JP2011098383A - Joined body of precision component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a joined body which does not sacrifice a shape and properties of each component, has high joint reliability and can withstand practical use. <P>SOLUTION: The joined body includes two or more precision components joined to each other. At least one of the precision components is formed of an alloy having an amorphous phase as a main phase. In the joined body of precision components, a joining base material, which is represented by a compositional formula shown by general formula (1), and melts in a temperature zone of a crystallization temperature or below of the alloy having the amorphous phase as the main phase, is used in a joint interface. Alternatively, in the joined body of precision components, a foil layer containing at least one of Au, Pt, Pd, and Ni is used on a joint interface side of a member formed of an alloy having an amorphous phase as a main phase, and a joining base material represented by a compositional formula shown by general formula (1) is used on a joint interface. General formula (1) is shown by: Au<SB>100-x</SB>M<SB>x</SB>wherein M represents any group of elements indispensably including at least one of Si, Ge, and Sn; and x is atom% and meets a requirement of 17.5≤x≤40. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a precision actuator made of an alloy having an amorphous phase as a main phase, which is used for a small actuator, an application using MEMS using semiconductor micromachining technology (hereinafter referred to as a MEMS application), or the like. The present invention relates to a joined body of a precision part made of an alloy having an amorphous main phase and a precision part made of a crystalline metal or a semiconductor material.

  Due to high functionality due to technological advancement, devices with a plurality of excellent functions have been developed. In order to provide these functions, it is generally necessary to increase the volume of the device. However, due to the recent demands for resource saving and space saving of equipment, as well as high added value such as minimally invasive medical treatment, there is a demand for equipment that is the same as or smaller than the conventional volume. There is a demand for further miniaturization of components incorporated in equipment.

  In recent years, small actuators manufactured with precision machining and high-precision assembly technology and MEMS applications have been put into practical use. These appearances play a big role in miniaturization of highly functional devices.

  In addition, amorphous alloys are attracting attention as new functional structural materials. Conventionally, almost all of the conventional metal materials that have been used in the history of mankind are constituted by a collection of crystals having a regular structure, that is, a polycrystal. On the other hand, an amorphous alloy is fundamentally different from conventional metal materials in that it is formed by freezing and solidifying while maintaining a liquid structure having no long-range ordered structure.

  Amorphous alloys do not have dislocations or lattice defects like conventional metal materials, so they exhibit a high strength that is almost as close as possible to the ideal strength of the original material, while the free volume between atoms is higher than that of crystals. It is large and supple. From this, the elastic strain limit of the amorphous alloy is as extremely large as about 2%, which is about three times that of the conventional metal material. In addition, since there are no precipitates due to grain boundaries or segregation, there is no unique site that becomes the starting point of corrosion, and it is possible to impart extremely high corrosion resistance by adding elements that form a passive film. is there. Furthermore, an amorphous alloy containing a large amount of magnetic elements such as Fe, Co, and Ni does not have anisotropy, and therefore has an extremely high magnetic permeability.

  In particular, a large number of amorphous alloys having a supercooled state that is so stable that a glass transition region extending to several tens to 100K or more is confirmed. Most of them are “consisting of three or more components”, “atomic radius ratio is 12% or more”, and three common rules of thumb are established: “the mixing enthalpy at the time of liquid generation is negative”. Although they are often referred to as “metallic glass” and “glass alloy” among amorphous alloys, they are essentially regarded as a part of the amorphous alloy. In addition, ultrafine crystals of several nanometers are precipitated, but in the analysis by the X-ray diffraction method, the characteristics of an alloy regarded as amorphous are very similar to those of an amorphous alloy in a strict sense. Generally, it is regarded as an amorphous alloy.

  By realizing the extremely stable supercooled state as described above, it is possible to form a massive amorphous alloy ranging from several millimeters to several tens of millimeters using a casting method. As with the crystalline metal material, it has become possible to form it as various massive parts.

  The solidified surface of the lump of the amorphous alloy is extremely smooth because it has no crystal grain boundary, and has a mold transfer property that can reproduce a nano-order fine structure. Further, since it is frozen and solidified directly from the liquid state, there is no coagulation shrinkage, and therefore its dimensional accuracy is extremely high. From the above, it is suitable for producing precision parts using a casting method from a molten state or an imprint method from a supercooled liquid state.

  Some parts do not need to be in an amorphous phase as a whole, but the practical use of precision parts made of an amorphous-based alloy using various properties of the amorphous phase Are being promoted, some of which have already been put into practical use.

  In the background as described above, precision parts made of an alloy whose main phase is an amorphous phase, or precision parts made of an alloy whose main phase is an amorphous phase and a crystalline metal, or a semiconductor material. There is a need to form a joined body with a component. As a joining method having a possibility of obtaining such a joined body, for example, a viscous flow joining method (Patent Document 1), a friction stir welding method (Patent Document 2), an electron beam joining method (Non-Patent Document 1), and the like. Are known.

