JP2627090B2 - Bonded body of boride ceramics and metal-based structural member and bonding method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a joined body and a joining method of a boride ceramic and a metal-based structural member, and more particularly, to a stoichiometric composition of each composite phase. Joins a boron-based composite ceramics sintered body with excellent strength, corrosion resistance, conductivity, hardness, oxidation resistance, etc., controlled to a specific atomic ratio and a metal-based structural member using a specific brazing material The present invention relates to a method and a conjugate obtained thereby. The joined body according to the present invention can be applied to wear-resistant members, various tools, dies, etc., particularly by utilizing the excellent characteristics of the boron-based composite ceramic sintered body constituting a part thereof. Can be used optimally for molds.

[Conventional technology]

Conventionally, glass molding dies include cast iron, wear-resistant steel,
Ni-based cemented carbide is used. Generally, the softening point of glass is 800 ° C. or higher, and it is necessary to heat the mold to a high temperature in order to prevent rapid cooling of the glass surface during molding. However, the upper limit of the heating temperature of the conventional mold material as described above is low, and even in a mold using a Ni-based cemented carbide, the upper limit of the heating temperature of the mold is about 600 ° C. When the mold is heated to a temperature in the vicinity or above, the mold surface is oxidized to a rough surface, and final molding is required. Therefore, the mold is heated to about 450-500 ° C, and the glass that has been heated and melted to a temperature above the softening point is molded under pressure. And a method of releasing the mold is adopted. However, there is a problem that the precision of the molded product is inferior to the method in which the molten glass is molded under pressure until it is sufficiently cooled. On the other hand, in the case of a mold of cast iron or wear-resistant steel, accuracy is further inferior to the case of using the mold of the above-mentioned Ni-based cemented carbide. Have been.

A boron-based composite ceramics sintered body is known as a material that may have better heat resistance, oxidation resistance, high-temperature durability, hardness, and the like than the above materials. However, there have been few development examples of boron-based composite ceramic sintered bodies, and various proposals and reports have been made in patents, papers, etc. on the composition of the sintered body, the obtained microstructure and various properties of the sintered bodies. It is only the present situation. In other words, according to the current knowledge, the composition and structure of each phase constituting the obtained composite ceramic sintered body are obtained even if the compounded sintering composition is constant due to inevitable factors included in the properties of the starting materials, sintering process conditions, etc. Can vary considerably on a microscopic scale, composite ceramics with the desired phase composition cannot be obtained, reproducibility of composite ceramics sintered body characteristics,
Reliability is generally low.

For example, the only prior art related to the present invention is:
Japanese Patent Publication No. Sho 56-43378 and "Powder and Powder Metallurgy", Vol. 27, No. 4, P31
Although there are ~ 38, 1980, as shown in these publications, TiB ₂ in -Ni-B based composite sintered body, the phase structure is TiB ₂ + NiB (Ni / B atomic ratio of 1 / 1) A sintered body having two phases has not yet been obtained.

[Problems to be solved by the invention]

The present applicant has previously developed a new high-performance and high-reliability boron which has not yet been achieved by the prior art and which has sufficiently controlled the stoichiometric composition of the ceramic phase in the boron-based composite ceramic sintered body to a specific atomic ratio. We have developed a sintered ceramic composite and have already applied for a patent. However, this boron-based composite ceramics sintered body has a drawback that its production cost is higher than that of conventional ceramics due to the characteristics in its manufacturing method (high-pressure synthesis, thermit reaction synthesis). As an economical use method of such a member, it is conceivable to use it only in a portion where the properties of the boride ceramics are required and to use it in connection with a structural material (base material).

In particular, in a glass molding die, the productivity and accuracy of a glass molded product can be improved by using boride ceramics having the above-described excellent properties for the die surface. However, it is economically very expensive to manufacture a mold using only boride ceramics, and it is technically difficult. Therefore, it is advantageous to form only the cavity surface of the mold with the above-mentioned boron-based composite ceramics sintered body and join it to another structural material to form a mold.

However, when the above-mentioned boron-based composite ceramics sintered body is joined to a structural material (base material), the joining material and the joining method become problems. When brazing is performed with a commonly used brazing material, there is a problem in that thermal stress is generated during cooling after heating and melting of the brazing material, and cracks, peeling, and the like occur at the ceramic / base metal interface.

