JPH03183667A - Joined body of boride ceramics and metal structural member, and joining method - Google Patents

Abstract

PURPOSE:To join a sintered body to a structural member with enough joint strength and joint durability by stacking a boron-composite ceramic sintered body and a metal structural member through a brazing material, heating them to a temp. over the melting point of the brazing material. CONSTITUTION:(A) A ceramic sintered body comprising M<1>/B (M<1> is Ni, Cr, V, Nb, Ta, Mo, W, Mn) ceramic phase with 1/1 atomic ratio, one or more kinds of diborates of IV group such as TiB2, ZrB2 and HfB2, and/or (Cr,Ni)3B4 ceramics and (B) a metal structural member are superposed through (C) a brazing material comprising Cu-Mn, Cu-Mn-Ni, Cu-Mn-Co, Cu-Mn-Co-Ni, Cu-Ni, or Ni-Mn and heated in vacuum or an inert atmosphere to a temp. higher than the melting point of the brazing material to melt the brazing material between the ceramic sintered body and metal structural member. Then the body is cooled to join the sintered body and the structural member.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a bonded body and a bonding method of boride ceramics and metal structural members, and more specifically, to the stoichiometric composition of each composite phase. A boron-based composite ceramic sintered body with excellent strength, corrosion resistance, conductivity, hardness, oxidation resistance, etc., whose atomic ratio is sufficiently controlled to a specific atomic ratio of 1i17, and a metal structural member are bonded using a specific brazing filler metal. The present invention relates to a method and a zygote obtained thereby. The bonded body according to the present invention can be applied to wear-resistant parts, various tools, dies, etc. by utilizing the excellent properties of the boron-based composite ceramic sintered body that constitutes a part thereof, and can be applied particularly to glass molding metals. It can be optimally used for molds.

[Conventional technology]

Conventionally, molds for glass molding have been made of cast iron, wear-resistant steel, N
I-base cemented carbide is used.

Generally, the softening point of glass is 800° C. or higher, and the mold also needs to be heated to a high temperature to prevent the glass surface from rapidly cooling during molding. However, the upper limit heating temperature of conventional mold materials as described above is low, and even in molds using Ni-based cemented carbide, the upper limit heating temperature of the mold is approximately 600°C.

If the mold is heated to a temperature above this range, the mold surface will be oxidized and become rough, necessitating I and final molding. Therefore, the mold is heated to about 450 to 500°C, and when press-molding the glass that has been heated and melted to a temperature above the softening point, the molding is performed in a short period of time before the mold temperature exceeds 600°C. A method is adopted in which the process is finished and the mold is released. However, compared to a method in which molten glass is pressure-formed until it is sufficiently cooled, there is a problem that the precision of the molded product is inevitably inferior. On the other hand, in the case of molds made of cast iron or wear-resistant steel, the Ni
Since the precision is even worse than when using a base cemented carbide mold, it is generally performed to first perform rough molding and then perform finishing processing.

A boron-based composite ceramic sintered body is known as a material that may have better heat resistance, oxidation resistance, high-temperature durability, hardness, etc. than the above-mentioned materials.

However, there are still few development examples of boron-based composite ceramic sintered bodies, and various proposals and reports have been made in patents, papers, etc. regarding the composition of the sintered bodies, the obtained microstructures, and the properties of these sintered bodies. The current situation is that it is no more than that. In other words, according to current knowledge, due to unavoidable factors included in the properties of the starting materials, sintering process conditions, etc., even if the blended sintered composition is constant, the composition, structure, etc. of each phase constituting the resulting composite ceramic sintered body may vary. In general, the reproducibility and reliability of the characteristics of sintered composite ceramics are low.

For example, as a prior art related to the present invention, there is only one example of the Japanese Patent Publication No. 5B-4337 regarding titanium diboride-based composite sintered bodies.
8 Publication and "Powder and Powder Metallurgy" Vol. 27, No. 4, P31-38.1980, but as shown in these publications, TiB2-Ni-B system composite In the sintered body, the phase composition is TiB2 + NiB (N
A sintered body having two phases (i/B atomic ratio 1/1) has not yet been obtained.

