempting to produce a large-sized metal glass molded body, a metal phase is not formed in the central part and a crystalline phase is likely to occur. It is difficult to obtain a good metallic glass molded body. Therefore, in the casting method, the size of the metal glass molded body that can be manufactured is limited, and it is difficult to obtain a large metal glass molded body having a large size.

  Aiming at the practical application of metal glass, it is required to obtain a large metal glass molded body. As a solution to this requirement, a method for producing a metal glass molded body using powdered metal glass is proposed. Has been. For example, in Patent Document 2, a metallic glass powder prepared by an atomizing method or the like is placed in a mold, and pulsed electric energy is applied to the metallic glass powder to heat the metallic glass powder to sinter the metallic glass powder. The compact is manufactured (discharge plasma sintering method). In the method described in Patent Document 2, it is possible to obtain a large-sized metal glass molded body as compared with the case where a metal glass molded body is manufactured by a casting method. It is necessary to prepare a mold according to the shape. Metallic glass has excellent characteristics as described above, but has a poor plastic deformation function, and therefore secondary processing is very difficult. Therefore, in the method described in Patent Document 2, when producing metal glass compacts having different sizes and shapes, there is a problem that different molds must be prepared one by one, and complicated shapes are required. It is also difficult to produce a metallic glass molded body.

  Therefore, when producing a metallic glass molded body using metallic glass powder, a metallic glass molded body that can easily produce a metallic glass molded body of a desired size and shape without using a molding die or the like. Proposal of a manufacturing method is desired. Therefore, in Patent Document 3, after forming a metallic glass layer by thinly laying a powdered metallic glass (first step), a specific region of the metallic glass layer is irradiated with a laser beam, By locally sintering the metal glass powder, a block body of the metal glass molded body was created (second step), and the first step and the second step were alternately repeated to be laminated vertically. A method for producing a metallic glass molded body (layered manufacturing method) by integrating each block body has been proposed.

Japanese Patent No. 4164851 JP 2004-204296 A JP 2010-222684 A

  In the method described in Patent Document 3, it is possible to easily produce a metal glass molded body having a desired size and shape, but it is necessary to prepare an expensive metal glass powder, such as cost and production efficiency. There is still plenty of room for improvement.

  The present invention has been made paying attention to the above-mentioned problems, and can easily produce a metal glass molded body having a desired size and shape, and can produce a metal glass molded body at low cost and efficiently. It aims at providing the manufacturing method of a possible metallic glass molded object.

  The object of the present invention is to provide a powder layer forming step of forming a material powder layer by laying a material powder in which a plurality of kinds of element powders or alloy powders constituting metal glass are mixed, and a laser in a predetermined region of the material powder layer. A block body forming step of forming a block body made of metal glass while producing metal glass from the material powder by irradiating light or electron beam and melting and solidifying the material powder of the laser light irradiation part, and the powder By repeating the formation of the material powder layer by the layer formation step, the production of the metal glass by the block body formation step and the formation of the block body, a metal glass formed body in which a plurality of the block bodies are laminated and integrated is obtained. This is achieved by a method for producing a metal glass molded body to be produced.

  In a preferred embodiment of the present invention, the material powder is characterized by containing at least one metal element selected from Zr, Ni, and Fe as a main component and an atomic ratio of 35 at% or more.

  In a further preferred embodiment of the present invention, the material powder is characterized by containing Zr as a main component and further containing at least two kinds of metal elements selected from Cu, Ni, Al, Ti and Be.

  In a further preferred embodiment of the present invention, the material powder is spread on a flat base material made of a material having high thermal conductivity, and the block body is formed on the base material. Moreover, material powder may be spread | laid on the surface of metal members, and the said block body may be modeled on the said metal members.

  In a further preferred embodiment of the present invention, the base material or the metal member is cooled by a cooling means when the block body is formed.

  In a further preferred embodiment of the present invention, formation of the material powder layer by the powder layer formation step, production of the metal glass by the block body formation step, and formation of the block body in reduced pressure or in an inert gas, Is repeatedly performed.

  According to the method for producing a metal glass molded body of the present invention, since it is not necessary to prepare expensive metal glass powder, a metal glass molded body having a desired size and shape can be manufactured at low cost and efficiently. . In addition, by freely changing the type and blending of the element powder or alloy powder in the material powder, a variety of metal glass molded bodies can be selected and manufactured according to the field in which the metal glass is used.

