JP2009155729A - Deformation working method for metal glass composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deformation working method for a metal glass composite material where the formation of defects, fractures or the like in a metal glass layer upon deformation working are extremely reduced. <P>SOLUTION: The deformation working method for a metal glass composite material includes: a forming step for a metal glass composite material where metal glass particles are laminated on the surface of a substrate, so as to form a metal glass layer; a homogenizing step where the metal glass layer is pressurized in a supercooled liquid state, so as to homogenize the metal glass layer; and a step where the homogenized metal glass layer is subjected to deformation working. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a deformation processing method for a metallic glass composite material, and more particularly to a deformation processing method capable of suppressing defects and breakage of a metallic glass layer during deformation processing.

  It is known to impart functionality such as corrosion resistance, wear resistance, heat resistance, high strength, and high hardness to the substrate surface by forming a highly functional metal film. Such composite materials are used after being processed into various shapes according to the purpose.

  There are various methods for easily forming a metal film on the surface of a substrate. For example, spraying can form a film on a large area relatively easily and directly, and a highly functional material is coated only on the surface of a substrate. Therefore, this method is advantageous in that it is excellent in weight reduction and economy, and is a dry process and has no problems such as wastewater treatment.

However, metal sprayed coatings usually have a large number of pores, and even if the sprayed coating is further sealed with a resin or the like in order to close the through-holes, functions such as corrosion resistance and wear resistance cannot be sufficiently achieved. In general, an amorphous alloy is superior in corrosion resistance and the like as compared with a crystalline alloy because there is no crystal grain boundary, but it is very difficult to obtain an amorphous alloy coating by thermal spraying.
For such problems, it has been reported that by spraying amorphous phase metallic glass particles in a supercooled liquid state, a very dense and amorphous phase metallic glass sprayed coating layer can be formed on the substrate surface. (Patent Document 1).

  One major feature of metallic glass is that when heated, it exhibits a distinct glass transition and a wide supercooled liquid region before crystallization. In the temperature range ΔTx = Tx−Tg indicated by the temperature range ΔTx = Tx−Tg between the crystallization start temperature (Tx (K)) and the glass transition temperature (Tg (K)), a deformation resistance is obtained due to the viscous flow state. Since it decreases significantly, processing becomes easy. It has also been reported that using such properties, the metal glass layer is pressed with a mold in a supercooled liquid state to give the metal glass layer an uneven shape (Patent Document 2).

However, when such a metallic glass composite material is deformed by pressing or the like, defects such as an increase in gaps between particles in the metallic glass layer even if the metallic glass layer is processed in the supercooled liquid temperature region. May be formed, or damage such as peeling or tearing may occur.
Japanese Patent Laid-Open No. 2006-21400 Japanese Patent Laid-Open No. 2006-122918

  The present invention has been made in view of the problems of the background art described above, and an object thereof is to provide a deformation processing method for a metal glass composite material in which there is very little defect formation or breakage of the metal glass layer during deformation processing. is there.

As a result of intensive studies by the present inventors in order to achieve the above-mentioned object, the metal glass layer of the composite material is preliminarily applied under pressure in a supercooled liquid state before performing deformation processing. It has been found that defect formation and breakage during deformation processing are significantly reduced.
The reason is not clear, but the metallic glass layer formed by laminating metal particles such as thermal spray is essentially non-uniform even if it appears to be dense and uniform at first glance. It was considered that there were non-uniform portions in properties (for example, oxidation, residual stress, pores, unwelded portions, etc.), and this might be the cause of the occurrence of defects and damage as described above. And, by applying a uniform pressure in the supercooled liquid state in advance to the metallic glass layer before the deformation process, complete adhesion between the adjacent laminated particles is promoted, and potential internals existing in the metallic glass layer are also promoted. It was considered that the diffusion or disappearance of defects was promoted and the metal glass layer was homogenized, and as a result, the formation of defects and the occurrence of breakage were significantly suppressed in the subsequent deformation process.

Therefore, the method for deforming a metal glass composite material according to the present invention includes a metal glass composite material forming step of forming a metal glass layer by laminating metal glass particles on a substrate surface,
A homogenization step of homogenizing the metal glass layer by pressurizing the metal glass layer in a supercooled liquid state;
Deforming the homogenized metallic glass layer;
It is characterized by providing.
In the method of the present invention, it is preferable to laminate the metal glass particles by thermal spraying.
In the method of the present invention, it is preferable that the deformation process is a press process.
In the method of the present invention, the homogenization step is preferably performed in a temperature range of glass transition temperature Tg (K) x 85% of metal glass to crystallization start temperature Tx (K) x 97%. It is suitable to carry out for 1 to 600 seconds at a pressure of 5 to 1000 MPa.
Moreover, in this invention, it is suitable for the process of a homogenization process to process with a uniform pressure with respect to the substrate surface.
In the method of the present invention, it is preferable that the deformation process is performed in a temperature range of glass transition temperature Tg (K) × 85% of metal glass to crystallization start temperature Tx (K) × 100%.
Moreover, in the method of this invention, it is suitable that the thickness of the board | substrate which laminates | stacks a metallic glass particle is 0.5 mm or less.
In the method of the present invention, it is preferable that the metallic glass layer and the base material, which have been homogenized in the deformation process, are integrally deformed.