Accordingly, an object of the present invention is to eliminate the above-described problems such as cracking and peeling at the ceramics / base metal interface,
An object of the present invention is to provide a method for joining a boron-based composite ceramics sintered body to a metal-based structural member with sufficient joining strength and joining durability.

Further, an object of the present invention is to provide a bonded body in which a boron-based composite ceramic sintered body having excellent strength, hardness, heat resistance, oxide resistance, corrosion resistance, and the like and a metal-based structural member are bonded with sufficient bonding strength and durability. In particular, it is an object of the present invention to provide a glass molding die in which a die cavity surface is formed of a boron-based composite ceramic sintered body.

[Means for solving the problem]

According to the present invention, in order to achieve the above object, (A) at least one or more M ^I / B (where M ^I is Ni, Cr, V,
Nb, and Ta, Mo, at least one member selected from the group consisting of W and Mn) atomic ratio is 1/1 M ^I B ceramic phase,
At least one group IV diboride ceramic phase selected from the group consisting of TiB ₂ , ZrB ₂ and HfB ₂ and / or (C
r, Ni) ₃ B ₄ ceramic phase and a boron-based composite ceramic sintered body formed consist, (B) a metallic structural member, (C) Cu-Mn-based, Cu-Mn-Ni-based, Cu -Mn-Co system, Cu-Mn
-A joined body characterized by being joined by a Co-Ni-based, Cu-Ni-based or Ni-Mn-based brazing material.

In particular, according to the present invention, there is provided a glass molding die in which a die cavity surface is formed by the boron-based composite ceramics sintered body.

Further, according to the present invention, the boron-based composite ceramics sintered body (A) and the metal-based structural member (B) are overlapped with each other via the brazing material (C), and the stacked materials are mixed together in a vacuum or in an inert atmosphere. A boron-based composite ceramics sintered body and a metal-based structure, characterized in that a melt of a brazing filler metal is generated between the boron-based composite ceramics sintered body and the metal-based structural member by heating to above the melting point, and then cooled. A method for joining members is provided.

[Function and Mode of the Invention]

As a brazing material for joining the boron-based composite ceramics sintered body and the metal-based structural member, the brazing material must not melt at a high temperature (especially, about 800 ° C. of softening point of glass) and maintain a certain degree of shear strength. It is necessary to be. The present inventors have investigated the brazing material having such properties, and as a result, as shown in the following Table 1, the Cu-Mn-based, Cu-
It has been found that Mn-Ni, Cu-Mn-Co, Cu-Mn-Co-Ni, Cu-Ni and Ni-Mn systems can be used. In this research and development, Ni and Cu were first used.
Starting from the evaluation of the wettability of the Ni-Mn binary alloy and the Cu-Ni binary alloy with the boride ceramic, and good results were obtained, the properties as a brazing material based on these, that is, melting temperature, strength Cu, Mn, C
Evaluate ternary and quaternary alloys added with o, Si, etc.
The invention of the brazing material including the Cu-Mn-Ni-Co system shown in the examples has been reached. Ni-Mn-based and Cu-Ni-based brazing materials are not shown in the examples, but it has been confirmed that they have a sufficient function as a brazing material for boride ceramic bonding. Is shown in FIG. When both members are joined by heating and melting the brazing material, thermal stress is generated at the time of cooling. This is because when joining by the composition deformation of the brazing material, thermal stress is generated at the time of cooling. Is absorbed by the plastic deformation of
As a result, cracks, peeling, and the like do not occur on the ceramic / base metal interface. Therefore, a joined body excellent in joining strength and joining durability can be easily manufactured.

Since the bonded body according to the present invention is obtained by bonding the boron-based composite ceramics sintered body to the metal-based structural member, the cost is reduced and the excellent characteristics of the boron-based composite ceramics sintered body are combined. It can be suitably used in various fields.

Table 1 shows the composition and physical properties of some examples of various brazing materials that can be used in the present invention.

As a brazing material, for example, silver brazing or brass brazing is generally used for cutting tools and the like. However, when the bonded body according to the present invention is used as, for example, a glass forming mold,
Because it is heated to high temperature and generates stress when cooling,
These general brazing materials are insufficient in heat resistance and the like.

