JPS623080A - Metal material for joint - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a method for bonding ceramic materials, particularly ceramic materials with a relatively low average coefficient of thermal expansion of 12X10-'/'C or less at 20 to 300°C. The invention relates to metal materials.

[Conventional technology]

Ceramics have excellent high-temperature strength and are resistant to oxidative corrosion in high-temperature atmospheres, so the use of ceramics as high-temperature components for turbochargers of internal combustion engines and turbine engines has recently been considered. Since ceramics are inherently brittle and have poor workability, it is almost impossible to construct the entire device from ceramics, and in order to use it as a high-temperature member, it is necessary to bond it to metal.

However, ceramics used for this type of member have a smaller coefficient of thermal expansion α than conventional metal materials. For example, the coefficient of thermal expansion α (
Hereinafter referred to as α. ) is as follows.

Ceramics 5i) N4 3X10-'/”C3i
C4,4X10 - 藝/℃ Z ro 2 11. OX 10-'/'CAl2O
,8,0x10-'/'C Metal Steel 11-1F If the thermal expansion coefficients of the materials differ greatly, distortion will occur due to the heating to cooling process during bonding and temperature changes during use.
This may reduce the bonding strength or even damage one of the bonded materials, such as ceramics.

Therefore, α
Special metal material with small temperature, e.g. α=6×10”6i℃
Kovar alloy, α= 1,2X 10-@/”C
Invar alloys are being considered. However, metal materials used in the vicinity of such high-temperature components are required to have appropriate strength from room temperature to high temperature, and the above-mentioned alloys are insufficient in this respect. In other words, the room temperature strength of both Invar and Kovar is about 50KBf/yns2, whereas the strength required for the material is 80Kgf/ωm2.
Because of the above, it cannot withstand use at all.

Therefore, it is possible to add precipitation-strengthening elements to Invar and Kovar alloys to improve their strength. As examples of this, alloys to which 3% Nb-1, 4% Ti-1% Al are added, and alloys to which 1.6% Ti is added have been used on a trial basis. With these additions, the strength is 80-110K
g4/mm”, reaching the desired level.

[Problems to be Solved by the Invention] However, as a result of a detailed study of these materials in terms of application to high-temperature components, the inventors found that these materials are not resistant to oxidation or high-temperature corrosion. It was concluded that this was sufficient.

The present invention has been made in order to solve the above-mentioned problems α of metal materials for joining ceramic ennon members, and has a small α, a desired level of strength, and sufficient acid resistance. The object of the present invention is to provide a metal material for joining that has corrosion resistance and high temperature corrosion resistance.

[Means for solving problems]

The metal material for bonding of the present invention has Ni: 35 to 5 in weight%.
0%, C: 0.05% or less, Mn and MO = 5 in total
% or less, Al: 1.2 to 8% is an essential component, and if necessary, 20% or less of Ni is replaced with the same amount of Co and/or Cu, and if necessary, Ti, Nb, V
, Zr, Ta, W, Hf or 2f! II
Add 0.3% or more of the above and 10% or less in total with Al, further add Si: 0.1-2% and/or Cr: 0.1-7% as necessary, and the balance is Fe. and unavoidable impurities.

The reason for limiting the composition range of each element added to the metal material for joining of the present invention will be explained below.

Ni: 35-50% Ni is the main element for adjusting a of the material. 3
Since a low α can be obtained in the range of 5 to 50%, the composition was limited to the above composition range.

C: 0.05% or less C is a deoxidizing element, and it is advantageous for melting to contain a small amount, but as the content increases, α increases, so 0.0
It was set to 5% or less.

Mn and MO = 5% or less in total Mn has a deoxidizing effect, and MO is an element that is effective for corrosion resistance and strength, so it is advantageous to contain a small amount,
If it is too large, α becomes large, so the total amount is set to 5% or less.