According to the method of the present invention, since the formation of defects and breakage of the metal glass layer when the metal glass composite material is deformed can be remarkably reduced, the yield when deforming into the shape of various members and Reliability can be increased. The larger the substrate is, the higher the probability that the metal glass layer covering it will be non-uniform, and it will be more prone to problems during deformation processing. Therefore, the method of the present invention is particularly useful.
In normal spraying, the surface of the base material is blasted to improve adhesion to the thermal spray coating layer. However, if the base material is thin, the base material itself may be deformed by the blasting process. In addition, sufficient blasting cannot be performed. For this reason, when the base material is thin, the adhesion between the thermal spray coating and the base material is inevitably lowered, and when the composite material is integrally deformed, the thermal spray coating is likely to be peeled off or torn from the base material. However, the method of the present invention is also effective against breakage of a composite material having such a thin substrate.

The deformation processing method of the metallic glass composite material according to the present invention,
(I) a metal glass composite material forming step of forming a metal glass layer by laminating metal glass particles on the substrate surface;
(II) a homogenization step of homogenizing the metal glass layer by pressurizing the metal glass layer in a supercooled liquid state;
(III) a step of deforming the homogenized metallic glass layer;
It is characterized by providing. An example of a typical deformation processing method of the present invention is schematically shown in FIG.

In FIG. 1, a metallic glass layer 12 is formed by laminating metallic glass particles on the surface of a substrate 10 to obtain a metallic glass composite material 14 (step I). Next, the metal glass layer 12 is homogenized by pressurization (step II), and then the entire composite material 14 is bent and deformed (step III).
Hereinafter, each step will be described.

(I) Forming process of metallic glass composite material In this process, the method of forming the metallic glass layer on the substrate surface is not particularly limited. For example, the metallic glass is formed by laminating metallic glass particles like spraying. The method of the present invention is particularly effective because the method of forming the layer tends to be non-uniform in nature.
Examples of the spraying method include atmospheric pressure plasma spraying, low pressure plasma spraying, flame spraying, high-speed flame spraying (HVOF), and cold spraying, and are not particularly limited. One suitable thermal spraying method includes high-speed flame spraying using metallic glass particles, and a high-quality thermal spray coating can be obtained.

  The shape of the metal glass particles is not particularly limited, and examples thereof include a plate shape, a chip shape, a particle shape, and a powder shape, and preferably a particle shape or a powder shape. Examples of the method for preparing the metal glass particles include an atomizing method, a chemical alloying method, and a mechanical alloying method, and those prepared by the atomizing method are particularly preferable in view of productivity.

  The particle size of the metallic glass particles is 1 to 80 μm, preferably 5 to 50 μm. If the particle size is too large, pores may increase in the sprayed coating or continuous pores may be generated. If the particle diameter is too small, the productivity tends to decrease, for example, the molten particles tend to adhere to the thermal spray barrel, or the number of thermal sprays increases to achieve a desired film thickness. Further, when the particles adhered and solidified in the barrel are peeled off and sprayed from the barrel, the uniformity of the sprayed coating is lowered.

When the thermal spray heat source is combustion energy, kerosene, acetylene, hydrogen, propane, propylene, or the like can be used as the thermal spray fuel. When electric energy is used as the thermal spraying heat source, argon, hydrogen, helium, or the like can be used as the plasma gas.
In spraying, N ₂ gas is usually used as a carrier gas, but the formation of nitrides may affect the coating composition and denseness. This can be improved by using air (dry air), oxygen, inert gas (Ar, He, etc.) as the carrier gas. Since there is concern about oxidation with air or oxygen, an inert gas is most preferably used as the carrier gas.
In order to obtain a high-quality bonded interface, it is usually preferable to apply a temperature load of 100 ° C. or higher to the base material. More preferably, it is 150 ° C. or higher, and the upper limit is not particularly specified, but it is usually not higher than the glass transition temperature, preferably 400 ° C. or lower.

Base materials include general-purpose metals such as iron, aluminum, and stainless steel, and some heat-resistant plastics such as ceramics, glass, and polyimide, but metal materials with high heat resistance, heat capacity, and heat conduction are particularly suitable, such as copper and stainless steel. It is. Also, light metals having a specific gravity of 3.0 or less, such as aluminum, magnesium, and alloys thereof can be used.
Moreover, in order to improve the bondability of a metal glass sprayed coating, a base material is used after roughening the surface of the base material by a known method such as blasting.