Although the brazing material according to the present invention is also a brazing material based on Cu, pure Cu has a problem that it erodes the grain boundaries of steel and has low shear strength. Ni and Mn prevent the intergranular erosion of such steel, and Mn forms a solid solution phase at the interface between the brazing material and the steel, indicating that it has the effect of improving the "wetability" of the brazing material and the steel. Was.

In addition, it was found that Co increases the hardness of the brazing filler metal and improves the "wettability" with the ceramic sintered body.

Also, Si has a great effect of increasing the hardness of the brazing material,
FIG. 5 shows the effect of the amount of Si added on the hardness of the copper alloy brazing material.
It was found to increase by 35 kg / mm ² .

On the other hand, as the brazing filler metal used in the present invention, it is preferable that the liquid phase generation temperature of the brazing filler metal is 950 ° C. or higher from the viewpoint of heat resistance.
1150 ° C or lower is desirable because it lowers the base metal strength.

Since Mn and Si lower the liquid phase formation temperature and Ni and Co increase, the combination of these alloy elements and the composition range are required to keep the liquid phase formation temperature of the brazing material in the range of 950 to 1150 ° C. There is a limit.

It was also found that the hardness of the brazing material strongly depends on the amount of Co and the amount of Si, especially on the amount of Si, but there is no linear relationship between the shear strength and the hardness of the joint. That is, as shown in Fig. 6, the shear strength of the joint increases with hardness up to a hardness of HV150, but decreases with a hardness of more than HV150.
Above is a brittle fracture state. Therefore, the amount of Co, especially the amount of Si, has an upper limit in terms of shear strength.

FIG. 6 shows the relationship between the brazing joint strength of the cemented carbide and the steel and the hardness of the brazing material measured according to the shear strength measurement method shown in FIG. It is considered that the same applies when a composite ceramics sintered body is used. In FIG. 7 schematically showing the above-mentioned method for measuring the shear strength, P indicates a load, 11 indicates a cemented carbide, 12 indicates steel brazed to both sides of the cemented carbide, and 13 indicates a cradle.

The optimum composition range of the brazing material for the present invention is comprehensively determined based on the characteristics of such alloy elements.
In Ni-Si system, 2 to 10% Ni, preferably 5 to 10% Ni, 1 to
8% Si; 10-25% Mn, 5-10% Ni, 0% for Cu-Mu-Ni system
３3% Si; or 15-30% Mn in Cu-Mn-Ni-Co system, 5
-10% Ni, 5-10% Co, 0-1.5% Si are suitable. In addition, the hardness of the brazing material is Vickers hardness of about 75 to 200 kg / mm ² ,
More preferably, the range is 100 to 200 kg / mm ² .

Also, among the brazing materials shown in Table 1, Cu (66)-from the relationship of copper alloys, particularly hardness vs. shear strength (see FIG. 6).
Mn (24) -Ni (10), Cu (63) -Mn (22) -Co (5)-
Ni (10) and Cu (86) -Mn (10) -Co (4) are suitable, and particularly, Cu (63) -Mn (22) -Co (5) -Ni (10) is most suitable. Ni-based brazing materials, on the other hand, have good wettability, but are inferior to copper alloys as glass forming members because cracks may occur when the joined body is repeatedly heated and cooled. .

FIG. 1 shows the basic structure of the joined body according to the present invention. In the figure, 1 is a boron-based composite ceramic sintered body, 2 is a brazing material,
Reference numeral 3 denotes a metal-based structural member. A ceramic sintered body 1 is laminated on a metal-based structural member 3 via a brazing filler metal 2 and heated to a temperature equal to or higher than the melting point of the brazing filler metal in a vacuum or an inert atmosphere to form a boron-based composite ceramic sintered compact and steel. Then, a normal brazing is performed in which a melt of the brazing material is formed and then cooled to solidify the brazing material. Thereby, a brazed joint having heat resistance and strength is obtained. FIG. 2 shows an example in which the present invention is applied to a glass molding die. Mold cavity surface 4
Is composed of a boron-based composite ceramics sintered body 1a. In addition, various metal-based structural materials can be used as a base material, but in a glass forming mold, a cemented carbide,
Metal-based structural materials such as high-speed steel and die steel can be suitably used.