It is process drawing explaining the process of the manufacturing method of the metal glass molded object which is one Embodiment of this invention. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. It is process drawing explaining the process of the manufacturing method of a metallic glass molded object following FIG. 2 is an X-ray diffraction pattern of a metal glass molded body (Zr—Cu—Ni—Al) of Example 1. FIG. It is a X-ray-diffraction figure of the metal glass molded object (Zr-Cu-Ni-Al) in case the scanning speed of a laser beam is 500 mm / sec. It is an X-ray diffraction pattern of the metal glass powder of a comparative example. It is a graph which shows the DSC measurement result of the metal glass molded object (Zr-Cu-Ni-Al) in case the scanning speed of a laser beam is 500 mm / sec. It is a graph which shows the DSC measurement result of the metal glass powder of a comparative example. It is a X-ray-diffraction figure of the metal glass molded object (Zr-Cu-Ni-Al) in the scanning speed of the laser beam of Example 2 at 500 mm / sec. It is a X-ray-diffraction figure of the metallic glass molded object (Ni-Nb-Ti-Zr) in the scanning speed of the laser beam of Example 3 at 800 mm / sec. It is a X-ray-diffraction figure of the metal glass molded object (Fe-Cr-Mo-CB) in which the scanning speed of the laser beam of Example 4 is 500 mm / sec.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. 1-9 is process drawing explaining the process of the manufacturing method of the metallic glass molded object which is one Embodiment of this invention. In the method for producing a metal glass molded body of the present embodiment, a material powder in which a plurality of kinds of element powders or alloy powders constituting a metal glass are mixed is spread on, for example, a base material 2 and a material powder layer 3 having a predetermined thickness. And the surface of the material powder layer 3 is irradiated with a laser beam or an electron beam to heat the material powder at the irradiated portion and then rapidly cool, thereby melting and solidifying the material powder to form the metallic glass 11 from the material powder. After modeling the block body 10 made of metal glass while producing, by repeating the formation of the new material powder layer 3 and the production of the metal glass 11 and the modeling of the new block body 10 on this block body 10, A metal glass molded body 1 in which a plurality of block bodies 10 are laminated and integrated is manufactured. In the present embodiment, the material vitrification of the material powder is not necessarily limited to an aspect in which the material powder is completely vitrified, but the metal vitrification having a crystal phase and the metal having a quasicrystalline phase If the density of the metal glass is high, such as vitrification, a crystal phase may be included.

  The manufacturing apparatus for manufacturing the metal glass molded body 1 includes a flat substrate 2 inside a chamber 4 surrounded by the periphery. Material powder is spread on the substrate 2. Examples of the material of the base material 2 include general metal materials such as iron, aluminum, carbon steel, alloy steel, stainless steel, and copper, and plastic materials having some heat resistance such as ceramics, glass, and polyimide. In particular, it is preferable to use a metal material having high heat resistance, heat capacity, and heat conductivity, such as copper, iron, steel, etc., from the point that metal vitrification of the material powder can be promoted. . Moreover, light metals, such as aluminum, magnesium, and those alloys, can also be used. The substrate 2 is connected to a cooling device (not shown) such as a water-cooled heat sink or a Peltier element, and the substrate 2 is always cooled. Thereby, the cooling control for preventing the heat generation associated with the irradiation of the laser beam and for converting the material powder into a metal glass is performed. In the present embodiment, the base material 2 is always cooled by the cooling device, but it is not always necessary to cool the base material 2 by the cooling device. Further, the surface of the substrate 2 is preferably subjected to a surface roughening treatment by a known method such as a blasting treatment in order to improve the bondability with the metallic glass (block body 10) to be shaped.

  A width plate-like squeegee 5 capable of reciprocating in the chamber 4 in the horizontal direction is provided on the base material 2 inside the chamber 4. When the material powder is supplied onto the substrate 2 by a material powder supply unit (not shown) that stores the material powder, the squeegee 5 slides and moves above the surface of the substrate 2 at a predetermined height. A flat material powder layer (material powder layer 3) having a substantially constant overall thickness is formed on the substrate 2. By adjusting the vertical position of the squeegee 5, the thickness of the powder material layer 3 can be changed as appropriate. The thickness of the powder material layer 3 is preferably thinner in order to improve the dimensional accuracy of the metal glass molded body to be produced.

  The manufacturing apparatus also includes a laser beam scanning device 6 that irradiates the material powder layer 3 with laser light. When the material powder layer 3 is irradiated with laser light, the material powder in the irradiated portion is heated and melted to be in a liquid state. By rapidly cooling and solidifying this, the metal glass 11 is produced from the material powder. Although not shown, the laser beam scanning device 6 includes a laser light source that emits a laser beam and an optical device such as a galvanometer mirror, and the laser beam is arbitrarily transmitted on the material powder layer 3 by the galvanometer mirror or the like. This area can be scanned with a predetermined pattern shape. Therefore, since only the specific region of the material powder layer 3 can be selected and the material powder can be locally heated by the laser beam, only the material powder of the laser beam irradiated portion is converted into a metal glass to obtain a metal glass having a desired shape and size. The block body 10 can be shaped. As the laser light emitted from the laser light source, various lasers such as a carbon dioxide laser, a YAG laser, a semiconductor laser, and a fiber laser can be used.