JP 9-323174 A Japanese Patent No. 3821656

Y. Kawamura and Y. Ohno, `` Successful Electron-Beam Welding of Bulk Metallic Glass '', Materials Transaction, 2001, Vol. 42, p.2476-2478

  However, as a conventional joining method, various methods have been developed including the method described above. Few examples have been applied to bonded parts made of an alloy whose main phase is amorphous. The reason for this is that in the conventional joining method, when joining, high pressure is applied to the joined parts, impact due to friction, thermal deformation, etc., the shape of the joined precision parts is deformed, and the characteristics are impaired. It is mentioned that.

  In order to join metals, an alloy having a melting point lower than that of the member is melted, and “brazing” is widely used as a method of joining without melting the member itself. In joining parts made of alloys as phases, the characteristics of the amorphous phase are lost by heating, and joining is difficult due to problems with stability and wettability, and there are no examples of application. .

  The present invention has been made in view of such problems, and in the joining of precision parts that are extremely difficult to handle, such as those used in small actuators and MEMS applications, the shape of each part is deformed and characteristics are improved. Precision parts made of an alloy with an amorphous phase as the main phase, or precision parts made of an alloy with an amorphous phase as the main phase, and crystallinity, without damage and with high bonding reliability and practical use An object of the present invention is to provide a joined body with a precision component made of a metal or semiconductor material.

  In order to solve the above-mentioned object, the invention according to claim 1 of the present invention is the case where at least one of two or more precision parts joined is made of an alloy having an amorphous phase as a main phase. This is a precision component bonded body using, as a bonding interface, a bonding base material that melts in a temperature range below the crystallization temperature of an alloy having an amorphous phase as a main phase.

The invention according to claim 2 is characterized in that the amorphous phase is the main phase when at least one of the two or more precision parts joined is made of an alloy having the amorphous phase as the main phase. This is a precision part joined body using a joining base material composed of a composition represented by the following general formula (1), which melts in a temperature zone equal to or lower than the crystallization temperature of the alloy, as a joining interface. In addition, the influence of the impurity element resulting from the raw material and the manufacturing process in manufacturing the base material is such an amount that can be clearly observed by, for example, an energy dispersive X-ray spectrometer (EDS). Otherwise, there is no problem.
General formula (1): Au _100-x M _x
However, M is an arbitrary element group that always includes at least one of Si, Ge, and Sn, and x is atomic%, and 17.5 ≦ x ≦ 40.

Further, in the invention according to claim 3, when at least one of the two or more precision parts joined is made of an alloy having an amorphous phase as a main phase, the amorphous phase is set as a main phase. In a precision component joined body that is melted in a temperature range equal to or lower than the crystallization temperature of the alloy and that is composed of a composition represented by the general formula (1), the alloy has an amorphous phase as a main phase. A precision component joined body having a foil layer containing at least one of Au, Pt, Pd and Ni provided in advance on the joining interface side of a member and a joining base material. In addition, the influence of the impurity element resulting from the raw material and the manufacturing process in manufacturing the base material is such an amount that can be clearly observed by, for example, an energy dispersive X-ray spectrometer (EDS). Otherwise, there is no problem.
General formula (1): Au _100-x M _x
However, M is an arbitrary element group that always includes at least one of Si, Ge, and Sn, and x is atomic%, and 17.5 ≦ x ≦ 40.

The invention according to claim 4 is configured by a composition in which at least one of the two or more precision parts to be joined is represented by the following general formula (2) and includes a combination of three or more elements. 4. The precision part joint according to claim 1, wherein the precision part is made of an alloy having an amorphous phase as a main phase. In addition, the influence of the impurity element resulting from the raw material and the manufacturing process in manufacturing the base material is such an amount that can be clearly observed by, for example, an energy dispersive X-ray spectrometer (EDS). Otherwise, there is no problem.
Formula _{(2): M1 a M2 b} M3 c M4 d Ln e M5 f M6 g
However, M1 is at least one element selected from Ti, Zr and Hf, M2 is at least one element selected from the group consisting of Fe, Co, Ni, Cu, V, Cr, Mn and Nb, and M3 is Zn. , Be, Al, Ga, Ge, In and Sn, at least one element selected from the group consisting of Sn, M4 is at least one element selected from the group consisting of Au, Pt, Pd and Ag, and Ln is Sc, Y , La, Ce, Nd, Sm, Gd, Tb, Dy, Ho, Yb and at least one element selected from the group consisting of Mm (Misch metal which is an aggregate of rare earth elements), M5 is Ta, W and Mo At least one element selected from the group consisting of M6, at least one element selected from the group consisting of Si, P, B and C, a, b, c, d, e and f each in atomic percent, 5 is ≦ a ≦ 85,15 ≦ b ≦ 85,0 ≦ c ≦ 25,0 ≦ d ≦ 25,0 ≦ e ≦ 10,0 ≦ f ≦ 10,0 ≦ g ≦ 10.

  According to a fifth aspect of the present invention, there is provided a joined body joined by a joining base material that melts in a temperature range equal to or lower than a crystallization temperature of an alloy having an amorphous phase as a main phase. 4. The precision part joined body according to claim 1, which is improved to a temperature higher than a crystallization temperature of an alloy having a crystalline phase as a main phase.