As shown in FIG. 2, in a mold in which the ceramic sintered body 1a is fitted to the structural member 3a, it is sufficient if the mold surface of the ceramic sintered body can be held so as not to move during heating. The bonding strength by attachment does not matter so much. However, if joint strength is a concern, a mechanical coupling element can be added in addition to the braze joint as shown in FIGS. Fig. 3 shows structural members
FIG. 4 shows an example in which a groove 5 is provided on the upper surface of 3b, a groove 6 is provided on the lower surface of the ceramic sintered body 1b, and the groove 6 is inserted into the groove 5 through the brazing material 2b. Is an example in which a screw 7 is used and screwed.

The boron-based composite ceramic sintered body used in the present invention is a M ^I / B ceramic phase constituting one phase of the composite sintered body, specifically, Ni / B, Ni + M ^II / B (M ^II : Cr , V a~VII a group element), Cr / B, Ni + Cr / B, Ni + Cr + M III / B (M III: V a~VI
It is characterized in that the atomic ratio of the ceramic phase (Ia group element) is sufficiently controlled to be 1/1, and thus the M ^I / B ceramic phase can be obtained regardless of whether Ni is replaced by another metal. By controlling the atomic ratio of 1/1 sufficiently, the compactness of the obtained sintered body and the uniformity of the composition of each phase are remarkably improved, and as a result, various properties such as toughness and strength are excellent. It will be.

More specifically, the boron-based composite ceramics sintered body of the present invention has a sintered body composition of a group IV diboride TiB ₂ , ZrB ₂ ,
M ^I / B (preferably Ni / B) with at least one of HfB ₂
M ^I B (preferably NiB) sintered body made of ceramic mixed phase having a controlled atomic ratio 1/1, and a Cr / B atomic ratio of 1 /
CrB phase was controlled to 1, and (Cr, Ni) ₃ and B ₄ phase and Ni + Cr / B atomic ratio controlled to 1/1 (Ni, Cr) base sintered body consisting of B-phase ceramic mixed phase, they Ni + M ^II / B ceramic phase with atomic ratio 1/1 (M ^II : V, Nb, Ta, Cr, Mo, W, Mn)
And a boron-based composite ceramics sintered body in which stoichiometric compounds are appropriately combined.

The group IV diboride ceramic used in the present invention is obtained by sufficiently controlling the atomic ratio of the Ni / B, Cr / B, and Ni + M ^II / B phases constituting the remainder of the sintered body to 1/1, and In order to improve the compactness, toughness, etc., it is preferable that the purity is high and the particle size is small.

Cr / B atomic ratio 1/1 ceramic phase, (Cr, Ni) ₃ N ₄ phase
As long as it is present as a sintered body, any form may be used as a starting material.

The raw material mixture is usually adjusted by uniformly mixing two or more of the above fine powders.

The sintered body of the present invention is prepared by firing these mixtures at 1600 ° C. or higher. As the sintering method, various methods (vacuum, inert, reducing atmosphere sintering method) can be adopted, but pressure sintering under solid pressure is preferable in consideration of the stability and reproducibility of the phase constitution.

The ratio of the phase composition in the sintered body of the present invention is, for example, Ti
In B ₂ -NiB based composite ceramic sintered body, 3～50V
ol% of a NiB phase with a 1/1 Ni / B atomic ratio is blended with a Group IV diboride.