  In addition, the manufacturing apparatus includes a gas tank that supplies atmospheric gas to the chamber 4 although not shown. By filling the chamber 4 with the atmospheric gas, oxidation of the material powder and the metal glass is prevented. As atmospheric gas, nitrogen gas, argon gas, helium gas etc. can be illustrated, for example. A reducing gas may be used instead of the atmospheric gas. In order to prevent oxidation of the material powder and metal glass, the inside of the chamber 4 may be depressurized by a vacuum pump or the like. Thereby, the oxidation of the material powder at the time of laser beam irradiation is prevented, and the vitrification of the material powder can be promoted.

  Next, in the manufacturing method of the present embodiment, the metal glass molded body is manufactured using a material powder in which a plurality of element powders or alloy powders constituting the metal glass are mixed instead of the metal glass powder. The material powder to be used will be described.

  In the present embodiment, the material powder is composed of at least three or more elemental powders, the atomic diameters of the three components differ from each other by 12% or more, and the mixing heat of the three components is negative. Elemental powder having the necessary conditions for metal vitrification, such as having a value of

  Examples of the metallic glass include a Zr-based metallic glass mainly composed of Zr (zirconium), a Ni-based metallic glass mainly composed of Ni (nickel), an Fe-based metallic glass mainly composed of Fe (iron), and Ti. It is possible to select a known metallic glass such as a Ti-based metallic glass mainly composed of (titanium), and these are manufactured such as ferromagnetism, high mechanical strength, high corrosion resistance, and high electrical conductivity. It is appropriately selected depending on the use of the metallic glass molded body.

For example, when Zr is a main component, the material powder contains 35 at% or more of Zr powder in order to exhibit various properties of metal glass, and other component element powders include Al, Ni, Cu, Ti, Nb, Sn, Pb, Hf, Ta, Ga, Co, Fe, Mo, W, V, Cr, Si, B, C, P, Be, Ag, Au, Pt, Pd, La, Y, Nd, Er, It is preferable to contain two or more of Pr, Dy and the like. Examples of the elemental composition of the material powder for producing the Zr-based metallic glass include Zr—Cu—Al, Zr—Cu—Ni, Zr—Cu—Ni—Al, Zr—Cu—Ni—Al—Ti, and Zr. -Cu-Ni-Al-Nb, Zr-Cu-Ni-Al-Ti-Nb, Zr-Cu-Ni-Al-Co, Zr-Cu-Ni-Al-Ta, Zr-Ni-Al-Y, Zr -Cu-Al-Ta, Zr-Ni-Al-Nd, Zr-Ni-Al-Pd, Zr-Cu-Al-Pd, Zr-Cu-Al-Pd-Fe, Zr-Cu-Ni-Al-Pd , Zr-Cu-Ni-Al-La, Zr-Cu-Ni-Al-Ag, Zr-C-Ti-Ni, Zr-Be-Ti-Ni-Cu, Zr-Be-Ti-Ni-Nb-Cu , Zr-Be-Ti-Co-Cu, etc. In _particular, it is possible to illustrate the _{Zr 55 Cu 30 Ni 5 Al 10} . The numbers represent the atomic ratio of each element.

When Ni is the main component, the material powder contains 35 at% or more of Ni powder in order to exhibit various properties of metal glass, and other component element powders include Al, Zr, Cu, Ti, Nb, Sn, Pb, Hf, Ta, Ga, Co, Fe, Mo, W, V, Cr, Si, B, C, P, Be, Ag, Au, Pt, Pd, La, Y, Nd, Er, Pr, It is preferable to contain 2 or more types from Dy. Examples of the elemental composition of the material powder for producing the Ni-based metallic glass include, for example, Ni—Nb—Ti—Zr, Ni—Nb—Ti—Hf, Ni—Nb—Ti, Ni—Nb—Sn, and Ni—Nb. -Zr, Ni-Nb-Ti-Zr-Fe, Ni-Nb-Ti-Zr-Co, Ni-Nb-Ti-Zr-Cu, Ni-Nb-Ti-Zr-Co-Cu, Ni-Nb-Ti -Zr-Ta, Ni-Nb-Ti-Zr-Pt, Ni-Ti-Zr-Si, Ni-Ti-Zr-Si-Sn, Ni-Nb-Ti-Zr-Si-Sn, Ni-Cr-P -B, Ni-Cr-P-B-Nb, Ni-Cr-P-B-Ta, Ni-Cr-P-B-Ta-Mo, Ni-Cr-P-B-Nb-Mo, Ni-Nb -Ta-P, Ni-Nb-Ta-Zr and the like can be preferably mentioned. ₆₀ Nb ₁₅ Ti ₁₅ Zr ₁₀ can be exemplified. The numbers in parentheses indicate the atomic ratio of each element.