[Problem to be solved by the invention]

The applicant has previously stated that the prior art has not yet achieved
We have developed a new high-performance, highly reliable boron-based composite ceramic sintered body in which the stoichiometric composition of the ceramic phase in the boron-based composite ceramic sintered body is well controlled to a specific atomic ratio, and have already applied for a patent. . However, this boron-based composite ceramic sintered body has a disadvantage in that the production cost is higher than that of conventional ceramics due to its manufacturing method characteristics (high-pressure synthesis, thermite reaction synthesis). An economical way to use such a member is to use it only in areas where the properties of boride ceramics are required, and to bond it to a structural material (base material).

Particularly in glass molding molds, by using boride ceramics having the above-mentioned excellent properties on the mold surface, it is possible to improve the productivity and precision of glass molded products. However, manufacturing a mold using only boride ceramics is economically very expensive and technically difficult. Therefore, it is advantageous to construct only the mold cavity surface from the boron-based composite ceramic sintered body and to form the mold by joining this to other structural materials.

However, when bonding the boron-based composite ceramic sintered body to a structural material (base material), the bonding material and bonding method pose problems. When brazing with a commonly used brazing filler metal, thermal stress occurs when the brazing filler metal is heated and melted and then cooled down, causing cracks and cracks at the ceramic/base metal interface.
There is a problem that peeling occurs.

Therefore, the object of the present invention is to
Tsutsumi (K.
It's about doing.

Furthermore, it is an object of the present invention to bond a boron-based composite ceramic sintered body having excellent strength, hardness, heat resistance, oxidation resistance, corrosion resistance, etc. and a metal structural member with sufficient bonding strength and durability. The object of the present invention is to provide a glass molding mold in which the body, particularly the mold cavity surface, is made of a boron-based composite ceramic sintered body.

[Means to solve the problem]

According to the present invention, in order to achieve the above object, (A) at least one type of Ml/B (where Ml is Ni, C
a MIB ceramic phase with an atomic ratio of 1/1, which is at least one selected from the group consisting of TiB2. ZrB2 and H
Group II diboride ceramics selected from the group consisting of fB2 and/or (Cr.

Ni) a boron-based composite ceramic sintered body composed of a 3Ba ceramic phase; (B) a metal-based structural member;
u-Mn-Co system, Cu-Mn-Co-Ni system, C
A bonded body is provided that is bonded using a u-Ni or Ni-Mn brazing filler metal.

Particularly, according to the present invention, there is provided a glass molding mold in which a mold cavity surface is formed of the boron-based composite ceramic sintered body.

Further, according to the present invention, the boron-based composite ceramic sintered body (A) and the metal-based structural member (B) are combined with the brazing material (C).
) and then heated in a vacuum or an inert atmosphere above the melting point of the brazing material to create a melt of the brazing material between the boron-based composite ceramic sintered body and the metal structural member, and then A method for joining a boron-based composite ceramic sintered body and a metal-based structural member is provided, which is characterized by cooling.

[Operation and mode of the invention]

The brazing material used to join the boron-based composite ceramic sintered body and the metal structural member must not melt at high temperatures (particularly around the softening point of glass, about 800°C), and must maintain a certain degree of shear strength. It is necessary to be present. The present inventors investigated brazing materials having such characteristics, and as a result, as shown in Table 1 below, the Cu-Mn-based brazing materials,
Cu-Mn-Ni system, Cu-Mn-C0 system, Cu
It has been found that -Mn-Co-Ni system, Cu-Ni system and Ni-Mn system can be used. When both members are joined by heating and melting the brazing filler metal, thermal stress is generated during cooling, but this is absorbed by plastic deformation of the brazing filler metal.

As a result, cracks, peeling, etc. do not occur at the ceramic/base material interface. Therefore, a joined body with excellent joint strength and joint durability can be easily produced.