  The “alloy having an amorphous phase as a main phase” as used in claims 1 to 5 means that no crystalline diffraction peak is observed by analysis by X-ray diffraction or analysis by X-ray diffraction. Even when a mixture of crystals is observed, a differential exothermic calorimetry indicates a clear exothermic reaction due to the presence of an amorphous phase. Here, even in the case of an ultrafine crystal phase of about several nanometers, no crystalline diffraction peak appears in the analysis by the X-ray diffraction method, and it is clear that it is caused by the glass transition or coarse crystallization in the differential scanning calorimetry. In this case, it is assumed that the exothermic reaction is an amorphous phase. The crystallization temperature is a temperature determined by an isothermal holding temperature and an isothermal holding time indicated by an isothermal transformation temperature curve (TTT curve).

  According to the invention of claim 1, an amorphous body is formed by forming a bonded body using a bonding base material that melts in a temperature zone equal to or lower than a crystallization temperature of an alloy having an amorphous phase as a main phase, as a bonding interface. It becomes possible to provide a joined body joined to the other part without damaging the characteristics of the part made of an alloy whose phase is the main phase even after joining.

  In general, the biggest factor that impairs the characteristics of a part made of an alloy having an amorphous phase as a main phase is crystallization of a phase regarded as amorphous. As crystallization starts, heat is generated due to the transition from the amorphous phase (metastable phase) to the crystalline phase (stable phase). At this time, the driving speed of crystallization is extremely fast, and the amorphous state is instantaneously generated. The phase considered quality disappears. Therefore, there is a very high risk that the excellent characteristics inherent to the amorphous alloy will be lost. For that purpose, the condition of “below the crystallization temperature” is necessary.

According to invention of Claim 2, since melting | fusing point of a joining base material can be lowered | reduced more reliably, it has the effect that a joined body excellent in stability can be provided. The alloys of Au, Si, Ge, and Sn all have a very deep binary eutectic composition. The melting point of each binary eutectic composition is Au _81.4 Si _18.6 : 363 ° C., Au ₇₂ Ge ₂₈ : 361 ° C., Au ₇₁ Ge ₂₉ : 278 ° C. (both atomic%). Further, it is possible to further lower the melting point by increasing the number based on these binary eutectic compositions. For example, the melting point of the ternary composition obtained by adding Bi to the Au—Si binary eutectic composition is Au _69.4 Si _18.6 Bi _12.0 : 295 ° C., and the ternary composition obtained by adding Ni to the Au—Sn binary eutectic composition. The melting point of Au _65.7 Sn _27.2 Ni _{7.1 is} 257 ° C., which is lower than the respective binary eutectic composition. That is, the bonding base material represented by the general formula (1) can be melted at the bonding interface below the crystallization temperature.

  Further, in addition to the above effects, since the bonding base material contains Au as a main component, the wettability with the bonded component is improved. When Au is contained as a main component in the joint interface, Au is negatively mixed with the main constituent element of the alloy having an amorphous phase as a main phase, and in many cases, the mixing enthalpy at the time of liquid generation is negative. Since it has the property of actively linking elements, it contributes greatly to the wettability with the joined parts. For example, the value of mixed enthalpy is Au-Ti: -47 kJ / mol, Au-Zr: -74 kJ / mol, Au-Hf: -63 kJ / mol, Au-Cu: -9 kJ / mol, and the like.

  According to the invention of claim 3, the foil layer containing at least one of Au, Pt, Pd and Ni is provided in advance on the joint interface side of the component made of an alloy having an amorphous phase as a main phase. Therefore, in addition to the above-described effects, the surface oxidation due to the heating of the component can be prevented. Parts made of an alloy having an amorphous phase as a main phase tend to form an oxidation passivated film by concentrating the most active elements with respect to oxygen in the atmosphere in the alloy constituent elements in the vicinity of the surface. Under heating, it is easy to form a stable oxidation passivation film that is thicker than room temperature. Therefore, the formation of the oxidation passive film can be prevented by providing the foil layer as described above. Examples of the method for forming the foil layer include PVD, CVD, sputtering, and printing.

  Furthermore, by providing the foil layer as described above, the wettability with the joining component is further improved, and a large role can be obtained for stable joining with the joining interface. This is because Au, Pt, Pd, and Ni have a property of attracting each other because they have a negative mixing enthalpy at the time of liquid generation among many elements. That is, the foil layer composed of these elements contributes to the improvement of the wettability with the parts in addition to the prevention of the formation of the above-described oxidation passive film. At the same time, a bond based on diffusion occurs between the bonding interface composed of the composition formula (1). In this case, the element is a bonding interface having a composition in which the element or element group constituting the foil layer diffuses in a gradient or intermittent manner on the bonding interface side of the composition formula (1).

  According to the invention of claim 4, when Au is contained as a main component in the bonding interface, Au is between the main constituent elements of the alloy having the amorphous phase represented by the general formula (2) as the main phase. In many cases, there is always an element that has a large negative enthalpy of mixing during liquid generation, and the property of actively linking elements is enhanced. As a result, stable wettability can be realized and high bonding strength can be obtained.