When Fe is the main component, the material powder contains 35 at% or more of Fe powder in order to exhibit various properties of metal glass, and other component element powders include Al, Ni, Cu, Ti, Nb, Sn, Pb, Hf, Ta, Ga, Co, Zr, Mo, W, V, Cr, Si, B, C, P, Be, Ag, Au, Pt, Pd, La, Y, Nd, Er, Pr, It is preferable to contain 2 or more types from Dy. Examples of the elemental composition of the material powder for producing the Fe-based metallic glass include, for example, Fe—Si—B—Nb, Fe—Co—Si—B—Nb, Fe—Cr—Si—B—Nb, and Fe—Co. -Si-B-Nb-Ni, Fe-Si-B-Mo-Ni, Fe-Co-Si-B-Mo-Ni, Fe-Co-Si-B-Nb-Ni, Fe-Ni-B, Fe -Y-B, Fe-Nd-B, Fe-Pt-B, Fe-Pt-Zr-B, Fe-Pt-Nb-B, Fe-Zr-B, Fe-Nb-B, Fe-Nb-Pr -B, Fe-Co-Pr-B, Fe-Co-Nd-B, Fe-Co-Nb-B, Fe-Cr-Mo-B, Fe-Cr-Mo-CB, Fe-Cr-Mo -C-P, Fe-Cr-Mo-C-B-P, Fe-Cr-Si-C-B-P, Fe-Nb-B-P, Fe-Si BP, Fe—Si—C—B—P, Fe—Ga—C—B—P, Fe—Ga—Si—C—B—P, Fe—Co—Ga—C—B—P, Fe— Cr—Mo—C—B—Y, Fe—Cr—Mo—C—B—Nb, Fe—Cr—Mo—C—B—Ta, Fe—Co—Cr—Mo—C—B—Y, Fe— Cr—Mo—C—B—Er, Fe—Mo—C—B—Er, Fe—Ni—Si—B—Nb, Fe—Cu—Nb—Si—B, Fe—Cu—Nb—Zr—B, Fe—Cu—Co—Zr—B, Fe—Al—Ga—P—C—B—Si, Fe—Mo—Ga—P—C—B—Si, Fe—Co—Zr—Mo—WB, Fe-Co-Nd-Dy-B and the like can be preferably exemplified, and particularly Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ can be exemplified. The numbers in parentheses indicate the atomic ratio of each element.

When Ti is the main component, the material powder contains 35 at% or more of Ti powder in order to exhibit various properties of metal glass, and other component element powders include Al, Ni, Cu, Zr, Nb, Sn, Pb, Hf, Ta, Ga, Co, Fe, Mo, W, V, Cr, Si, B, C, P, Be, Ag, Au, Pt, Pd, La, Y, Nd, Er, Pr, It is preferable to contain 2 or more types from Dy. Examples of the elemental composition of the material powder for producing the Ti-based metallic glass include Ti-Zr-Cu-Ni-Hf, Ti-Zr-Cu-Ni-Nb, Ti-Zr-Cu-Ni-Ta, and Ti. -Zr-Cu-Ni-V, Ti-Zr-Cu-Ni-Sn, Ti-Zr-Cu-Ni-Al, Ti-Zr-Cu-Ni-Si, Ti-Zr-Cu-Ni-Pb, Ti -Zr-Cu-Ni-Ga, Ti-Zr-Cu-Ni-Y, Ti-Zr-Cu-Ni-B, Ti-Zr-Cu-Ni-Be, Ti-Zr-Ni-Be, Ti-Zr -Cu-Pd, Ti-Zr-Cu-Pd-Nb, Ti-Zr-Cu-Pd-Ta, Ti-Zr-Hf-Cu-Ni-Si, Ti-Zr-Hf-Cu-Ni-Sn, Ti -Zr-Cu-Ni-Si-B, Ti-Cu-Ni-Fe-Mo, i-Zr-Cu-Ni-Al-Si-B, Ti-Cu-Ni-Co, Ti-Cu-Ni-Sn, Ti-Cu-Ni-Sn-Be, Ti-Cu-Ni-Sn-Si- B, Ti—Cu—Pd—Zr—Sn and the like can be preferably exemplified, and Ti ₄₀ Zr ₁₀ Cu ₃₆ Pd ₁₄ can be particularly exemplified. The numbers in parentheses indicate the atomic ratio of each element.