Since the bonded body according to the present invention is a boron-based composite ceramic sintered body bonded to a metal structural member, the cost is reduced and the boron-based composite ceramic sintered body has excellent properties. It also has the following properties and 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 the brazing material, for example, in cutting tools, silver solder or bitter copper solder is generally used. However, when the bonded body according to the present invention is used, for example, as a mold for molding glass, it is heated to a high temperature and generates stress when cooled, so these general brazing fillers have disadvantages in terms of heat resistance, etc. It is enough.

The brazing material according to the present invention is also a brazing material based on Cu, but pure Cu has problems in that it erodes the grain boundaries of steel and has low shear strength.

Ni and Mn prevent such grain boundary erosion of steel, and Mn also forms a solid solution phase at the interface between the brazing metal and steel, which has the effect of improving the "wettability" of the brazing metal and steel. I understand.

It has also been found that Co increases the hardness of the brazing filler metal and improves its "wettability" with the ceramic sintered body.

Furthermore, Si has a large effect of increasing the hardness of the brazing filler metal by 1, and as is clear from FIG.
It was found that HV increased by 25-35 kg/-.

On the other hand, from the viewpoint of heat resistance, it is desirable for the brazing filler metal used in the present invention to have a liquid phase formation temperature of 950°C or higher, and if the temperature exceeds 1150°C, the crystal grains of the steel will become coarse and the base metal strength will increase. It is desirable that the temperature be 1150°C or lower.

Since Mh and St lower the liquid phase formation temperature, and Ni and Co raise it, the liquid phase formation temperature of the brazing filler metal should be set at 950 to 1150°C.
In order to achieve this range, there are limits to the combinations of these alloying elements and their composition ranges.

It was also found that although the hardness of the brazing filler metal strongly depends on Coff1 and the amount of Si, especially the amount of Si, there is no linear relationship between the shear strength of the joint and the hardness. That is, the shear strength of the joint is, as shown in Figure 6, hardness HV150.
The hardness increases with hardness up to HV200, but it decreases above this, and in particular, when the hardness is HV200 or more, it becomes a brittle fracture state.

Therefore, there is an upper limit to the amount of Co11, especially Si, in terms of shear strength.

Furthermore, Fig. 6 shows the relationship between the brazing joint strength of cemented carbide and steel and the hardness of the brazing filler metal measured according to the shear strength measurement method shown in Fig. 7. It is thought that the same holds true when a composite ceramic sintered body is used. In FIG. 7, which schematically shows the shear strength M1 formula, P is a load, 11 is a cemented carbide, 12 is steel brazed to both sides of the cemented carbide, and 13 is a stand.

The optimum composition range of the brazing filler metal for the present invention has been comprehensively determined based on the characteristics of the alloying elements.
For Ni-3i system, 2 to 10% Ni, preferably 5 to 10%
%Ni, 1-8%Si; 10-8% for Cu-Mn-Ni system
25% Mn, 5-10% Ni, 0-3% Si, or C
In the u-Mn-Ni-Co system, M n is 15 to 30%.

5-10% Ni, 5-10% Co, and 0-1.5% Si are suitable. In addition, the hardness of the brazing metal is about 7 Vickers hardness.
5-200 kg/+ma, more preferably 100-2
A range of 00 kg/nua is preferred.

Among the carving materials shown in Table 1, copper alloys, especially Cu (
66) -Mn (24) -N i (10), C
u (63)-Mn (22)-Co (5)-Ni
(10), Cu(86)-Mn(10)-Co
(4) is preferred, especially Cu (63)-Mn (2
2)-Co(5)-Ni(10) is optimal. On the other hand, Ni-based brazing filler metals have good wettability, but are inferior to copper alloys when used as glass forming materials because they may cause cracks when the joined body is repeatedly heated and cooled. .