Al: 1.2-8% Al is an element for ensuring oxidation resistance and high-temperature corrosion resistance, and also has a precipitation effect and contributes to improving strength. If it is less than 1.2%, the above effect is insufficient, and if it is more than 8%, it will become brittle, so it was limited to a binary composition range.

Co and Cu: 20% or less Like Ni, this is used to adjust α, and is particularly effective in suppressing the increase in α when Al or the following Ti, Nb, V, Zr, Ta, W, and Hf are contained. be. However, 20
% or more would actually increase α, so it was set to 20% or less.

One or two of Ti, Nb, V, Zr, Ta, W, HE? ! 1 or more in a total of 0.3% or more and a total of 10% or more with Al. Like Al, the strength is improved by precipitation strengthening. However, like Al, the effect on oxidation resistance is small, if it is less than 0.3%, the effect is small, and if the total amount with Al is more than 10%, it will become brittle and at the same time α will increase, so it was set to be less than 10%. .

Si: 0.1-2%, Cr: 0. Both 1 to 7% are deoxidizing elements, which are useful for melting and are effective in improving oxidation resistance and high-temperature corrosion resistance. At 0.1% or less, the effect is small. If Si exceeds 2%, it becomes brittle and α increases, and if C exceeds 7%, α increases, so the composition was limited to the above range.

Due to the above ingredients, 80-140Kgf/+Tsuru 2 at room temperature
A strength of about 50 to 100 Kgf/mm2 at 600°C can be obtained, or about 6 to 9X-10=/''C.A practically sufficient level of oxidation resistance can be obtained.

Since the material of the present invention improves strength due to the precipitation effect, high strength can usually be obtained by maintaining the material at a temperature of about 500 to 750'C for 0.5 to 5 hours.

Utilizing this, it is possible to make adjustments such as, for example, bonding with ceramics in a low strength state and increasing the strength before use.

Needless to say, this alloy can be used as a composite by bonding to ceramics, as well as as an intermediate material for bonding with other ordinary metals with large α.

〔Example〕

Examples of the present invention will be described to clarify the effects of the present invention.

Using a vacuum induction furnace, each f! An alloy of I1m was melted. In Table 1, the force of the invention example is N0.
1 to N0.3 are the first invention examples in which the content of Al was gradually increased, and N0.4 to N0.6 are the third invention examples in which a part of Ni in the basic composition was replaced with Co and Cu. Yes, N
017, No.8, and No.11 are the fifth invention examples in which a part of N is replaced with Co and Ti and Nb are added. Co
In addition to adding Ti, Si or Cr is added.
This is the sixth invention example in which .

N0.11 and N0.12 are the first invention examples containing relatively large amounts of Mn or Mo. On the other hand, the comparative example No.
.

14 to 16 are improved alloys of Invar and Kovar alloys, and N0. No. 17 is a comparative example containing higher carbon than the composition range of the present skin, and similarly No. 18 is high G.

, N0. No. 19 has high Ti and Nb, and No. 20 has high Si. 21 is high Cr, N0.22 is high Mn
, Mo, respectively.

Heat the lump to 1150-1200℃ and forge it to a diameter of 2.
It was made into a round bar of 0I. This forged piece was heated to 1030℃←Ginsaka 1
After solution treatment of heating for a time and cooling with water, aging treatment was performed at an appropriate temperature of 580 to 770°C depending on the composition to increase the strength. Test pieces were taken from this material and subjected to d-tensile tests at room temperature and 600°C, average coefficient of thermal expansion from room temperature to 400°C, and oxidation weight gain by heating in the air at 600°C for 500 hours. The results are shown in Table 1.

As shown in Table 1, the average coefficient of thermal expansion from room temperature to 400℃ (all units are 10-'/'C) is No.
.

The inventive examples with numbers 1 to 0.11 have values of 7.2 to 8.8, while the comparative examples with numbers 0.15 to 0.20 have values of 10.
2 to 11.2, it was confirmed that the material of the present invention had a relatively low α.