The thickness of the metal glass sprayed coating can be appropriately set depending on the purpose, but it is usually preferably 50 μm or more, and more preferably 100 μm or more in consideration of homogenization by pressurization or deformation processing. The upper limit is not particularly limited, but if it is too thick, the economic efficiency and lightness are reduced. For example, for the purpose of imparting corrosion resistance, 500 μm is sufficient.
The thermal spray coating can be formed on a substrate having various shapes, and can also be formed by patterning by masking or the like. A substrate having an irregular shape on the surface or a porous body can also be used.

The higher the density and uniformity of the metal glass layer before the homogenization treatment, the easier the subsequent homogenization. Further, since the crystallized metal glass layer is likely to be damaged by deformation processing, it is desirable that the metal glass layer before the homogenization treatment has as few crystalline phases as possible as an amorphous phase.
When forming a sprayed coating consisting of a uniform metallic glass amorphous solid phase with few pores and no continuous pores, use amorphous glass metallic particles as the thermal spraying raw material and use the supercooled liquid state of the metallic glass. It can be carried out.

In the supercooled liquid state, the metallic glass exhibits viscous flow and has a low viscosity. For this reason, when the metallic glass in the supercooled liquid state collides with the substrate surface, it is crushed instantly and spreads on the substrate surface, and a good splat having a very thin thickness can be formed. A dense spray coating without continuous pores can be formed by depositing such splats.
Moreover, since the splat is cooled in the supercooled liquid state, a crystalline phase is not generated, and only an amorphous phase is obtained.

In general, in the case of thermal spraying in the air, the oxide of the thermal spray material is included in the coating, which adversely affects the properties of the coating. There is almost no influence of oxidation.
Therefore, if the metal glass particles in the amorphous phase are sprayed, and the metal glass spray particles are solidified and laminated on the surface of the base material in a supercooled liquid state to form a sprayed coating, it is composed of a uniform amorphous solid phase of the metal glass. It is advantageous to obtain a sprayed coating that is almost free from continuous pores.

  By such a method, a metal glass sprayed coating layer having a very dense and amorphous phase can be formed on the substrate surface. For example, a sprayed coating having a porosity of 2% or less and no pinholes can be obtained. Regarding the porosity, an arbitrary cross section of the metal glass layer can be image-analyzed, and the maximum area ratio of the pores can be adopted as the porosity. Further, the absence of pinholes can be confirmed by image analysis of an arbitrary cross section of the metal glass layer. Such a method is described in Patent Document 1.

In this invention, it does not restrict | limit especially as a metallic glass, What is necessary is just to select and use a well-known thing suitably according to the target function. For example, a metallic glass is composed of a plurality of elements and contains at least one of Fe, Co, Ni, Ti, Zr, Mg, Cu, and Pd as a main component in a range of 30 to 80 atomic%. Is mentioned.
A preferred composition of the Cu-based metallic glass is, for example, Cu ₅₅ Zr ₄₀ Al ₅ (hereinafter, the subscript indicates atomic%). A preferable composition of the Zr-based metallic glass is, for example, Zr ₆₀ Al ₁₅ Ni _7.5 Co _2.5 Cu ₅ . Examples of a preferable composition of the Ni-based metallic glass include Ni ₅₆ Cr ₂₄ P ₁₆ B ₄ and Ni ₆₅ Cr ₁₅ P ₁₆ B ₄ . A preferred composition of the Fe-based metallic glass is, for example, Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ .

In addition, as a metallic glass having excellent corrosion resistance, Cu _100-ab (Zr + Hf) _a Ti _b or Cu _100-abcd (Zr + Hf) _a Ti _b M _c T _d [wherein M is Fe , Cr, Mn, Ni, Co, Nb, Mo, W, Sn, Al, Ta, one or more elements selected from the group consisting of rare earth elements, T is from Ag, Pd, Pt, Au One or more elements selected from the group consisting of 5 <a ≦ 55 atomic%, 0 ≦ b ≦ 45 atomic%, 30 <a + b ≦ 60 atomic%, 0.5 ≦ c ≦ 5 atomic% And 0 ≦ d ≦ 10 atomic%] (see JP 2002-256401 A). As the _{Ni-based, Ni 80-x Cr x P} 16 B 4 [ however, 3 ≦ x ≦ 30 atomic%] and those having a composition represented by the like (Material Transactions, Vol.48, No.12 (2007) pp. 3176-3180). As the _{Fe-based, Fe 100-ab-c Cr} a TM b (C 1-X B X P y) c [ In the formula, TM = V, Nb, Mo , Ta, W, Co, Ni, At least one kind of Cu, a, b, c, x, and y, are 5 atomic% ≦ a ≦ 30 atomic%, 5 atomic% ≦ b ≦ 20 atomic%, 10 atomic% ≦ c ≦ 35 atomic%, and 25 atoms, respectively. % ≦ a + b ≦ 50 atomic%, 35 atomic% ≦ a + b + c ≦ 60 atomic%, 0.11 ≦ x ≦ 0.85, 0 ≦ y ≦ 0.57], etc. 2001-303218).
Moreover, the supercooled liquid temperature area | region (DELTA) Tx = Tx-Tg of metal glass is used suitably for 30K or more.