FIG. 1 shows the basic configuration of a joined body according to the present invention. In the figure,
1 is a boron-based composite ceramic sintered body, 2 is a brazing material, and 3 is a metal-based structural member. Ceramic sintered body 1 is laminated on metal structural member 3 via brazing filler metal 2, and this is heated above the melting point of the brazing filler metal in a vacuum or an inert atmosphere to form a boron-based composite ceramic sintered body and steel. Normal brazing is performed by forming a melt of the brazing filler metal between the two and then cooling the filler metal to solidify the filler metal. This results in a brazed joint with heat resistance and strength. FIG. 2 shows an example in which the present invention is applied to a mold for molding glass. The mold cavity surface 4 is composed of a boron-based composite ceramic sintered body 1a. Note that various metal-based structural materials can be used as the base material, and metal-based structural materials such as cemented carbide, high speed steel, and die steel can be suitably used in the glass molding mold.

As shown in FIG. 2, in a mold in which the ceramic sintered body 1a is combined with the structural member 3al at 11%, it is sufficient to hold the mold surface of the ceramic sintered body so that it does not move during heating. The joint strength by brazing is not so much of a problem. However, if bond strength is a concern, brazing can add a mechanical coupling element in addition to bonding, as shown in FIGS. 3 and 4.

FIG. 3 shows an example in which a dovetail 5 is provided on the upper surface of the structural member 3b, a dovetail 6 is provided on the lower surface of the ceramic sintered body 1b, and the dovetail 6 is inserted into the dovetail groove 5 through the brazing material 2b. On the other hand, FIG. 4 shows an example in which screws 7 are used to fasten the parts.

The boron-based composite ceramic sintered body used in the present invention has an Ml/B ceramic phase constituting one phase of the composite sintered body, specifically, N i /BN i +, Mm /
B (Ml: Cr, Va ~■a group element), C
r/B, Ni+Cr/B, Ni+Cr+Mm/B
The atomic ratio of the ceramic phase of (, Mm: Va to ■a group elements) is well controlled to 171, and regardless of whether Ni is replaced with other metals, Ml /B ceramic phase atomic ratio is 1/1
By fully controlling the
It has excellent properties such as toughness and strength.

More specifically, the boron-based composite ceramic sintered body of the present invention has a sintered body composition of group Ⅰ diboride TiB2. Z
rB2. At least one type of HfB2 and Ml/B
(preferably Ni/B) M with an atomic ratio controlled to 1/1
A sintered body consisting of a ceramic mixed phase with lB (preferably NiB), a CrB phase with a Cr/B atomic ratio controlled to 1/1, a (Cr, Ni)3B4 phase, and a Ni
+ C;, the r/B atomic ratio was controlled to 1/1 (
Ni.

A sintered body consisting of a mixed phase of ceramics (Cr)B phase is used as an example, and a ceramic phase (Mm: V, Nb, Ta, Cr, M
The gist is a boron-based composite ceramic sintered body in which stoichiometric composition compounds are further added and stoichiometric composition compounds are further added.

The group Ⅰ diboride ceramic used in the present invention is produced by sufficiently controlling the atomic ratio of the Ni/B, Cr/B, and Ni+Mm/B phases constituting the remainder of the sintered body to 1/1. In order to improve the density, toughness, etc. of kf, it is desirable that the purity is high and the particle size is small.

Cr/B atomic ratio 1/1 ceramic phase, (Cr, N
i) 3B4kan only needs to live as a sintered body, so
Any form of starting material may be used.

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

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

The phase composition ratio in the sintered body of the present invention is, for example, Ti
In the B2-NiB composite ceramic sintered body, 3
~50vo1% NiB with a Ni/B atomic ratio of 1/1
The phase is blended with a group II diboride.