  According to the invention of claim 5, the heat resistance of the bonding base material having a low melting point is improved by improving the fusion temperature of the bonded interface after bonding to the crystallization temperature or higher of the alloy having the amorphous phase as the main phase. The effect is that the problem can be solved.

  As described above, according to the present invention, when at least one precision component is made of an alloy having an amorphous phase as a main phase, the amorphous phase is mainly used even if the size is difficult to bond by the conventional method. It has become possible to provide a joined body joined to the other part without damaging the properties and part shape of the part made of the alloy as the phase even after joining.

It is a figure which shows the typical temperature change curve at the time of the hot-plate heating in a present Example. It is a figure which shows the external appearance of the conjugate | zygote of the precision component obtained in the present Example. It is a figure which shows sectional drawing of the joining interface observed with the scanning magnification electron microscope (Scanning Electron Microscope: SEM) at the magnification of 20,000 times. It is a figure which shows the result of having analyzed the element distribution of the area | region observed in FIG. 3 using the energy dispersive X-ray spectrometer (Energy Dispersive X-ray Spectrometer: EDS). It is a figure which shows the result of having graphed the element distribution amount shown by FIG. 4 relatively.

  The bonded body of the present invention is a crystal of an alloy having an amorphous phase as a main phase when at least one of two or more precision parts being bonded is made of an alloy having an amorphous phase as a main phase. The present invention is characterized in that a bonding base material that melts in a temperature range equal to or lower than the annealing temperature is used for the bonding interface.

  The joined body of the present invention includes a precision part made of an alloy having an amorphous phase as a main phase, or a precision part made of an alloy having an amorphous phase as a main phase and a part made of a crystalline metal or a semiconductor material. It is a joined body.

  As described above, an “alloy having an amorphous phase as a main phase” means that even if a crystalline diffraction peak is not observed or a mixture of crystals is observed by analysis by X-ray diffraction, It refers to an alloy that shows a clear exothermic reaction due to the presence of an amorphous alloy phase in differential thermal analysis.

In order to prevent deterioration of the characteristics of the joined part due to joining, it is necessary to use a joining base material that melts in a temperature range below the crystallization temperature of the precision part. is there. Specifically, it is preferable to use a bonding base material constituted by the composition represented by the general formula (1). In addition, the influence of the impurity element resulting from the raw material and the manufacturing process in manufacturing the base material is such an amount that can be clearly observed by, for example, an energy dispersive X-ray spectrometer (EDS). Otherwise, there is no problem.
General formula (1): Au _100-x M _x
However, M is an arbitrary element group that always includes at least one of Si, Ge, and Sn, and x is atomic%, and 17.5 ≦ x ≦ 40.

  With regard to the composition range x of the bonding interface, if x is less than 17.5, the melting point of the bonding base material is increased, so that there is a very high possibility that a bonding interface that melts in a temperature zone below the crystallization temperature cannot be formed. It is not preferable. In addition, if x exceeds 40, the melting point of the bonding base material increases depending on the composition. Therefore, there is a very high possibility that a bonding interface that melts in a temperature range below the crystallization temperature cannot be formed. This is not preferable because it is difficult to contribute to the wettability. Therefore, the composition range x of the bonding interface is preferably 17.5 ≦ x ≦ 40.

  Parts made of an alloy having an amorphous phase as a main phase tend to form an oxidation passive film by concentrating the most active elements with respect to oxygen in the atmosphere in the vicinity of the surface among the alloy constituent elements. In particular, under heating, it is easy to form a stable oxide passivation film that is thicker than at room temperature. This oxidation passivated film is a major cause of poor bonding.

  Therefore, in order to suppress the formation of an oxidation passivating film on the surface of a part made of an alloy having an amorphous phase as the main phase, the bonding interface side of the alloy having the amorphous phase as the main phase is the stage before bonding. It is preferable to provide a foil layer containing at least one of Au, Pt, Pd and Ni. Au, Pt, Pd, and Ni prevent surface oxidation accompanying heating of a component made of an alloy having an amorphous phase as a main phase. Furthermore, it plays a major role in stable joining between a part made of an alloy having an amorphous phase as a main phase and a joining interface consisting of the composition formula (1). However, it is more preferable to form Ni together with Au, Pt and Pd because the standard free energy of formation for oxidation is low.