Even in a composite material in which a dense metallic glass film is formed by thermal spraying, a gap between particles may increase due to expansion during heat deformation processing, or damage such as peeling or tearing may occur. This is presumably because even though it appears to be a dense and uniform amorphous phase coating, the inside of the sprayed coating is essentially non-uniform and has potential internal defects. And the larger the sprayed area, the higher the abundance of such non-uniformity and potential internal defects.
As in the present invention, by homogenizing the metallic glass layer of the composite material prior to deformation processing, such non-uniformity and potential internal defects are eliminated, and defects increase or break during deformation processing. Is significantly suppressed.

(II) Homogenization step In this step, pressure is applied to homogenize the metal glass layer. The pressurization is performed so that the nonuniformity and potential internal defects of the metal glass layer are eliminated. Preferably, it is performed so that the thickness of the metallic glass layer is uniformly compressed at least in the region to be deformed. For example, it can be performed by pressing at a uniform pressure from the metallic glass surface toward the bonding interface with the substrate. At this time, the layer thickness of the homogenized metallic glass layer is usually compressed uniformly, but the substrate is not deformed. In addition, the homogenization process may be performed at once or a plurality of times.

  The pressurizing method is not particularly limited as long as it can achieve the object of the present invention, and a known method can be adopted. For example, a flat press using a mold or a roller, a method such as HIP can be mentioned, and it is desirable to press at least the region to be deformed and the metal glass layer in the peripheral portion thereof as uniformly as possible. As a simple method, there is a method in which a metal glass layer surface is pressurized toward a bonding interface with a base material using a mold that matches the shape of the composite material. Moreover, it can also carry out, moving a pressurization site | part using a roller etc.

The pressurization is performed by heating the metal glass layer to a temperature at which vitrification can be performed to form a supercooled liquid state (vitrified state). Since it becomes a viscous fluid in the supercooled liquid state, latent internal defects can be diffused into the metallic glass layer and homogenized in a short time.
In general, the glass transition temperature Tg of a metallic glass is measured by DSC (differential scanning calorimeter), but the shift in the endothermic direction of the DSC curve due to vitrification of the metallic glass draws a curve, and therefore usually the baseline of the DSC curve. The temperature at the intersection of the endothermic shift and the tangent of the endothermic shift is measured as the glass transition temperature Tg for convenience. As a result, Tg is measured higher than the actual endothermic reaction start temperature (vitrification start temperature). Therefore, even if it is temperature lower than Tg, if it is more than vitrification start temperature (endothermic reaction start temperature), it is possible to vitrify metal glass. Specifically, for example, homogenization is preferably performed at a temperature of 85% or more of the glass transition temperature Tg (K), and further, homogenization is preferably performed at Tg (K) or more.

However, if the temperature is too high, a crystal phase is generated during the homogenization step, which is not preferable. When a subsequent deformation process is performed on a metallic glass layer containing a crystal phase, cracks may occur starting from the crystal phase grown under a further heat load during the deformation. As in the case of Tg, the crystallization start temperature Tx measured by DSC measurement is usually measured higher than the temperature at which the shift in the endothermic direction due to vitrification shifts to the shift in the exothermic direction due to crystallization. In order to avoid the formation of the crystal phase in the homogenization process, not only the crystallization start temperature Tx (K) but also the exothermic reaction temperature region immediately before Tx where the structural change to crystallization is considered to occur is Should be avoided. Specifically, for example, it is preferable to perform homogenization at a temperature of 97% or less of the crystallization start temperature Tx (K).
In the present invention, Tg (K) and Tx (K) are both values measured by DSC under an argon atmosphere under a temperature increase rate of 20.0 ° C./min.
In order to achieve the target temperature, the composite material may be directly heated, or heat may be indirectly supplied from a mold, a roller, or an atmosphere. Moreover, both can be combined.