Composite ceramic sintered body T i B 2 N i B
This will be explained using a system as an example. In this composite sintered body, Ti8
When 2 particles are uniformly distributed in a ceramic phase with a Ni/B atomic ratio of 1/1, the reproducibility of thermal conductivity, strength, etc. from the NiB side to the TiB2 side is extremely good depending on the volume ratio. A sintered body is obtained. That is, especially T
On the iB2 side, the random and unavoidable appearance of Ni4B3 phase and Ni3B phase is suppressed, and the reliability of sintered body characteristic values such as thermal conductivity and strength is improved. In order to make the present composite ceramic sintered body dense, the NiB phase must contain at least 1% or more of 3Vo. When NiB is less than 3 Vol%, TiB
The two particles cannot be bonded together sufficiently in the NiB phase, and T i B
Many contact areas between the two particles become visible. As a general rule, pores tend to gather in this TiB2-TiB2 contact area, resulting in a large number of pores in this contact area. In addition, if the sintering temperature is increased to reduce these pores,
In particular, abnormal grain growth of TiB2 particles occurs at the TiB2-TiB2 contact area. Defects and non-uniformity in the above-mentioned microstructure significantly reduce reliability of properties such as strength and thermal conductivity of the sintered body. On the other hand, N i B ) [
An increase of 1 is preferable for densification of the sintered body, but an increase in N
When the volume of iB phase exceeds 50Vo 1%, the hardness of the sintered body decreases.
Since the effect of TiB2 ceramic composite on properties such as thermal conductivity will be significantly reduced, the amount of NiB phase should be 50
Vo should be kept below 1%.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1 Creation of boron-based composite ceramic sintered body.

TiB2 powder with an average particle size of 1 μm and Ni powder with an average particle size of 5 μm
Powder B was blended at a volume ratio of 4/1 and mixed for 80 minutes using a plastic pot and ball in a hexane solvent. The obtained powder was sufficiently heated and dried in a vacuum to be used as a raw material for sintering. This powder is φ30 x 5','n
After CIP (cold isostatic pressure) molding to ++*, it is charged into a belt-type high-pressure sintering device and heated at 1700°C under 10,000 atmospheres.
A sintered body was obtained by heating for 10 minutes.

Creation of joined body: TiB2 (80)-NiB (
20) Grind the surface of the composite boride ceramics (Vol% is shown in parentheses) with a diamond grindstone,
Finished with a flat plate of mi'.

On the other hand, as a structure to which this is attached, high-speed steel is processed as shown in Fig. 2, and the upper end surface of the structure is made of Cu (6
3)-Mn(22)-C.

(5) -Ni (10) (wt% in parentheses) and a sheet-like brazing filler metal with a thickness of 0.3 mm were set.

The above-mentioned boride ceramic plate was placed on top of this, and a vacuum (1
The mixture was heated at 1100° C. for 10 minutes in 0-' Torr) and cooled in the furnace. As a result, a good bonded body was obtained without any cracks or peeling at the ceramic/steel interface.This bonded body has excellent glass baking resistance, high temperature oxidation resistance, etc. of the bonded boride ceramics. Taking advantage of its properties, it can be used as a mold for glass molding at high temperatures.

The synthesis and characteristics of the boron-based composite ceramic sintered body used in the present invention are described in the specification of Japanese Patent Application No. 1-175735, and some synthesis examples thereof are shown below (the above-mentioned patent specification (The contents of this document are incorporated herein by reference).

Synthesis Example 1 ZrB2 powder with an average particle size of 3 μm and Ni with an average particle size of 5 μm
Powder B was mixed at a volume ratio of 4/1, treated in the same manner as in Example 1, and heated at 1800°C for 10 minutes under 10,000 atm using a belt-type high-pressure sintering device to obtain a sintered body. . The characteristics of the obtained sintered body are a relative density of 98% or more and a microhardness of 1650.
kg/-1 thermal conductivity 55 W/m K, bending strength 9
It was 00 MPa. According to X-ray diffraction, its phase composition is Zr.
It was confirmed that it was a B2-NiB two-phase composite ceramic. Regarding the reproducibility of the characteristics, similar to Example 1, good results were obtained.

Synthesis Example 2 1% of CrB powder 60Vo with an average particle size of 2 μm and the balance of Ni powder with an average particle size of 2 μm and boron powder of 0.5 μm (added at an atomic ratio of 1/1) were mixed, and after mixing, 1% of CrB powder 60Vo was used for sintering. Used as raw material. This powder was sintered into a size of φ30 x 5'mm at 1600°C under 10,000 atmospheres using a CIP hollow-bottom belt type high-pressure sintering machine.
A sintered body was obtained by heating for 1 minute. According to powder X-ray diffraction, this sintered body contains CrB, (Cr, Ni)3 B4. (Ni.