The “precise part made of an alloy having an amorphous phase as a main phase” constituting the joined body of the present invention is preferably composed of a composition represented by the following general formula (2). In addition, the influence of the impurity element resulting from the raw material and the manufacturing process in manufacturing the base material is such an amount that can be clearly observed by, for example, an energy dispersive X-ray spectrometer (EDS). Otherwise, there is no problem.
Formula _{(2): M1 a M2 b} M3 c M4 d Ln e M5 f M6 g
However, M1 is at least one element selected from Ti, Zr and Hf, M2 is at least one element selected from the group consisting of Fe, Co, Ni, Cu, V, Cr, Mn and Nb, and M3 is Zn. , Be, Al, Ga, Ge, In and Sn, at least one element selected from the group consisting of Sn, M4 is at least one element selected from the group consisting of Au, Pt, Pd and Ag, and Ln is Sc, Y , La, Ce, Nd, Sm, Gd, Tb, Dy, Ho, Yb and at least one element selected from the group consisting of Mm (Misch metal which is an aggregate of rare earth elements), M5 is Ta, W and Mo At least one element selected from the group consisting of M6, at least one element selected from the group consisting of Si, P, B and C, a, b, c, d, e and f each in atomic percent, 5 ≦ a ≦ 85, 15 ≦ b ≦ 85, 0 ≦ c ≦ 25, 0 ≦ d ≦ 25, 0 ≦ e ≦ 10, 0 ≦ f ≦ 10, 0 ≦ g ≦ 10, shown in the general formula (2) Examples of the alloys include alloys represented by the following general formulas (2-a) to (2-y).
Formula (2-a): M1 _a M2 _b
Formula (2-b): M1 _a M2 _b M3 _c
Formula (2-c): M1 _a M2 _b M4 _d
Formula _{(2-d): M1 a} M2 b Ln e
Formula (2-e): M1 _a M2 _b M5 _f
General formula (2-f): M1 _a M2 _b M6 _g
Formula (2-g): M1 _a M2 _b M3 _c M4 _d
Formula _{(2-h): M1 a} M2 b M3 c Ln e
Formula (2-i): M1 _a M2 _b M3 _c M5 _f
General formula (2-j): M1 _a M2 _b M3 _c M6 _g
Formula _{(2-k): M1 a} M2 b M4 d Ln e
General formula (2-1): M1 _a M2 _b M4 _d M5 _f
General formula (2-m): M1 _a M2 _b M4 _d M6 _g
Formula _{(2-n): M1 a} M2 b Ln e M5 f
Formula (2-o): M1 _a M2 _b M5 _f M6 _g
Formula _{(2-p): M1 a} M2 b M3 c M4 d Ln e
General formula (2-q): M1 _a M2 _b M3 _c M4 _d M5 _f
Formula (2-r): M1 _a M2 _b M3 _c M4 _d M6 _g
Formula _{(2-s): M1 a} M2 b M4 d Ln e M5 f
General formula (2-t): M1 _a M2 _b M4 _d M5 _f M6 _g
Formula _{(2-u): M1 a} M2 b Ln e M5 f M6 g
Formula _{(2-v): M1 a} M2 b M3 c M4 d Ln e M5 f
General formula (2-w): M1 _a M2 _b M3 _c M4 _d M5 _f M6 _g
Formula _{(2-x): M1 a} M2 b M4 d Ln e M5 f M6 g
Formula _{(2-y): M1 a} M2 b M3 c M4 d Ln e M5 f M6 g

  An alloy composed of the combination of the general formula (2-a) has many combinations that form an amorphous phase even in the binary composition of M1 and M2, and by combining three or more elements, An amorphous phase is more easily formed. In particular, M1 is an important element for obtaining a stable bonding interface, and if the composition range a of M1 is less than 15, the wettability is reduced. Accordingly, the composition range b of M2 is also limited to 85 or less. When the composition range a of M1 exceeds 85, an amorphous phase is very difficult to be formed regardless of what element M2 has. Accordingly, the composition range b of M2 is also limited to 15 or more.

  An alloy composed of a combination of the general formulas (2-b) to (2-y) is obtained by adding M3, Ln, M4 and M5 based on the general formula (2-a). In precision parts made of an alloy having an amorphous phase as a main phase used in the joining member of the present invention, the additive elements or additive element groups M3, Ln, M4 and M5 cannot be the main components of the alloy. This is because a higher crystallization temperature can be obtained when either M1 or M2 is a main component, which is suitable for the joined body of the present invention. However, since these additive elements or additive element groups contribute to the stabilization of the amorphous phase and the like and do not cause a major problem in bonding, there is no problem even if they are contained.

  However, when the composition ranges c and d of M3 and M4 exceed 25, an amorphous phase is very difficult to be formed. Therefore, these composition ranges c and d are limited to 25 or less. In addition, since Ln, M5, and M6, which is a non-metal, have their composition ranges e, f, and g exceeding 10, it is difficult to form an amorphous phase. Therefore, these composition ranges e, f, and g are 10 It is limited to the following.

  Further, the element (group) constituting the joining component or the element (group) constituting the foil layer formed at the joining interface and the joining base material may cause diffusion, or the joining base material may be intentionally oxidized. If there is a problem with the heat resistance of the bonding base material, it is possible to improve the melting temperature of the bonded interface after bonding to be higher than the crystallization temperature of the alloy having the amorphous phase as the main phase. As the method, in the case where the bonding base material represented by the general formula (1) is used, a method of hypoeutecticizing by diffusing Si, Ge, or Sn into the bonding interface of the bonded component, and a foil layer Examples thereof include a method of hypoeutecticization by increasing the thickness and reducing the thickness of the bonding base material to diffuse both.