The pressure and time for pressurization are appropriately set according to the pressurization temperature, the type of metal glass, the layer thickness, etc., but if the pressure treatment is carried out for a long time at a high temperature, the crystal phase or oxide is applied to the metal glass layer. A phase is likely to be generated. Therefore, it is preferable to apply pressure so that homogenization can be performed in as short a time as possible. For example, pressurization can be performed at 5 to 1000 MPa, further 20 to 500 MPa, 1 to 600 sec, and further 10 to 200 sec.
If the strain rate [= (deformation amount / length of object) / time required for deformation] is too high during pressurization, stress overshoot may occur and hinder homogenization. The strain rate during pressurization is preferably 7.0 × 10 ⁻¹ / s or less.
In addition, the pressurization may be usually performed in the atmosphere, but may be performed in an inert gas when the influence of oxidation is concerned.

(III) Deformation process The composite material homogenized as described above can be deformed by a known method. In the present invention, only the metallic glass layer may be deformed by deformation processing (for example, the surface of the metallic glass layer is made uneven). However, the method of the present invention seems to bend the substrate simultaneously with the metallic glass layer. It is particularly useful in such cases. For example, if an attempt is made to bend the entire composite material by pressing with a mold or the like, even if the metal glass layer is processed in the supercooled liquid temperature region, damage such as peeling or breakage of the metal glass layer will occur, but homogenization Such breakage is significantly suppressed in the treated composite material.

The deformation conditions may be set as appropriate according to the type and application of the metal glass composite material, but the metal glass layer is heated and deformed so as to be in the temperature region including the supercooled liquid temperature region (Tg to Tx). If it processes, since the deformation stress of a metallic glass layer is small, it is more preferable. If the Young's modulus is significantly lowered and softens at the ambient temperature in the supercooled liquid temperature region, deformation can be performed at such a temperature. Also, if the homogenized pre-deformed metallic glass layer does not contain a crystalline phase, even if it becomes a temperature near the crystallization start temperature during or after the deformation process, it will deform without peeling or breakage. It is possible to process.
Specifically, for example, it is preferable to set within a range of 85% or more of the glass transition temperature Tg (K) of the metal glass to 100% or less of the crystallization start temperature Tx (K), Further, it is preferable to perform deformation processing within a temperature range of Tg to Tx.

The deformation process may be performed continuously following the homogenization process, or may be performed intermittently by cooling once.
It is also possible to use a mold so that a desired shape (for example, unevenness or mirror surface) is formed on the surface of the metal glass layer simultaneously with bending during deformation processing.
EXAMPLES Hereinafter, although this invention is further demonstrated based on an Example, this invention is not limited to these.

Test example 1
(I) Manufacture of composite material Gas atomized powder of Cu ₅₅ Zr ₄₀ Al ₅ metal glass (25 to 53 μm) composed of amorphous single phase is sprayed on SUS304 base material (15 × 15 × 0.5 mm, blasted finish) Thus, a metallic glass composite material was obtained. When the metal glass powder was subjected to DSC measurement (differential scanning calorimeter DSC8270 (manufactured by Rigaku Corporation), heating rate 20.0 ° C./min, argon atmosphere), the glass transition temperature was 459 ° C. (732 K), the crystallization start temperature. Was 506 ° C. (779 K).
The metal glass layer of the obtained composite material was about 160 μm. Moreover, it confirmed that the metal glass layer of the obtained composite material was an amorphous single phase from the halo pattern of X-ray diffraction.
The spraying conditions were as follows.

(Spraying conditions)
HVOF apparatus: JP-5000 manufactured by PRAXAIR / TAFA
Powder carrier gas: N ₂
Fuel: Kerosene, 3GPH
Oxygen: 2000 SCFH
Thermal spray distance (distance from spray gun tip to substrate surface): 250 mm
Thermal spray gun moving speed: 600mm / sec

(II) Homogenization The composite material obtained in (I) above is heated at a heating rate of 99 to 350 ° C./min, and when it reaches a predetermined temperature, a circular plane of Φ10 mm as shown in FIG. Using a mold having a load of 4000 kgf to 6000 kgf (pressure of about 499 MPa to 749 MPa), a mold feed rate of 2 mm / min, a strain rate of 2.1 × 10 ⁻¹ / s with respect to the metal glass layer (160 μm), and about Plane pressing was performed from the metallic glass layer side for 120 to 180 seconds.

(III) Deformation processing Using the composite material homogenized in (II) above, deformation processing was performed into a shape as shown in FIG. The composite material is heated at a temperature increase rate of 99 to 350 ° C./min. When a predetermined temperature is reached, a mold is used on both sides of the composite material, and a load of about 4000 kgf (pressure of about 174 MPa) and a pressure of about 150 to about Pressed for 180 seconds. Feed rate of the mold 1.2~2mm / min, the strain rate is met approximately 1.3 × ^{10 -1} /s~2.2×10 -1 / s to the metallic glass layer (about 0.15 mm) It was.