Furthermore, the tensile strength Kgf/mad'' at room temperature of the present invention example is 90 to 140, and the value at 600°C is 75 to 10.
1, and the expected values were obtained for all the alloys of the invention examples. On the other hand, the weight gain due to oxidation is 1.9- for N0.12 to N0.14, which are improved copper and invar alloys.
4,5egg/CIx2, whereas the present invention's N0.
It was confirmed that the alloy of the present invention has excellent oxidation resistance.

Next, from the round bar after the above aging treatment, a diameter of 15 am and a length of 5
A 0 mm test piece was taken and the ground was processed into 38 mm to make a bonding test piece. On the other hand, Si3 with a diameter of 15 mm and a length of 50+ us
After finishing the end face of the N, sintered body with a #600 diamond grindstone, a metallizing base mainly composed of Mo was applied and baked to metallize. This was sandwiched with a suitable buffer layer, and then joined to the above alloy using brass solder. After bonding, room temperature -550℃ in the atmosphere
Repeated heating for 15 minutes was performed 200 times, and damage to the ceramics and metals and oxidation damage to the metal parts were inspected. The results are shown in Table 1.

As shown in Table 1, No. 1 to No. of the present invention.

In No. 11, no cracks in the ceramic or metal or wear and tear on the metal parts were observed, whereas in No. 11 of the comparative example
No. In No. 14, wear and tear on the metal parts was observed, and N0.15.
Cracks in the ceramic were observed at ~N0.20. As a result, it was found that the alloy of the present invention has excellent properties as a joining material.

〔Effect of the invention〕

The metal material for joining of the present invention has N: 35 to 50% by weight,
C: 0.05% or less, Mn and Mo2 total 5% or less, AGl, 2-8% as essential Ijt, Ni replaced with Co and/or Cu'C' as necessary, and further as necessary. Depending on the situation, one or more of Ti, Nb, 'V, Zr, Ta, W, and Hf may be added, and if necessary, Si and/or Cr may be added, and the remaining S may be a material consisting essentially of Fe. Therefore, it is a metal material for joining that has a small coefficient of thermal expansion α, can obtain a sufficiently satisfactory value in terms of strength, and has excellent IT oxidation resistance and high temperature corrosion resistance.

Procedural amendment (voluntary) July 11, 1985 2. Name of the invention Metal material for joining 3. Person making the amendment Relationship to the case Patent applicant 4. Agent address 18-5 Hoko 2-chome, Naka-ku, Nagoya No. 6 Building 5 for No. 2
3. Number of inventions increased due to 11'Il correction 11. Subject of amendment Column 2 of claims of the specification, Claim (1) A material for bonding with ceramics,
Its composition is in weight%: Ni: 35-50%, C: 0.0
5% or less, Mn and Mo2 total 5% or less, Al: ], 2
A bonding material characterized in that the balance is 288% FeB and unavoidable impurities.

(2) A material for bonding with ceramics,
What is its composition? Ni: 35-50%, C: 0.
05% or less, Mn and Mo2 total 5% or less, AI:1
．． 2 to 8%, and further Si: 0.1 to 2% and/or Cr: 0. A bonding material characterized in that it contains 1 to 7% of Fe, with the remainder being Fe and unavoidable impurities.

(3) A material for joining ceramics,
Its composition is 1% by weight, Ni: 35-50%, C: 0.0
5% or less, Mn and MO = 5% or less in total, Al: 1.2
8%, wherein 20% or less of Ni is replaced with the same amount of Co and/or Cu''C, and the remainder is Fe and unavoidable impurities.

4 For ceramics and A, the composition is JJLX: Ni: 35-500, C: 50F
・, Mn and Mo 2 now'' Engineering 95' C, A I: 1.
2 to (6) A material for bonding with ceramics, +y'ym formation 1 [Xff 1%, Ni: 35-
50%, C: 0.05% or less, Mn and Mo: 5% in total
Below, AI: 1.2-8%, 20 of N1
% or less with the same amount of Co and/or Cu, and further with Ti, Nb, and V.