In this embodiment, precision parts made of an alloy having an amorphous phase as a main phase, or precision parts made of an alloy having an amorphous phase as a main phase and precision parts made of a crystalline metal or a semiconductor material are used. It is an example of a typical technique and conditions for providing a joined body, and is not limited only to these techniques and conditions. In the following examples, Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ (hereinafter referred to as Z alloy), Cu ₆₀ Zr ₃₀ Ti ₁₀ (hereinafter referred to as Z alloy) are used as precision parts made of an alloy having an amorphous phase as a main phase. C alloy), Ti ₄₀ Zr ₁₀ Cu ₃₆ Pd ₁₄ (hereinafter referred to as T alloy), and Ni ₅₃ Nb ₂₀ Ti ₁₀ Zr ₈ Co ₆ Cu ₃ (hereinafter referred to as N alloy) respectively. Show.

  It is known that a Zr-TM (transition metal) -Al-based alloy typified by a Z alloy has a high strength exceeding 1500 MPa and is excellent in corrosion resistance against acids and the like. Furthermore, the supercooled liquid region (glass transition region) indicated by the temperature difference between the glass transition temperature (Tg) and the crystallization temperature is extremely wide, and in the case of Z alloy, 80 to 90 K is further heated at 40 K / min, and the composition is further prepared. As a result, alloys exceeding 100K can be produced. Further, the critical cooling rate for forming the amorphous is about several to several tens of K / s, which is regarded as one of the alloy systems having the most stable amorphous state. For this reason, it is possible to form cm-class samples and parts made of an amorphous phase, and this alloy system is most actively studied for practical use as an amorphous alloy.

  Cu- (Zr, Hf) -Ti-based alloys represented by C alloy are inferior to the stability of the amorphous state compared to Zr-TM (transition metal) -Al-based alloys, but Zr-TM (transition metal) It has been known that it has properties similar to those of a) Al-based alloy and has superior strength properties, and has a strength of the order of 2000 MPa. An example in which corrosion resistance and strength are further improved by adding about several percent of Ni, Nb, Ta, Be or the like to a Cu— (Zr, Hf) —Ti alloy is reported. Zr-TM (transition metal) -Al alloy is an alloy system that is particularly effective when mechanical properties are insufficient, and is also an alloy system that has been actively studied for practical use.

  Ti-Cu-Zr-Pd alloys, represented by T alloys, were developed as biomaterials that do not contain biotoxic elements, and have mechanical properties equivalent to Zr-TM (transition metal) -Al alloys. In addition to having excellent corrosion resistance with respect to Hanks solution over pure Ti and Ti-6Al-4V alloy, it is known to have excellent biocompatibility by performing bioactivation treatment. Since it can contain a large amount of expensive Pd, it is not practical as a mechanical structural material, but it is considered to be put to practical use in applications such as precision parts to be inserted or embedded in living bodies and minimally invasive precision applications using the parts. It is an alloy system.

  Ni-Nb- (Ti, Zr) -based alloys represented by N alloys have the least amorphous stability in the examples, but have a very high tensile strength of 3000 MPa and are suitable for all acids. It is known to have excellent corrosion resistance. This tensile strength corresponds to the highest class among alloys capable of forming an amorphous phase as a lump. In the basic evaluation test on the durability of the planetary gear mechanism using the N alloy ultra-precision gear of the module 0.04, the present inventors compared with the planetary gear mechanism using the tool steel ultra-precision gear of the same specifications. And it has been confirmed that it has excellent durability on the order of 100 times. In addition, it has become clear that it has excellent durability on the order of 10 times as compared with a planetary gear mechanism using a Z alloy, and practical application has been studied for a microstructure member requiring a high load. Alloy system. At the same time, it is an alloy system that is expected to be applied to separators by utilizing its excellent corrosion resistance and hydrogen permeability.

  As described above, it is indispensable to properly join a precision part that has various excellent characteristics of an alloy having an amorphous phase as a main phase without damaging the characteristics or the shape of the part. is there.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  As a model of a precision part used in this example, a small piece having a shape of a diameter φ1 mm and a thickness 1 mm, which is a size expected to be difficult to join by a conventional method, was produced. Next, the surface of the object to be joined is subjected to mirror polishing using a resin plate with a polishing liquid in which an oxide fluid abrasive having an average particle size of less than 1 μm is mixed with an aqueous solvent in an amount of 10 to 20% by volume. It was. Thereafter, the surfaces to be joined were cleaned by immersion cleaning using an acid. Further, after evacuating to the order of 1 Pa, Au and / or Ni, Pt, etc. were deposited to a total thickness of about 100 nm.

On the other hand, Au ₇₁ Sn ₂₉ was used as a bonding base material constituting the bonding interface. This joining base material was manufactured by a liquid rapid solidification process using a single roll in a sealed environment in which a vacuum was reduced to about 0.02 MPa by Ar substitution after evacuation of the order of 10 ⁻³ Pa. The number of rotations of the roll was controlled so that the thickness of the joining member was about 20 μm.