  Furthermore, as other metallic glasses than these, Cu (copper), Mg (magnesium), Pd (palladium), La (lanthanum), Co (cobalt), Ca (calcium), Nd (neodymium) ), Pr (praseodymium), Pt (platinum), and Au (gold).

  In the above-described embodiment, the material powder is a mixture of a plurality of elemental powders constituting the metal glass. However, the present invention is not limited to this, and the material powder is a metal glass. You may use what mixed the element powder to comprise and the alloy powder in which the one part element which comprises metal glass was alloyed. For example, in the case of Zr-based or Ti-based metallic glass, Zr powder or Ti and other constituent elements are alloyed instead of Zr powder or Ti powder, considering that Zr powder alone or Ti powder alone is easily oxidized. It is also possible to use alloyed powders.

  Next, the manufacturing method of the metal glass molded object of this embodiment is demonstrated. First, as shown in FIG. 1, by supplying a material powder obtained by mixing a plurality of elemental powders constituting the metal glass onto the base material 2 and moving the squeegee 5 in the horizontal direction (arrow A direction), A material powder is spread on the base material 2 to form a flat material powder layer 3 having a substantially constant thickness (powder layer forming step). At this time, the material powder layer 3 having a desired thickness H1 can be formed by adjusting the vertical position of the squeegee 5.

  Next, as shown in FIG. 2, the laser beam scanning device 6 irradiates an arbitrary region on the surface of the material powder layer 3 with laser light, and heats the material powder in the irradiated portion. Thereby, the metal powder 11 is produced from the material powder by melting and solidifying the material powder of the laser beam irradiation portion, and by irradiating the laser beam along a desired scanning path as shown in FIG. The block body 10 made of metal glass is formed (block body forming step). The material powder remains around the metallic glass block 10.

  In the present embodiment, laser light is irradiated along a scanning path based on three-dimensional CAD data. The scanning path of the laser beam is created in advance from the three-dimensional CAD data of the metal glass molded body to be formed. That is, the data of the metallic glass molded body created using 3D CAD software or the like is converted into a contour shape data group of each cross section sliced into a plurality of layers at an equal pitch, and this contour shape data is used to vertically A scanning path of the laser beam is created for each of the material powder layers 3 to be stacked. By irradiating the material powder layer 3 developed in parallel with the xy plane along this scanning path with laser light, the material powder is locally converted to metal vitrification, and the metal glass block 10 having a desired shape is obtained. Is formed. By repeating this many times, a metallic glass molded body having a desired three-dimensional shape can be obtained.

  Then, as shown in FIG. 4, a new material powder is supplied onto the previously formed metallic glass block 10 and the remaining material powder, and the squeegee 5 is moved in the horizontal direction to obtain a desired thickness. A new material powder layer 3 composed of the thickness H2 is formed (powder layer forming step). Each time a new material powder layer 3 is formed, the new material powder layer 3 is laminated on the previously formed material powder layer 3 by raising the squeegee 5.

  Next, similarly, the surface of the new material powder layer 3 is scanned with laser light, and a desired range of the material powder layer 3 is irradiated with the laser light. Thereby, as shown in FIG. 5 and FIG. 6, the material powder in the irradiated portion is locally heated, and the material powder is turned into a metal vitrification, thereby forming a new block body 10 made of the metal glass 11 ( Block body modeling process). When the metal powder block 10 is formed by melting and solidifying the material powder, it is joined to the lower-layer metal glass block 10 that has been previously formed, so that the newly formed metal glass block 10 10 is integrated with the lower metallic glass block 10.

  The above-described powder layer forming step and the block body forming step are repeatedly performed, and the block body 10 having a predetermined pattern shape is stacked in multiple layers by repeatedly performing the stacking n of the block bodies 10 until the predetermined number of layers N is reached. Thus, an integrated metallic glass molded body 1 is formed (see FIGS. 7 to 9). And if the surrounding material powder is removed, the metallic glass molded body 1 having a desired three-dimensional shape can be obtained.

  In irradiating the material powder layer 3 with laser light, the laser light scanning conditions, that is, the laser light scanning speed, scanning width, scanning interval, output, and the like are determined according to the type and particle size of the material powder used. It can be set as appropriate depending on the shape of the metal glass molded body 1 to be used. For example, when the scanning speed of the laser beam is high, the heat generated by the laser beam irradiation does not stay in the material powder layer 3 and the material powder is easily cooled accordingly, so that the material powder is easily converted into a metal glass, but the final There is a risk that the modeling accuracy of the metallic glass molded body 1 manufactured in a practical manner is lowered. On the other hand, if the scanning speed of the laser beam is slow, the finally produced metal glass molded body 1 can be accurately shaped, but the heat generated by the laser beam irradiation is trapped in the material powder layer 3 and the material powder is cooled. Therefore, there is a possibility that a crystal phase such as an oxide is likely to be generated. Therefore, a high-density metallic glass compact with few crystal phases can be formed by appropriately selecting the output of the laser light and appropriately adjusting the scanning speed according to the type of material powder.