  4 is a cross-sectional photograph of the composite material obtained in the above (I), FIG. 5 is a cross-sectional photograph in which the deformation processing of (III) is directly performed without performing the homogenization treatment of (II), and FIG. It is a cross-sectional photograph in the case of performing the deformation processing step of (III) after performing the homogenization processing of (II) (both homogenization processing temperature and deformation processing temperature are 480 ° C. (753 K)).

When FIG. 4 and FIG. 5 are compared, compared with the deformation | transformation process (FIG. 4), it was very densified near the recessed corner | angular part of a metal glass layer (FIG. 5 (a)).
However, when the flat part of the upper part of the convex angle of the metallic glass layer is seen, as shown in FIG. 5 (b), the gaps between the adjacent laminated particles (parts that appear black) are remarkably increased. This is because the flat part at the top of the convex corner is pushed by the mold from the substrate side, and the pressure is smaller than the concave corner part, etc., so that the laminated particles expand and contract by heating / cooling rather than densification by pressurization. It is considered that the separation between the metal glass particles was promoted by the deformation in the lateral direction due to the pressurization from the substrate side of the metal glass layer.

Moreover, in the convex corner part, as shown in FIG. 5C, breakage of the metallic glass layer was observed as the gap between the laminated particles increased. This is because the separation of the laminated particle gap by heating / cooling was promoted more than the densification by pressurization even at the convex corner, and further, the metallic glass layer having such internal defects was pulled and damaged. It is done.
Thus, even if the composite material is simply deformed in the supercooled liquid temperature region, it has been very difficult to deform the composite material without causing defects or breakage in the metal glass layer.

On the other hand, in FIG. 6 in which the deformation process is performed after the homogenization process, not only (a) the concave corner portion but also (b) the flat portion at the top of the convex corner and (c) the convex corner portion as shown in FIG. There is no increase in the gaps between the laminated particles of the metal glass layer and the occurrence of breakage as seen in Fig. 1, and the extremely dense metal glass layer is deformed and integrated with the base material. I understand.
As described above, when the metal glass composite material is deformed without performing such pretreatment by uniformly applying pressure in the supercooled liquid state to the metal glass layer in the region to be deformed at least before the deformation processing of the metal glass composite material. As compared with, the occurrence of defects and breakage of the metal glass layer during deformation processing is suppressed.

Table 1 below shows the results of investigating the presence / absence of defects and breakage after deformation when homogenization and deformation are performed at each processing temperature. In the evaluation (defect / breakage column after deformation processing), “Yes” was given if a corner had a defect or breakage, and “None” was given otherwise.
As can be seen from Table 1, if the homogenization treatment is performed in the range of Tg × 85% to Tx × 97%, it is possible to obtain a suppressing effect on the occurrence of defects and breakage of the metal glass layer during deformation processing. However, when the deformation temperature is too low (Test Example 1-a) or too high (Test Example 1-f), defects or breakage may occur at the corners. 7 and 8 show cross-sectional photographs of Test Example 1-a and Test Example 1-f.

  For this reason, it is considered preferable to perform the deformation process in the temperature range of Tg × 85% to Tx × 100% after performing the homogenization treatment in the range of Tg × 85% to Tx × 97%. It was.

Test example 2
(I) Manufacture of composite material Gas atomized powder of Cu ₅₄ Zr ₂₂ Ti ₁₈ Ni ₆ metal glass (25 to 53 μm) made of amorphous single phase made of SUS304 base material (15 × 15 × 0.5 mm, blasted finish) The metal glass composite material was obtained by thermal spraying. When the metal glass powder was subjected to DSC measurement, the glass transition temperature was 438 ° C. (711 K), and the crystallization start temperature was 487 ° C. (760 K).
The metal glass layer of the obtained composite material was about 130 μm. Moreover, it confirmed that the metal glass layer of the obtained composite material was an amorphous single phase from the halo pattern of X-ray diffraction.
The spraying conditions were as follows.

(Spraying conditions)
HVOF apparatus: JP-5000 manufactured by PRAXAIR / TAFA
Powder carrier gas: N ₂
Fuel: Kerosene, 2GPH
Oxygen: 2000 SCFH
Thermal spray distance (distance from spray gun tip to substrate surface): 250 mm
Thermal spray gun moving speed: 600mm / sec

(II) Homogenization The obtained composite material was heated at a heating rate of 99 ° C./min, and when it reached 460 ° C. (733 K), using the circular mold of FIG. 499 MPa), a feed rate of 2 mm / min, a strain rate of 2.6 × 10 ⁻¹ / s with respect to the metal glass layer (130 μm), and plane pressing from the metal glass layer side for about 180 seconds.

(III) Deformation Using the composite material homogenized in this way, the deformation process temperature was 460 ° C. (733 K), and deformation was performed in the same shape as in Test Example 1 (III). As a result, no defects or breakage due to deformation processing were observed.