  The produced joining base material was cut out into 1 mm x 1 mm, and it was set as the state pinched | interposed into two precision components of joining object. Thereafter, heat treatment in an Ar-substituted atmosphere under atmospheric pressure was performed on the hot plate for a predetermined time. Although it cannot be said that the heat treatment in this example is the optimum condition for each material, the maximum heating temperature was set to 400 ° C. and the holding time at the maximum temperature was unified to 10 minutes. A typical temperature change curve at the time of heating the hot plate is shown in FIG. According to this, the temperature rising rate between 200 ° C. and 400 ° C. is about 30 to 50 K / min, and the cooling rate is about 10 to 25 K / min although it varies depending on the temperature. In this example, only a trial manufacture of a joined body in which the combination of parts is made of the same kind of material was carried out. However, only for the Z alloy, prototypes of joined bodies with crystalline metal materials were also produced as various representatives. Regarding the possibility of the joining member, it was accepted that the joining was sufficiently performed to withstand handling. In addition, regarding the presence or absence of crystallization of precision parts made of an alloy having an amorphous phase as a main phase, the X-ray diffraction profile is measured before and after joining after removing the foil layer adhering to the face of the joining interface of the precision parts. In comparison, the differential scanning calorimetry was further evaluated by confirming the presence or absence of an exothermic peak accompanying crystallization at a heating rate of 40 K / min.

As a comparative example, a case where La ₅₅ Al ₂₅ Cu ₁₀ Ni ₅ Co ₅ (hereinafter referred to as L alloy) is applied to precision parts made of an alloy having an amorphous phase as a main phase will be described. Although the L alloy is slightly inferior in strength to other alloy systems, the L alloy is excellent in stability in an amorphous state like the Z alloy, and the supercooled liquid region (glass transition region) is 90 to 100 K when heated at 40 K / min. It extends to. Since this stable supercooled liquid has very good fluidity, there have been many reports on the production of precision parts with extremely fine shape transferability in viscous fluid processing. It is an alloy system suitable for. However, this alloy system is mainly composed of La and deviates from the condition where M1 or M2 represented by the general formula (2) is the main component. When Ln (rare earth element) is a main component, the crystallization temperature is considerably lower than that of an alloy system mainly containing M1 or M2, and is about 270 ° C. under heating at 40 K / min. This is a slight temperature difference compared to the melting point 257 ° C. of Au _65.7 Sn _27.2 Ni _7.1 represented by the general formula (1). L alloy is crystallized by heat treatment at 400 ° C. Therefore, 260 ° C, which is slightly higher than the melting point 257 ° C of Au _65.7 Sn _27.2 Ni _7.1 represented by the general formula (1), is set as the highest temperature, and there is no holding time. (0 minutes) and 10 minutes of heat treatment were performed.

The results of this example are shown in Table 1. Moreover, the external appearance of the joined body of precision parts is shown in FIG. Even after joining, no change was found in the shape of the joined parts.

  As described above, in Examples 1 to 7 according to the present invention, it was confirmed that any two precision parts were joined. In addition, no significant crystal diffraction peak was observed in the X-ray diffraction profiles before and after the treatment under the treatment conditions in this example. In addition, a clear exothermic peak accompanying crystallization was observed in differential scanning calorimetry. On the other hand, in Comparative Example 8, although it was possible to join by heating for 10 minutes, expression of a crystalline diffraction peak suggesting crystallization was observed. When there was no holding time, it did not come to join. Furthermore, the expression of a crystalline diffraction peak suggesting crystallization was observed even without holding time. Further, in the differential scanning calorimetry, no clear exothermic peak accompanying crystallization was observed.

  Next, a detailed analysis result at the bonding interface of the joined body of the example of the present invention will be described based on Example 1 of the present invention. The bonded body is cut in a direction perpendicular to the bonding interface, and mirror polishing is performed with a resin plate using a polishing liquid in which 10 to 20% by volume of an oxide-based fluid abrasive having an average particle size of less than 1 μm is mixed with an aqueous solvent. Processing was performed to obtain a cross section of the bonding interface. FIG. 3 shows a cross-sectional image of the bonding interface observed at a magnification of 20,000 with a scanning electron microscope (SEM). The bright image on the left is a portion made of a bonding base material component, and the dark image on the right is a portion made of a Z alloy having an amorphous phase. No peeling or cracking was observed at all at the bonding interface, and it was confirmed that a good bonding interface was obtained. Moreover, it has been seen that it has a relatively clear contrast.

  In addition, regarding the constituent elements of the bonding base material and the main constituent elements of the Z alloy, Au, Sn, Zr, Cu, Al, and Ni, the element distribution in the region formed by the same observation image is expressed by an energy dispersive X-ray spectrometer (Energy). Analysis was performed using Dispersive X-ray Spectrometer (EDS). The result is shown in FIG. Also from this analysis result, the distribution of each element that closely matched the appearance of the bonding interface was confirmed. Further, FIG. 5 shows the result of relatively graphing the element distribution amount. A concentration gradient is expected to occur near the junction interface, but the range is approximately 500 nm to 1 μm, and the measurement resolution of EDS (theoretical value in the case of 15 kV and several nA is approximately 500 nm). From this, it was suggested that the range of the concentration gradient near the bonding interface may be narrower than 500 nm.