  In addition to the metal glass density, in order to manufacture the metal glass molded body 1 with high modeling accuracy, first, the scanning speed of the laser light is set to be slow, and the material powder layer 3 is irradiated with the laser light having a slow scanning speed. After forming the shape of the metal glass molded body 1 finally formed with high accuracy, the scanning speed of the laser beam is set fast, and the material powder layer 3 is irradiated with the laser beam having a high scanning speed. It is also possible to make various ideas such as promoting the vitrification of metal.

  As described above, in the method for producing a metal glass molded body of the present embodiment, the powder layer forming process and the block body forming process are basically performed, and the powder layer forming process and the block body forming process are alternately repeated to obtain a desired size. Since the metal glass molded body 1 having the thickness and shape is manufactured, there is no need for secondary processing after the molded body is manufactured, and the metal glass molded body having a desired size and shape, including large and complex shapes. Can be easily manufactured.

  In addition, as a powder material for manufacturing a metal glass molded body, not a metal glass powder as in the prior art, but a mixture of a plurality of kinds of elemental powders constituting a metal glass is used, so an expensive metal Since it is not necessary to prepare glass powder, the manufacturing cost can be reduced, and the production of the metal glass 11 and the modeling of the block 10 of the metal glass are performed simultaneously in the block modeling process, so the number of processes can be reduced. Thus, the manufacturing efficiency can be improved.

  Furthermore, the kind and mixing | blending of the element powder included in material powder can be changed freely, and the metal glass molded object 1 according to a use use can be manufactured rapidly by changing the kind and mixing | blending of element powder suitably. Can do.

  As mentioned above, although one Embodiment of this invention was explained in full detail, the specific aspect of this invention is not limited to the said embodiment. For example, in this embodiment, a laser beam is used as a heating source for the material powder, but an electron beam may be used instead of the laser beam.

  In the present embodiment, the metal glass molded body 1 is formed by spreading the material powder on the flat plate-like base material 2. It is also possible to install the metallic glass molded body 1 integrally with the component by placing the material powder on the component and spreading the material powder on the component. According to this embodiment, a metallic glass molded body having a desired size and shape can be formed easily and quickly integrally with a component or the like.

  Further, in the present embodiment, it is possible to form a metallic glass molded body having a desired size and shape without performing secondary processing or the like, but in the formation process of the metallic glass molded body, if necessary, For example, after shaping the block body 10 of one or more layers of metal glass, various processes such as cutting the surface of the shaped block body 10 are performed, and the block body 10 after machining is again processed. The metal glass block body 10 may be layered and formed to form the final metal glass molded body 1. According to this embodiment, it is possible to reduce the surface roughness and improve the dimensional accuracy of the formed metallic glass molded body.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(1) Example 1
As a material powder, a mixture of four types of Zr powder, Cu powder, Ni powder, and Al powder constituting Zr-Cu-Ni-Al, which is one of Zr-based metallic glasses, was prepared. The particle size, purity, and composition ratio of each elemental powder are shown in Table 1 below.

  The material powder having the above-described configuration was spread on the base material, and the thickness of the material powder layer to be vitrified was set to 0.1 mm. Thereafter, the thickness of the material powder layer repeatedly laminated on the material powder layer was also set to 0.1 mm. A carbon steel (S50C) plate was used as the substrate. A carbon dioxide laser was used as the laser beam, and the output was set to 200 W, the laser beam scanning speed was set to 200 to 600 mm / sec, and the scanning interval was set to 0.2 mm. The atmosphere around the material powder was an argon gas atmosphere, and the oxygen concentration in the atmosphere around the material powder was set to about 400 ppm.

Under the above-described conditions, a cylindrical metal glass formed body was formed by alternately repeating the powder layer forming step and the block body forming step. This metal glass molded body was subjected to structural analysis by X-ray diffraction (XRD). The analysis result is shown in FIG. FIG. 11 shows the XRD analysis result of the metal glass molded body when the scanning speed of the laser beam is 500 mm / sec. Moreover, the thermal stability accompanying the glass transition and crystallization of a metallic glass molded body was analyzed using a differential scanning calorimeter (DSC). Analysis by DSC was performed by raising the temperature of the metal glass molded body at 0.67 ° C./s in an argon gas atmosphere. FIG. 13 shows a DSC analysis result (thermal analysis curve) of the metal glass molded body when the scanning speed of the laser beam is 500 mm / sec. As a comparative example, XRD analysis and DSC analysis were also performed on Zr ₅₅ Cu ₃₀ Ni ₅ Al ₁₀ metallic glass powder, and the results are shown in FIGS.