Test example 3
(I) Manufacture of composite material Zr ₆₀ Al ₁₅ Ni _7.5 Co _2.5 Cu ₅ metal glass gas atomized powder (25 to 53 μm) composed of an amorphous single phase was used as a SUS304 substrate (15 × 15 × 0. Thermal spraying to 5 mm (blasting finish) gave a metallic glass composite material. When the metal glass powder was subjected to DSC measurement, the glass transition temperature was 416 ° C. (689 K), and the crystallization start temperature was 493 ° C. (766 K).
The metal glass layer of the obtained composite material was about 130 μm. Moreover, it confirmed that the metal glass layer of the obtained composite material was an amorphous single phase from the halo pattern of X-ray diffraction.
The spraying conditions were as follows.

(Spraying conditions)
HVOF apparatus: JP-5000 manufactured by PRAXAIR / TAFA
Powder carrier gas: N ₂
Fuel: Kerosene, 3GPH
Oxygen: 2000 SCFH
Thermal spray distance (distance from spray gun tip to substrate surface): 250 mm
Thermal spray gun moving speed: 600mm / sec

(II) Homogenization The obtained composite material was heated at a heating rate of 99 ° C./min, and when it reached 470 ° C. (743 K), using the circular mold of FIG. 499 MPa), a feed rate of 2 mm / min, a strain rate of 2.6 × 10 ⁻¹ / s with respect to the metal glass layer (130 μm), and plane pressing from the metal glass layer side for about 180 seconds.

(III) Deformation processing Using the composite material homogenized in this way, the deformation processing temperature was 470 ° C. (743 K), and deformation processing was performed in the same shape as in Test Example 1 (III). As a result, no defects or breakage due to deformation processing were observed.

Test example 4
(I) Manufacture of composite material A gas atomized powder of Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ metal glass (under 25 μm sieve ) made of an amorphous single phase and a SUS304 substrate (15 × 15 × 0.5 mm, blasted) Thermal spraying was performed to obtain a metallic glass composite material. When the metal glass powder was subjected to DSC measurement (differential scanning calorimeter DSC8270 (manufactured by Rigaku Corporation), heating rate 20.0 ° C./min, argon atmosphere), the glass transition temperature (Tg) was 597 ° C. (870 K), crystals The onset temperature (Tx) was 688 ° C. (961 K).
The metal glass layer of the obtained composite material was about 60 μm. Moreover, it confirmed that the metal glass layer of the obtained composite material was an amorphous single phase from the halo pattern of X-ray diffraction.
The spraying conditions were as follows.

(Spraying conditions)
HVOF apparatus: JP-5000 manufactured by PRAXAIR / TAFA
Powder carrier gas: N ₂
Fuel: Kerosene, 5.1GPH
Oxygen: 1800 SCFH
Thermal spray distance (distance from spray gun tip to substrate surface): 355mm
Thermal spray gun moving speed: 600mm / sec

(II) Homogenization The composite material (metal glass layer thickness: about 0.2 mm) obtained in the same manner as in the above (I) was heated at a heating rate of 99 ° C./min and reached 650 ° C. (923 K). At that time, pressing was performed from the metallic glass layer side for about 180 seconds under a load of about 4000 kgf (pressure of about 499 MPa) using a mold having a circular plane of Φ10 mm as shown in FIG. The mold feed rate was 2 mm / min, and the strain rate was about 1.7 × 10 ⁻¹ / s with respect to the metal glass layer (0.2 mm).

(III) Deformation processing The composite material subjected to homogenization treatment was deformed into a shape as shown in FIG. The composite material was heated at a temperature increase rate of 99 ° C./min, and when it reached 650 ° C. (923 K), it was pressed for about 180 seconds using a mold at a load of about 4000 kgf (pressure of about 174 MPa). The mold feed rate was 2 mm / min, and the strain rate was about 2.2 × 10 ⁻¹ / s with respect to the metallic glass layer (about 0.15 mm).

  FIG. 9 is a cross-sectional photograph of the composite material obtained in the above (I), FIG. 10 is a cross-sectional photograph in which the deformation processing of (III) is performed directly without performing the homogenization treatment of (II), and FIG. It is a cross-sectional photograph at the time of performing the deformation process of (III) after performing the homogenization process of said (II).

Comparing FIG. 9 and FIG. 10, it was very dense in the vicinity of the concave corner of the metallic glass layer (FIG. 10 (a)) as compared to before deformation (FIG. 9).
However, when the flat part of the upper part of the convex angle of the metallic glass layer is viewed, as shown in FIG. 10B, the gaps between the adjacent laminated particles (parts that appear black) are remarkably increased. This is because the flat part at the top of the convex corner is pushed by the mold from the substrate side, and the pressure is smaller than the concave corner part, etc., so that the laminated particles expand and contract by heating / cooling rather than densification by pressurization. It is considered that the separation between the metal glass particles was promoted by the deformation in the lateral direction due to the pressurization from the substrate side of the metal glass layer.