  In addition, Table 2 shows the results of quantitative analysis at the points of about 1 μm, about 2 μm, and about 5 μm away from the bonding interface for each region of the bonding base material observed in the bright image and the Z alloy observed in the dark image. Show.

  From this result, it has been clarified that the composition ratio of the Z alloy can be regarded as almost homogeneous. On the other hand, the composition of the bonding base material in the vicinity of the bonding interface has a composition close to the β phase shown in the Au-Sn binary phase diagram, and the composition is significantly more Au than the composition before bonding. It became clear. In addition, the Sn content tends to increase as the distance from the bonding interface increases. The composition is expected to be mainly composed of the ζ phase at a distance of about 2 μm, and a slight excess of Sn is excessive at a distance of about 5 μm. It was found to have a crystal composition. This is a result that suggests that Au having a negative mixing enthalpy at the time of liquid generation contributes greatly to wettability with Zr and Cu, which are the main constituent elements of the Z alloy.

  From the above, when at least one of two or more precision parts being joined is made of an alloy having an amorphous phase as a main phase, it is assumed that joining is difficult with the conventional method. The bonded phase is formed by using a bonding base material that melts in a temperature zone below the crystallization temperature of an alloy having an amorphous phase as a main phase as a bonding interface. It has become possible to provide a joined body joined to the other part without damaging the characteristics and part shape of the part made of an alloy having the main phase after joining. In other words, in the joining of precision parts that are extremely difficult to handle, such as those used in small actuators and MEMS applications, the characteristics of each part are not impaired even after joining, and the joining reliability is high and can withstand practical use. To provide a joined body of precision parts made of an alloy having a crystalline phase as a main phase or a precision part made of an alloy having an amorphous phase as a main phase and a precision part made of a crystalline metal or a semiconductor material. Became possible.

Claims (5)

  In the case where at least one of the two or more precision parts being joined is made of an alloy having an amorphous phase as a main phase, in a temperature range lower than the crystallization temperature of the alloy having an amorphous phase as a main phase. A precision component assembly using a molten base material for the joint interface. In the case where at least one of the two or more precision parts being joined is made of an alloy having an amorphous phase as a main phase, in a temperature range lower than the crystallization temperature of the alloy having an amorphous phase as a main phase. Bonded general formula (1) of a precision part using a bonding base material having a composition represented by the general formula (1) that melts as a bonding interface: Au _100-x M _x
However, M is an arbitrary element group that always includes at least one of Si, Ge, and Sn, and x is atomic%, and 17.5 ≦ x ≦ 40. In the case where at least one of the two or more precision parts being joined is made of an alloy having an amorphous phase as a main phase, in a temperature range lower than the crystallization temperature of the alloy having an amorphous phase as a main phase. In the precision component joint used for the joining interface constituted by the composition represented by the general formula (1) to be melted, Au, in advance on the joining interface side of a member made of an alloy having an amorphous phase as a main phase. Bonded base material of precision parts characterized by having a foil layer containing at least one of Pt, Pd and Ni, a bonding base material, and a bonding base material: Au _100-x M _x
However, M is an arbitrary element group that always includes at least one of Si, Ge, and Sn, and x is atomic%, and 17.5 ≦ x ≦ 40. An alloy whose main phase is an amorphous phase composed of a composition of at least one of the two or more precision parts being joined represented by the general formula (2) and comprising a combination of three or more elements. a precision parts made of a conjugate of general formula precision part according to any one of claims 1 to _{3 (2): M1 a M2} b M3 c M4 d Ln e M5 f M6 g
However, M1 is at least one element selected from Ti, Zr and Hf, M2 is at least one element selected from the group consisting of Fe, Co, Ni, Cu, V, Cr, Mn and Nb, and M3 is Zn. , Be, Al, Ga, Ge, In and Sn, at least one element selected from the group consisting of Sn, M4 is at least one element selected from the group consisting of Au, Pt, Pd and Ag, and Ln is Sc, Y , La, Ce, Nd, Sm, Gd, Tb, Dy, Ho, Yb and at least one element selected from the group consisting of Mm (Misch metal which is an aggregate of rare earth elements), M5 is Ta, W and Mo At least one element selected from the group consisting of M6, at least one element selected from the group consisting of Si, P, B and C, a, b, c, d, e and f each in atomic percent, 5 is ≦ a ≦ 85,15 ≦ b ≦ 85,0 ≦ c ≦ 25,0 ≦ d ≦ 25,0 ≦ e ≦ 10,0 ≦ f ≦ 10,0 ≦ g ≦ 10.   In a joined body joined by a joining base material that melts in a temperature zone below the crystallization temperature of an alloy having an amorphous phase as a main phase, the melting temperature after joining of the alloy having an amorphous phase as a main phase The precision part joined body according to any one of claims 1 to 3, which is improved to a temperature equal to or higher than a crystallization temperature.