One or more of Zr, Ta, W, I (f in total 0.3% or more and Al in total 10% or less, Si:
A bonding material containing 0.1 to 2% and/or 0.1 to 7% Cr, with the remainder being Fe and one unavoidable impurity.

(7) A material for bonding with ceramics, the composition of which is in weight%: Ni: 35-50%, C: 0.05
% or less, Mn and MO = 5% or less in total, Al: 1.2 ~
8%, and further contains Ti, Nb, V, Zr, Ta, W
, Hf, or 2!1 or more in total of 0.3% or more and Al and 10% or less in total, the balance being Fe and inevitable impurities.

(8) A material for bonding with ceramics,
Its composition is in weight%: Ni: 35-50%, C: 0.0
5% or less, Mn and MO: 5% or less in total, Al: 1.2
~8%, and further contains Ti, Nb, V, Zr, T
0.3% in total of one or more of a, W, and Hf
The total amount with Al is 10% or less, and Si: 0.1 to 2%.
and/or Cr:0. Contains 1 to 7%, the remainder F
A bonding material characterized by containing eB and inevitable impurities.

Claims (1)

[Claims] (1) A material for bonding with ceramics, the composition of which is Ni: 35-50%, C: 0.05% by weight.
% or less, Mn and Mo: 5% or less in total, Al: 1.2~
8%, the balance being Fe and unavoidable impurities. (2) A material for bonding with ceramics, the composition of which is in weight percent: Ni: 35-50%, C: 0.05
% or less, Mn and Mo: 5% or less in total, Al: 1.2~
8% and further contains Si: 0.1 to 2% and/or Cr: 0.1 to 7%, with the balance being Fe and inevitable impurities. (3) A material for joining ceramics, the composition of which is in weight percent: Ni: 35-50%, C: 0.05
% or less, Mn and Mo: 5% or less in total, Al: 1.2~
8% of Ni, 20% or less of Ni is replaced with the same amount of Co and/or Cu, and the remainder is Fe and unavoidable impurities. (4) A material for bonding with ceramics, the composition of which is Ni: 35-50%, C: 0.05% by weight.
% or less, Mn and Mo: 5% or less in total, Al: 1.2~
8%, 20% or less of Ni is replaced with the same amount of Co and/or Cu, and further Ti, Nb, V, Zr
, Ta, W, Hf in total of 1 or 2 or more.
．． Contains 3% or more Al and 10% or less in total, and the balance is F.
A bonding material characterized in that it contains e and unavoidable impurities. (6) A material for bonding with ceramics, the composition of which is in weight percent: Ni: 35-50%, C: 0.05
% or less, Mn and Mo: 5% or less in total, Al: 1.2~
8%, 20% or less of Ni is replaced with the same amount of Co and/or Cu, and further Ti, Nb, V, Zr
, Ta, W, Hf in total of 1 or 2 or more.
．． 3% or more Al and 10% or less in total, Si: 0.1
2% and/or Cr: 0.1 to 7%, with the balance being Fe and inevitable impurities. (7) A material for bonding with ceramics, the composition of which is in weight%: Ni: 35-50%, C: 0.05
% or less, Mn and Mo: 5% or less in total, Al: 1.2~
8%, and further contains Ti, Nb, V, Zr, Ta, W
, 0.3% or more of one or more types of Hf in total A
1. A bonding material comprising 10% or less in total of Fe and unavoidable impurities. (8) A material for bonding with ceramics, the composition of which is in weight percent: Ni: 35-50%, C: 0.05
% or less, Mn and Mo: 5% or less in total, Al: 1.2~
8%, and further contains Ti, Nb, V, Zr, Ta, W
, 0.3% or more of one or more types of Hf in total A
10% or less in total, Si: 0.1-2% and/or Cr: 0.1-7%, the balance being Fe and inevitable impurities.