A description will be given by taking a composite ceramic sintered body TiB ₂ -NiB system as an example. In the composite sintered body, the TiB ₂ particles Ni / B atomic ratio of 1 /
1, evenly distributed in the ceramic phase, thermal conductivity,
With respect to strength and the like, a sintered body having extremely good reproducibility from the NiB side to the TiB ₂ side can be obtained according to the volume ratio. That is,
Particularly on the TiB ₂ side, the random and inevitable appearance of the Ni ₄ B ₃ phase and the Ni ₃ B phase is suppressed, and the reliability of the sintered body characteristic values such as thermal conductivity and strength is improved. In order to densify the composite ceramic sintered body, the NiB phase must be at least 3 Vol% or more. N
When the iB phase is 3 Vol% or less, the TiB ₂ particles cannot be sufficiently bonded by the NiB phase, and many contact portions between the TiB ₂ particles are recognized. Normally, pores tend to collect at the TiB ₂ -TiB ₂ contact portion, so that a large number of pores are generated at the contact portion. In addition, when the sintering temperature is increased to reduce the pores, abnormal grain growth of TiB ₂ particles occurs particularly at the TiB ₂ -TiB ₂ contact portion. Defects and non-uniformity in the above microstructure significantly reduce the reliability of properties such as strength and thermal conductivity of the sintered body. On the other hand, an increase in the NiB phase is preferable for densification of the sintered body, but when the volume of the NiB phase exceeds 50 Vol%, the use of TiB ₂ ceramics composites for properties such as hardness and thermal conductivity of the sintered body is increased. The effect will be significantly reduced,
The NiB phase content must be up to 50 Vol%.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples.

Example 1 Production of boron-based composite ceramics sintered body: TiB ₂ powder having an average particle diameter of 1 μm and NiB powder having an average particle diameter of 5 μm were mixed in a volume ratio of 4/1, and then added in a plastic pot in a hexane solvent. Mix for 8 hours using a ball. The obtained powder was sufficiently dried by heating in a vacuum to obtain a raw material for sintering. CIP this powder φ30 × 5 ^H mm (cold isostatic)
After molding, it was charged into a belt-type high-pressure sintering apparatus, and heated at 1700 ° C. under 10,000 atmospheres for 10 minutes to obtain a sintered body.

Preparation of bonded body: The surface of TiB ₂ (80) -NiB (20) composite boride ceramics (volume in parentheses indicates Vol%) sintered by the above method is ground with a diamond grindstone to form a flat plate of φ25 × 5 mm ^t Finished.

On the other hand, as a structure to which this is to be attached, high-speed steel is processed as shown in Fig. 2 and the upper surface of this structure is composed of Cu (63)
-Mn (22) -Co (5) -Ni (10) (wt% in parentheses),
A sheet-like brazing material having a thickness of 0.3 mm was set. The boride ceramics plate is allowed to stand on this, and is placed in a vacuum (10 ^-3 Torr).
Heating was performed at 1100 ° C for 10 minutes to cool the furnace. as a result,
A good bonded body was obtained without cracking or peeling off at the ceramic / steel interface.

This bonded body can be used as a glass molding die used at a high temperature by utilizing the properties of the bonded boride ceramics such as glass seizure resistance and high temperature oxidation resistance.

The synthesis and properties of the boron-based composite ceramic sintered body used in the present invention are described in Japanese Patent Application No. 1-175735, and some examples of the synthesis are shown below (see the above-mentioned patent specification). Are referred to in this specification).

Synthesis Example 1 A ZrB ₂ powder having an average particle diameter of 3 μm and a NiB powder having an average particle diameter of 5 μm were mixed in a volume ratio of 4/1, treated in the same manner as in Example 1, and subjected to a belt-type high-pressure sintering apparatus at 10,000 atm. 10 at lower 1800 ℃
After heating for a minute, a sintered body was obtained. The characteristics of the obtained sintered body are as follows: relative density of 98% or more, micro hardness of 1650 kg / mm ² , thermal conductivity of 55 W / mK,
It has a bending strength of 900MPa, and its phase structure is determined by X-ray diffraction.
It was confirmed to be a ZrB ₂ -NiB two-phase composite ceramics. As for the reproducibility of the characteristics, good results were obtained as in Example 1.

Synthesis Example 2 60% by volume of CrB powder having an average particle size of 2 μm, Ni powder having an average particle size of 2 μm, and boron powder having an average particle size of 0.5 μm (added at an atomic ratio of 1/1) were mixed. did. This powder is φ
After CIP molding to 30 × 5 ^H mm, 10,000 in belt type high pressure sintering machine
The sintered body was obtained by heating at 1600 ° C. under 0 atm for 5 minutes. According to powder X-ray diffraction, this sintered body is composed of CrB, (Cr, Ni) ₃ B ₄ , (Ni, Cr) B phase, and the Ni / Cr atomic ratio in (Ni, Cr) B phase by EPMA 9/1, and the volume ratio of the (Ni, Cr) B phase was found to be 25 Vol%.