  As shown in FIG. 10, in the XRD analysis of the metallic glass molded body of this example (laser beam scanning speed: 200, 300, 400, 500, 600 mm / sec), a sharp peak due to the crystal phase is also observed, A broad peak peculiar to the metallic glass phase is also observed, and it can be judged that the metallic glass phase is generated. In particular, when the scanning speed of the laser beam is high, for example, when the scanning speed of the laser beam shown in FIG. 11 is 500 mm / sec, even if compared with the XRD analysis result of the metallic glass powder of the comparative example shown in FIG. Although some crystallization was observed, it was found that it had an extremely large metallic glass phase portion from the wide diffraction background of the XRD image.

  In addition, according to the thermal analysis curve (see FIG. 13) of the metal glass molded body at a scanning speed of the laser beam from which a large metal glass phase portion was obtained (see FIG. 13), the metal glass is clear before crystallization when heated. One major characteristic is that it exhibits a glass transition and a wide supercooled liquid region, and the thermal analysis curve of the metallic glass molded body of this example shows a clear state of the supercooled liquid state and subsequent crystallization. The glass transition is shown. The glass transition temperature Tg is 410 ° C., the crystallization temperature Tx is 490 ° C., and the supercooled liquid region ΔTx (= Tx−Tg) is calculated to be 80 ° C. Moreover, even if it compares the thermal analysis curve of the metal glass molded object of this Example 1, and the thermal analysis curve of the metal glass powder of the comparative example shown in FIG. 14, the glass of the metal glass molded object of this Example 1 The transition temperature Tg (410 ° C.) and the crystallization temperature Tx (490 ° C.) are very close to the glass transition temperature Tg (413 ° C.) and the crystallization temperature Tx (491 ° C.) of the metal glass powder of the comparative example. In addition, the supercooled liquid temperature region is related to the stabilization of the amorphous alloy structure, and the larger the supercooled liquid region is, the higher the glass forming ability is. It was confirmed that the supercooled liquid region ΔTx is 80 ° C. and has a very high glass shape performance. Then, it is recognized that a metallic glass molded body having a particularly high laser beam scanning speed exhibits a high glass forming ability, and the method for producing a metallic glass molded body according to the present invention makes the metallic glass molded body easy and low-cost. In addition, it was confirmed that a high-quality metallic glass molded body could be manufactured.

(2) Example 2
A cylindrical metal glass molded body is formed under the same conditions as in Example 1 except that copper (oxygen-free copper plate) having higher thermal conductivity than the carbon steel (S50C) plate is used as the material of the base material. did. As in Example 1, a material powder prepared by mixing Zr powder, Cu powder, Ni powder, and Al powder was prepared. The particle size, purity, and composition ratio of each elemental powder are shown in Table 1. It is as follows. The laser beam scanning speed was 500 mm / sec. This metal glass molded body was subjected to structural analysis by X-ray diffraction (XRD). The analysis result is shown in FIG.

  As shown in FIG. 15, when an oxygen-free copper plate having excellent thermal conductivity is used for the base material, the results of XRD analysis when a carbon steel (S50C) plate is used for the base material shown in FIG. In comparison, a broad peak peculiar to the metallic glass phase was observed, and it was confirmed that the intensity of the sharp peak due to the crystal phase was reduced overall. Therefore, it was confirmed that the metal glass molded body to be shaped has a larger metal glass phase portion by using a material having excellent thermal conductivity as the base material.

(3) Example 3
As the material powder, a mixture of four kinds of Ni powder, Nb powder, Ti powder, and Zr powder constituting Ni-Nb-Ti-Zr, which is one of Ni-based metallic glasses, was prepared. The specific particle size, purity, and composition ratio of each elemental powder are as shown in Table 2 below.

  The material powder having the above-described configuration was spread on the base material, and the thickness of the material powder layer to be vitrified was set to 0.1 mm. Thereafter, the thickness of the material powder layer repeatedly laminated on the material powder layer was also set to 0.1 mm. An oxygen-free copper plate was used as the substrate. As the laser beam, a carbon dioxide laser was used, and the output was set to 200 W, the laser beam scanning speed was set to 800 mm / sec, and the scanning interval was set to 0.2 mm. The atmosphere around the material powder was an argon gas atmosphere, and the oxygen concentration in the atmosphere around the material powder was set to about 400 ppm. Under the above-described conditions, a cylindrical metal glass formed body was formed by alternately repeating the powder layer forming step and the block body forming step. This metal glass molded body was subjected to structural analysis by X-ray diffraction (XRD). The analysis results are shown in FIG.