Moreover, in the convex corner part, as shown in FIG. 10C, breakage of the metallic glass layer was observed with an increase in the gap between the laminated particles. This is because the separation of the laminated particle gap by heating / cooling was promoted more than the densification by pressurization even at the convex corner, and further, the metallic glass layer having such internal defects was pulled and damaged. It is done.
Thus, even if the composite material is simply deformed in the supercooled liquid temperature region, it has been very difficult to deform the composite material without causing defects or breakage in the metal glass layer.

  On the other hand, in FIG. 11 in which deformation processing is performed after the homogenization processing, (b) not only the concave corners, but also (b) a flat portion at the upper convex corner, (c) a convex corner, (d) (a) In any of the whole including-(c), no increase in the gap between the laminated particles of the metal glass layer as seen in FIG. 10 or occurrence of breakage was observed, and a very dense metal glass layer was formed. It can be seen that the deformation processing is performed in an integrated state with the base material.

A composite material having the shape of FIG. 3 was obtained in the same manner except that the homogenization process and the deformation process were performed at the temperatures shown in Table 2 below.
Table 2 also suggests that it is preferable to perform the deformation process in the temperature range of Tg × 85% to Tx × 100% after performing the homogenization treatment in the range of Tg × 85% to Tx × 97%. Is done.

It is the schematic of the deformation | transformation processing method concerning one Example of this invention. It is the schematic of the metal mold | die used for the homogenization process in one Example of this invention. It is (a) front view and (b) sectional view of the shape of the metallic glass composite material deformed in one embodiment of the present invention.

It is a cross-sectional photograph of the obtained _Cu 55 _Zr 40 Al ₅ metallic glass composites by thermal spraying. It is a cross-sectional photograph of (a) concave corner, (b) flat top of convex angle, and (c) convex corner of Cu ₅₅ Zr ₄₀ Al ₅ metallic glass composite material deformed without homogenization. It is a cross-sectional photograph of (a) concave corner, (b) flat top of convex angle, and (c) convex corner of the Cu ₅₅ Zr ₄₀ Al ₅ metallic glass composite material deformed after homogenization.

A cross-sectional photograph of after homogenization was deformed at Tg × 80% Temperature _{(K) Cu 55 Zr 40 Al} 5 metallic glass composites. A cross-sectional photograph of deformation processed _Cu 55 _Zr 40 Al ₅ metallic glass composite material Tx × 102% temperature after homogenization treatment (K). It is a cross-sectional photograph of the obtained _{Fe 43 Cr 16 Mo 16 C 15} B 10 metallic glass composites by thermal spraying.

It is a cross-sectional photograph of (a) concave corner, (b) flat top of convex angle, and (c) convex corner of Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ metallic glass composite material deformed without homogenization. . Fe ₄₃ Cr ₁₆ Mo ₁₆ C ₁₅ B ₁₀ metallic glass composite material deformed after homogenization treatment (a) concave corner, (b) flat top of convex corner, (c) convex corner, (d) (a It is the whole cross-sectional photograph including (c)-(c).

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Base material 12 Metal glass layer 14 Metal glass composite material

Claims (9)

A metal glass composite material forming step of forming a metal glass layer by laminating metal glass particles on a substrate surface;
A homogenization step of homogenizing the metal glass layer by pressurizing the metal glass layer in a supercooled liquid state;
Deforming the homogenized metallic glass layer;
A method for deforming a metallic glass composite material, comprising:   2. The method of deforming a metal glass composite material according to claim 1, wherein the metal glass particles are laminated by thermal spraying.   The method according to claim 1 or 2, wherein the deformation process is a press process.   4. The method according to claim 1, wherein the homogenization step is performed in a temperature range of glass transition temperature Tg (K) × 85% of metal glass to crystallization start temperature Tx (K) × 97%. A method for deforming a metallic glass composite material.   The method according to any one of claims 1 to 4, wherein the homogenization step is performed at a pressure of 5 to 1000 MPa for 1 to 600 seconds.   6. The method for deforming a metal glass composite material according to claim 1, wherein the homogenizing step is performed at a uniform pressure on the substrate surface.   7. The method according to claim 1, wherein the step of deforming is performed in a temperature range of glass transition temperature Tg (K) × 85% of metal glass to crystallization start temperature Tx (K) × 100%. A method for deforming a metallic glass composite material.   8. The method for deforming a metal glass composite material according to claim 1, wherein the thickness of the substrate on which the metal glass particles are laminated is 0.5 mm or less.   9. The method for deforming a metal glass composite material according to claim 1, wherein the metal glass layer and the base material that have been homogenized in the deformation process are integrally deformed.