Change the mixing ratio of CrB powder, Ni powder, and B powder
When a sintered body having a (Ni, Cr) B phase volume of 10 Vol% or less with an i + CR / B atomic ratio of 1/1 was produced, the toughness of the sintered body was significantly deteriorated. Fracture toughness of the sintered body of the present Synthesis Example is a 6MNm ^-3/2, (Ni, Cr) when B phase volume is equal to or less than 10Vol% 2MNm
It dropped to ^-3/2 .

On the other hand, the volume of the (Ni, Cr) B phase having an atomic ratio of Ni / Cr of approximately 9/1 is 8
If the content is 0 Vol% or more, a sintered body containing a CrB phase cannot be obtained, and the high-temperature hardness is significantly reduced in addition to the similar decrease in toughness. Therefore, to maintain good toughness and hardness, (Ni, Cr)
The phase B volume ratio must be 10 to 80 Vol%.

CrB powder shown in Synthesis Example 3 Synthesis Example 2, and Ni powder, the volume mixing ratio of B powder constant, TiB ₂ powder and blended to create a sintering raw material powder at a volume ratio of these mixed powder as a 20 vol% , Synthesis Example 2
Sintering was performed under the same conditions.

The phase composition of the obtained sintered body was TiB ₂ , CrB, (Ni, Cr) B, (C
r, Ni) ₃ made of each phase of the B _4, the characteristics of relative density of 99%
Above, fracture toughness is 7MNm ^-3/2, showed very good oxidation resistance even at heating 800 ° C. in air.

CrB, similar to (Ni, Cr) B, ( Cr, Ni) 3 at least the volume ratio of formed ceramic phase of two or more B ₄ is not more than 3 vol% is described in TiB ₂ -NiB Composite Ceramics For this reason, non-uniformity such as pores and abnormal grain growth occurs in the microstructure, and the reliability of the sintered body characteristics is significantly reduced. On the other hand, if it exceeds 50% by volume, the effect of the TiB ₂ ceramic composite on the properties such as the hardness of the sintered body and the thermal conductivity is significantly reduced, so that CrB, (Ni, Cr) B, (Cr, Ni) ₃ B The volume of the ceramic phase composed of at least two types of ₄ is 50
It is necessary to keep up to Vol%.

In a similar sintering test, 70 vol% of a diboride ceramic compounded at a volume ratio of ZrB ₂ / HfB ₂ powder of 1/2 and the CrB
Powder, Ni powder, B powder mixed volume 30Vol%, mix
It was heated at 1800 ° C. under 000 atm for 5 minutes to obtain a sintered body. The oxidation resistance of the obtained sintered body in the air at 800 ° C. was about twice that of the TiB ₂ system. (Here, the oxidation resistance is 800 ° C1
Judgment is made based on the fact that the degree of increase in oxidation during heating for a long time is small, and the rate of increase during heating for a long time is extremely small. Synthesis Example 4 Ta powder having an average particle diameter of 1 μm, W powder having an average particle diameter of 0.5 μm, and boron powder having an average particle diameter of 0.5 μm were synthesized at a stoichiometric composition of TaB and WB at 3 Vol% and 10 Vol%, respectively. It was blended with the sintering raw material powder shown in No. 2 and uniformly mixed to obtain a sintering raw material. This powder was subjected to CIP molding to φ30 × 5 mm ^H, and then heated at 1600 ° C. for 10 minutes under 10,000 atmospheres using a belt-type high-pressure sintering apparatus to obtain a sintered body. From the results of powder X-ray diffraction and EPMA analysis of the sintered body, the sintered body contained Ni + Cr + Ta in addition to the CrB, (Cr, Ni) ₃ B ₄ and (Ni, Cr) B phases.
It became clear that the (Ni, Cr, Ta, W) B phase having an atomic ratio of + W / B 1/1 was contained at 50 Vol%. The characteristics of this sintered body, the fracture toughness value 6MNm ^-3/2 shown in Synthesis Example 2 while being maintained, an increase in the microhardness ^{(1200kg / mm 2 → 1600kg /} mm 2) is confirmed, oxidation In addition to heat resistance, heat resistance also improved. Synthesis Example 2
The volume fraction of (Ni, Cr, M) B phase (M: Ta, W) is 1
At 0 Vol% or less, a significant decrease in fracture toughness occurs.
If the content is 80 Vol% or more, the oxidation resistance is lowered because the CrB phase disappears. Therefore, in order to obtain good fracture toughness, oxidation resistance, and heat resistance, the (Ni, Cr, M ^III ) B phase (M ^III : V, Nb,
(Ta, Mo, W, Mn) volume ratio must be in the range of 10 to 80 Vol%.