(Cr)B phase, and is composed of (Ni, Cr) phase by EPMA.
) The N i /Cr atomic ratio in phase B is 9/1, and (
It became clear that the volume ratio of Ni, Cr) B phase was 25 Vol%.

By arbitrarily changing the mixing ratio of CrB powder, Ni powder, and B powder, (Ni, Cr
) When a sintered body having a B phase volume of 10 Vo 1% or less was produced, the toughness of the sintered body was significantly deteriorated. The fracture toughness value of the sintered body of this synthesis example is 6MNm-”2, but (Ni, Cr
) When the B phase volume is 10 Vol% or less, 2 M N m
−”’ decreased.

On the other hand, (Ni,
If the Cr)B phase volume is 80Vo 1% or more, a sintered body containing the CrB phase cannot be obtained, and in addition to a similar decrease in toughness value, high temperature hardness also decreases significantly.

Therefore, to maintain good toughness values and hardness, (Ni,
Cr) B phase volume ratio needs to be 10 to 80 Vol%.

Synthesis Example 3 The volume mixing ratio of the CrB powder, Ni powder, and B powder shown in Synthesis Example 2 was kept constant, and the volume ratio of these mixed powders was 20V0.
A sintering raw material powder was prepared by blending it with TiB2 powder at a concentration of 1%, and sintering was performed under the same conditions as in Synthesis Example 2.

The phase structure of the obtained sintered body was TiB2. CrB.

It is composed of the following phases: (Ni, Cr)B, (Cr, Ni)3B4, and its characteristics include a relative density of 99% or more, a fracture toughness value of 7 M N m-'', and a resistance to heating at 800℃ in the air. It also showed extremely good oxidation resistance.

CrB, (Ni, Cr)B, (Cr, Ni)3
When the volume ratio of the ceramic phase composed of at least two or more types of B4 is 3Vo 1% or less, pores, abnormal grain growth, etc. occur in the microstructure for the same reason as described for TiB2-NiB composite ceramics. Heterogeneity occurs;
The reliability of the sintered body properties is significantly reduced. On the other hand, 50Vo
If it exceeds 1%, the properties such as sintered body hardness and thermal conductivity will be affected.
Since the iB2 ceramic composite effect will be significantly reduced, CrB, (Ni, Cr)B, (Cr, Ni)3
The volume of the ceramic phase composed of at least two types of B4 needs to be 50 Vol% or less.

In a similar sintering test, diboride ceramic 70V mixed at a ZrB2/HfB2 powder volume ratio of 1/2 was tested.
o Mixed volume 3 of 1% and the CrB powder, Ni powder, and B powder
Mix 1% of QVo and heat under 10,000 atmospheres at 18
The sintered body was heated at 00°C for 5 minutes. The oxidation resistance of the sintered body at 11100°C in the atmosphere is T i B
Approximately twice the characteristics of the 2nd system were obtained. (Here, what is oxidation resistance?
The degree of oxidation i flattening during heating at 800°C for 1 hour is small,
Furthermore, even when heated for a long time, the filtration rate is extremely small, which determines "fil".)Synthesis Example 4 Ta powder with an average particle size of 1 μm, W powder with an average particle size of 0.5 μm,
Boron powder with an average particle size of 0.5 μm was added to the sintering raw material powder shown in Synthesis Example 2 at a TaB and WB stoichiometric composition of 3Vo 1% and 1QVo 1%, mixed uniformly, and sintered. It was used as a raw material for condensation. CI this powder to φ30X5mm'
After P-molding, it was heated for 10 minutes at 1600° C. under 10,000 atmospheres using a belt-type high-pressure sintering device to obtain a sintered body. From the results of powder X-ray diffraction and EPMA analysis of the sintered body, it was found that CrB, (Cr, Ni)3B4゜(Ni,Cr)B was present in this sintered body.
In addition to the phase, (N
It became clear that the B phase (i, Cr, Ta, W) contained 1% of 50Vo. The characteristics of this sintered body include an increase in microhardness (1200 kg/oua) while maintaining the fracture toughness value of 5 M N m-'' shown in Synthesis Example 2.
-1600 kg/-), and the heat resistance was improved in addition to the oxidation resistance. As shown in Synthesis Example 2, (Ni, C
r, M) The volume fraction of B phase (M: Ta, W) is 1OVol%
A significant decrease in fracture toughness value occurs below 8.
If 0Vo is 1% or more, the CrB phase disappears, resulting in a decrease in oxidation resistance. Therefore, in order to obtain good fracture toughness, oxidation resistance, and heat resistance, (Ni, Cr,, Mm)B
The volume fraction of the phase (Mm: V, Nb, Ta, Mo, W, Mn) needs to be in the range of 10 to 80 VO1%.