  As shown in FIG. 16, in the XRD analysis of the metal glass molded body of Example 3 (laser beam scanning speed: 800 mm / sec), a broad peak peculiar to the metal glass phase can be observed. It can be determined that it is generated. A sharp peak due to the crystal phase was also observed and some crystallization was observed, but it was confirmed that it had a very large metallic glass phase portion from the wide diffraction background of the XRD image. From the above, it is recognized that the metal glass molded body of Example 3 also exhibits high glass forming ability, and the method for manufacturing a metal glass molded body according to the present invention easily and inexpensively manufactures a metal glass molded body. Further, it was confirmed that a high-quality metallic glass molded body can be produced.

(4) Example 4
As the material powder, a mixture of five types of Fe powder, Cr powder, Mo powder, C powder, and B powder constituting Fe-Cr-Mo-CB, which is one of Fe-based metallic glasses, is used. Prepared. The specific particle size, purity, and composition ratio of each elemental powder are as shown in Table 3 below.

  The material powder having the above-described configuration was spread on the base material, and the thickness of the material powder layer to be vitrified was set to 0.1 mm. Thereafter, the thickness of the material powder layer repeatedly laminated on the material powder layer was also set to 0.1 mm. An oxygen-free copper plate was used as the substrate. As the laser beam, a carbon dioxide laser was used, and the output was set to 200 W, the laser beam scanning speed was set to 500 mm / sec, and the scanning interval was set to 0.2 mm. The atmosphere around the material powder was an argon gas atmosphere, and the oxygen concentration in the atmosphere around the material powder was set to about 400 ppm. Under the above-described conditions, a cylindrical metal glass formed body was formed by alternately repeating the powder layer forming step and the block body forming step. This metal glass molded body was subjected to structural analysis by X-ray diffraction (XRD). The analysis result is shown in FIG.

  As shown in FIG. 17, in the XRD analysis of the metallic glass molded body (laser beam scanning speed: 500 mm / sec) of Example 4, a broad peak peculiar to the metallic glass phase can be observed. It can be determined that it is generated. A sharp peak due to the crystal phase was also observed and some crystallization was observed, but it was confirmed that it had a very large metallic glass phase portion from the wide diffraction background of the XRD image. As mentioned above, it is recognized also about the metallic glass molded object of this Example 4, and the manufacturing method of the metallic glass molded object which concerns on this invention manufactures a metallic glass molded object easily and at low cost. Further, it was confirmed that a high-quality metallic glass molded body can be produced.

DESCRIPTION OF SYMBOLS 1 Metal glass molded object 2 Base material 3 Material powder layer 6 Laser beam scanning apparatus 10 Block body 11 Metal glass

Claims (7)

A powder layer forming step of forming a material powder layer by spreading a material powder in which a plurality of kinds of element powders or alloy powders constituting the metal glass are mixed;
A block for forming a block body made of metal glass while producing metal glass from the material powder by irradiating a predetermined region of the material powder layer with a laser beam or an electron beam and melting and solidifying the material powder of the laser beam irradiation part A body shaping process,
Metal glass molding in which a plurality of block bodies are laminated and integrated by repeating the formation of the material powder layer by the powder layer forming process, the production of the metal glass by the block body modeling process, and the modeling of the block body. The manufacturing method of the metal glass molded object which manufactures a body.   2. The method for producing a metallic glass molded body according to claim 1, wherein the material powder contains at least one metal element selected from Zr, Ni, and Fe as a main component in an atomic ratio of 35 at% or more.   3. The metal glass molded body according to claim 2, wherein the material powder contains Zr as a main component and further contains at least two kinds of metal elements selected from Cu, Ni, Al, Ti, and Be. Method.   The material powder is spread on a flat base material made of a material having high thermal conductivity, and the block body is formed on the base material. A method for producing a metal glass molded body.   The method for producing a metallic glass molded body according to any one of claims 1 to 3, wherein the material powder is spread on a surface of a metal member, and the block body is formed on the metal member.   The method for manufacturing a metal glass molded body according to claim 4 or 5, wherein the base member or the metal member is cooled by a cooling means when the block body is formed.   The formation of the material powder layer by the powder layer formation step, the production of metal glass by the block body formation step, and the formation of the block body are repeatedly performed during decompression or in an inert gas. Item 7. A method for producing a metal glass molded body according to any one of Items 1 to 6.

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