〔The invention's effect〕

As described above, according to the method of the present invention, since a boron-based composite ceramics sintered body and a metal-based structural member are joined using a high-strength brazing material, cracks and peeling at the boundary surface may occur. Thus, a joined body excellent in joining strength and joining durability can be obtained at relatively low cost.

In addition, the bonded body of the present invention utilizes the excellent characteristics because the bonded boron-based composite ceramic sintered body has excellent strength, hardness, heat resistance (high-temperature hardness), oxidation resistance, corrosion resistance, and the like. It can be applied to a wide range of uses such as glass molding dies, wear-resistant members, various tools and dies. In particular, when the bonded body of the present invention is used as a glass forming mold, the properties of the bonded boron-based composite ceramics sintered body, such as anti-seizure resistance and high-temperature oxidation resistance, are effectively utilized to form molten glass. Since it can be cooled while being held in the mold as it is, advantages such as excellent molding accuracy and, therefore, no need for the post-processing as in the prior art, leading to excellent productivity are obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing a basic configuration of a joined body of the present invention,
FIG. 2 is a cross-sectional view showing an example in which the present invention is applied to a glass molding die, FIGS. 3 and 4 are cross-sectional views showing other structural examples of the joined body of the present invention, and FIG. 5 is a copper alloy. 6 is a graph showing the relationship between the hardness of the brazing material and the amount of Si added, FIG. 6 is a graph showing the relationship between the brazing strength (shear fracture strength) of the cemented carbide and steel and the hardness of the brazing material, and FIG. FIG. 3 is a schematic configuration diagram of an intensity measuring method. 1,1a, 1b, 1c are boron-based bonded ceramics sintered bodies, 2,2a, 2b,
2c is a brazing material, and 3,3a, 3b, and 3c are metal structural members.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-186271 (JP, A) JP-A-61-209966 (JP, A) JP-A-56-23246 (JP, A) 40967 (JP, A) JP 58-23348 (JP, B2)

Claims (14)