〔Effect of the invention〕

As described above, according to the method of the present invention, boron-based U Since the composite ceramic sintered body and the metal structural member are bonded using a high-strength brazing filler metal, a bonded body with excellent bonding strength and bonding durability is created without cracking or peeling at the interface. Obtained relatively cheaply.

In addition, the bonded body of the present invention has excellent properties such as strength, hardness, heat resistance (temperature resistance), oxidation resistance, and corrosion resistance of the bonded boron-based ceramic sintered body. Furukawa's products can be applied to a wide range of applications, including glass and molds, wear-resistant parts, various tools, and dies. In particular, when the bonded body of the present invention is used as a glass molding mold,
The properties of the bonded boron-based composite ceramic sintered body, such as glass seizure resistance and high temperature oxidation resistance, are effectively utilized, and the molten glass can be held in the mold as it is and cooled after forming.
It has excellent molding accuracy, and therefore has advantages such as excellent productivity because it eliminates the need for post-processing as in the past.

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram showing the basic configuration of the 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 mold for molding glass, 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. System brazing filler metal hardness and Si
A graph showing the relationship between the addition amount. Figure 6 is a graph showing the relationship between the brazing strength (shear fracture strength) of cemented carbide and steel and the hardness of the brazing filler metal. Figure 7 is a schematic diagram of the shear strength measurement method. It is. 1, la, lb, lc are boron-based composite ceramic sintered bodies, 2, 2a, 2b, 2c are brazing materials, 3.3a, 3b, 3
c is a metal structural member. Figure 3 ht-~ ^! A Co. Si addition (wtX) Fig. 2 Hardness of brazing filler metal (kg/mm2)

Claims (14)