(57) [Claims] (A) at least one kind of M ^I / B (provided that
M ^I is at least one or more selected from the group consisting of Ni, Cr, V, Nb, Ta, Mo, W and Mn.) M ^I B ceramic phase having an atomic ratio of 1/1, TiB ₂ , ZrB _A boron-based composite ceramics sintered body composed of at least one or more group IV diboride ceramic phase and / or (Cr, Ni) ₃ B ₄ ceramic phase selected from the group consisting of HfB ₂ and HfB ₂ (B) a metal-based structural member; (C) Cu-Mn-based, Cu-Mn-Ni-based, Cu-Mn-Co-based, Cu-Mn
-A joined body characterized by being joined by a Co-Ni-based, Cu-Ni-based, or Ni-Mn-based brazing material. 2. The joined body according to claim 1, wherein the joined body is a glass molding mold having a mold cavity surface formed by the boron-based composite ceramics sintered body. 3. The brazing material according to claim 1, wherein said brazing material has a composition of 15 to 30% by weight Mn, 5 to 10% by weight Ni, 5 to 10% by weight Co, 0 to 1.5% by weight Si, and the balance Cu. 3. The joined body according to claim 1, which is a Co brazing material. 4. The brazing material according to claim 1, wherein said brazing material has a composition of 10 to 25% by weight Mn, 5 to 10% by weight Ni, 0 to 3% by weight Si, and the balance Cu.
The joined body according to claim 1 or 2, which is a brazing filler metal. 5. The joined body according to claim 1, wherein the brazing material is a Cu-Mn-Co-based brazing material having a composition of 86% by weight Cu, 10% by weight Mn, and 4% by weight Co. 6. The brazing material is 2 to 10% by weight Ni, 0 to 8% by weight.
The joined body according to claim 1, wherein the joined body is a Cu—Ni-based brazing material having a composition of Si and the balance of Cu. 7. The sintered body of a boron-based composite ceramic is made of Ti
At least one selected from the group consisting of B ₂ , ZrB ₂ and HfB ₂
At least one group IV diboride ceramic phase and M ¹ / B (however,
M ¹ is at least one or more selected from the group consisting of Ni, Cr, V, Nb, Ta, Mo, W and Mn.) The M ¹ ceramic phase has an atomic ratio of 1/1. ³ to 50 V for IB ceramic phase
The conjugate according to any one of claims 1 to 6, wherein the conjugate contains ol%. Wherein said M ^I B ceramic phase, Ni / B atomic ratio of 1
The joined body according to claim 7, wherein the joined body is a NiB ceramic phase of / 1. Wherein said M ^I B ceramic phase, Ni + M ^II / B (where, M ^II is V, Nb, Ta, Cr, Mo, at least one or more selected from the group consisting of W and Mn) Atomic ratio of 1/1 (Ni,
The joined body according to claim 7, wherein M ^II ) is a B ceramic phase. 10. The sintered body of a boron-based composite ceramic,
Furthermore, a CrB ceramic phase with a Cr / B atomic ratio of 1/1, Ni + Cr
(Ni, Cr) B ceramic phase with an atomic ratio of 1/1 / B and (Cr, N
i) ₃ B ₄ assembly according to claim 9 comprising at least two ceramic phases selected from ceramic phase. 11. The sintered body of a boron-based composite ceramic,
Cr / B atomic ratio of 1/1 CrB ceramic phase, Ni + Cr / B atomic ratio is composed of 1/1 of (Ni, Cr) B ceramic phase and (Cr, Ni) ₃ B ₄ ceramic phase, the (Ni The joined body according to any one of claims 1 to 6, comprising 10 to 80 Vol% of a (Cr) B ceramic phase. 12. The boron-based composite ceramics sintered body is
Cr / B atomic ratio of 1/1 CrB ceramic phase, Ni + Cr / B atomic ratio of 1/1 of (Ni, Cr) B ceramic phase and (Cr, Ni) ₃ B ₄ at least two species selected from ceramic phase 3-50Vol% of ceramic phase, TiB ₂ , Zr
Assembly according to any one of B ₂ and claim 1 to 6 from at least one or more kinds of group IV diboride ceramic phase selected from the group consisting of HfB ₂ are those composed. 13. The sintered body of a boron-based composite ceramic,
Cr / B atomic ratio of 1/1 CrB ceramic phase, Ni + Cr / B atomic ratio of 1/1 of (Ni, Cr) B ceramic _{phase, (Cr, Ni) 3 B} 4 ceramic phase and ^{Ni + Cr + M III / B} ( where , M ^III is V, Nb, Ta,
Mo, W and at least one member selected from the group consisting of Mn) atomic ratio 1/1 (Ni, Cr, consists M ^III) B ceramic phase, the (Ni, Cr, M ^III) The joined body according to any one of claims 1 to 6, comprising 10 to 80 Vol% of the B ceramic phase. (A) at least one kind of M ^I / B (where M ^I is at least one kind selected from the group consisting of Ni, Cr, V, Nb, Ta, Mo, W and Mn) and there) atomic ratio is 1/1 M ^I B ceramic phase, TiB _2, ZrB ₂ and at least one or more of group IV selected from the group consisting of HfB ₂ diboride ceramic phase and / or (Cr, Ni ) ₃ B ₄ and the ceramic phase become consists boron-based composite ceramic sintered body, and (B) a metallic structural member, (C) Cu-Mn-based, Cu-Mn-Ni system, Cu-Mn- Co-based, Cu-Mn
-Co-Ni-based, Cu-Ni-based or Ni-Mn-based brazing filler metal is interposed and heated in a vacuum or inert atmosphere to a temperature equal to or higher than the melting point of the brazing filler metal to form a boron-based composite ceramic sintered body and a metal-based A method for joining a boron-based composite ceramics sintered body and a metal-based structural member, wherein a melt of a brazing filler metal is generated between the structural member and the molten metal, and then cooled.