[Claims] (1) (A) At least one type of M^l/B (however,
M^l is at least one selected from the group consisting of Ni, Cr, V, Nb, Ta, Mo, W, and Mn) M^lB ceramic phase with an atomic ratio of 1/1, and TiB
A boron-based composite ceramic sintered body composed of at least one group IV diboride ceramic phase and/or (Cr, Ni)_3B_4 ceramic phase selected from the group consisting of _2, ZrB_2, and HfB_2; (
B) Metallic structural members, (C) Cu-Mn system, Cu-Mn-Ni system, Cu-Mn system
- A joined body characterized by being joined by a Co-based, Cu-Mn-Co-Ni-based, Cu-Ni-based, or Ni-Mn-based brazing material. (2) The joined body according to claim 1, which is a glass molding mold in which a mold cavity surface is formed of the boron-based composite ceramic sintered body. (3) The brazing filler metal contains 15 to 30% by weight Mn and 5 to 10% by weight.
wt% Ni, 5-10 wt% Co, 0-1.5 wt% S
The bonded body according to claim 1 or 2, which is a Cu-Mn-Ni-Co brazing filler metal having a composition of i and the balance being Cu. (4) The brazing filler metal contains 10 to 25% by weight Mn, 5 to 10
The joined body according to claim 1 or 2, which is a Cu-Mn-Ni brazing filler metal having a composition of %Ni by weight, 0 to 3% by weight Si, and the balance Cu. (5) the brazing filler metal is 86% by weight Cu and 10% by weight Mn;
The joined body according to claim 1 or 2, which is a Cu-Mn-Co brazing filler metal having a composition of 4% by weight Co. (6) The joined body according to claim 1 or 2, wherein the brazing filler metal is a Cu-Ni brazing filler metal having a composition of 2 to 10% by weight Ni, 0 to 8% by weight Si, and the balance Cu. (7) The boron-based composite ceramic sintered body is TiB_
2. at least one group IV diboride ceramic phase selected from the group consisting of ZrB_2 and HfB_2;
M^l/B (However, M^l is Ni, Cr, V, Nb, T
a, Mo, W, and Mn) with an atomic ratio of 1/1, and the M^lB ceramic phase is
The zygote according to any one of claims 1 to 6, which contains ~50 Vol%. (8) The joined body according to claim 7, wherein the M^lB ceramic phase is a NiB ceramic phase with a Ni/B atomic ratio of 1/1. (9) The M^lB ceramic phase is Ni+M^m/
B (where M^m is at least one selected from the group consisting of V, Nb, Ta, Cr, Mo, W and Mn) (Ni, M^m)B with an atomic ratio of 1/1 The joined body according to claim 7, which is a ceramic phase. (10) The boron-based composite ceramic sintered body further includes a CrB ceramic phase with a Cr/B atomic ratio of 1/1, a N
The joined body according to claim 9, comprising at least two types of ceramic phases selected from a (Ni, Cr)B ceramic phase and a (Cr, Ni)_3B_4 ceramic phase with an i+Cr/B atomic ratio of 1/1. (11) The boron-based composite ceramic sintered body has Cr/
CrB ceramic phase with B atomic ratio of 1/1, Ni+Cr
It is composed of a (Ni, Cr)B ceramic phase and a (Cr, Ni)_3B_4 ceramic phase with a /B atomic ratio of 1/1, and the (Ni, Cr)B ceramic phase is
The conjugate according to any one of claims 1 to 6, which contains 0 Vol%. (12) The boron-based composite ceramic sintered body has Cr/
CrB ceramic phase with B atomic ratio of 1/1, Ni+Cr
3 to 50 Vol of at least two types of ceramic phases selected from a (Ni, Cr)B ceramic phase and a (Cr, Ni)_3B_4 ceramic phase with a /B atomic ratio of 1/1.
%, the remainder of the ceramic phase is TiB_2, ZrB_2
The joined body according to any one of claims 1 to 6, which is composed of at least one group IV diboride ceramic phase selected from the group consisting of HfB_2 and HfB_2. (13) The boron-based composite ceramic sintered body has Cr/
CrB ceramic phase with B atomic ratio of 1/1, Ni+Cr
(Ni, Cr)B ceramic phase with /B atomic ratio of 1/1, (Cr, Ni)_3B_4 ceramic phase and Ni+
Cr+M^m/B (However, M^m is V, Nb, Ta, M
o, W, and Mn) with an atomic ratio of 1/1 (Ni, Cr, M^m)
It is composed of the B ceramic phase, and the above (Ni, Cr, M
^m) The joined body according to any one of claims 1 to 6, which contains 10 to 80 vol% of the B ceramic phase. (14) (A) At least one kind of M^l/B (However, M^l is at least one kind selected from the group consisting of Ni, Cr, V, Nb, Ta, Mo, W, and Mn. ) M^lB ceramic phase with an atomic ratio of 1/1 and TiB
A boron-based composite ceramic sintered body composed of at least one group IV diboride ceramic phase and/or (Cr, Ni)_3B_4 ceramic phase selected from the group consisting of _2, ZrB_2, and HfB_2; (B) Metallic structural members, (C) Cu-Mn-based, Cu-Mn-Ni-based, Cu-Mn
-Co, Cu-Mn-Co-Ni, Cu-Ni, or Ni-Mn brazing filler metals are layered together and heated above the melting point of the brazing filler metal in a vacuum or inert atmosphere to create a boron-based composite. A method for joining a boron-based composite ceramic sintered body and a metal structural member, characterized by generating a melt of a brazing filler metal between the ceramic sintered body and the metal structural member, and then cooling it.