JP2536547B2 - Ni-based heat-resistant alloy - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a rotary kiln used in a calcination and firing step in manufacturing a ceramic electronic component such as a ceramic capacitor, a ceramic piezoelectric element, a ceramic semiconductor, and a thermistor. Such as lining materials,
The present invention relates to a Ni-base heat-resistant alloy suitable for use as a mesh tray on which it is placed and various members that come into contact with the ceramic electronic components such as a container for accommodating it.

[Conventional technology]

Generally, in ceramic capacitors, ceramic piezoelectric elements, etc., BaTiO ₃ or Pb (Ti, Zr) O ₃ powder is sintered and electrodes are formed on the sintered body, so Ag paste or Ag-Pd is formed on the surface.
After printing or applying the alloy paste, it was placed on a box-shaped or mesh-shaped tray and continuously fired at 800 to 900 ° C. Conventionally, stainless steel such as SUS304 or SUS310 or pure Ni was used for this tray. These materials are 80
When used at a temperature of 0 to 900 ° C. for a long time, there is a problem that the oxide scale generated on the surface peels off and adheres to the paste to deteriorate the properties of the object to be fired. The inventors previously provided the Ni-base heat-resistant alloy of Japanese Patent Application No. 61-243387, and have been used in this field to show the effect.

[Problems to be solved by the invention]

However, recently, new ceramics have been developed one after another with the aim of improving piezoelectric characteristics and dielectric characteristics. Regarding piezoelectric elements, Pb (Ti, Zr) O ₃ in which a part of Pb is replaced with Ba or Sr, or ( Mg, Nb) O ₃ -PbTiO ₃ a three-component system of -PbZrO _3, etc. have emerged one after another.

Among these new electronic ceramics, there has been a problem that the firing of the Ni-based heat-resistant alloy or the stainless steel tray causes discoloration of the contact portion between the ceramic and the tray, resulting in deterioration of electromagnetic characteristics. There was no discoloration problem in the pure Ni tray, but there was contamination due to peeling of the oxide scale, and a similar phenomenon was observed in the TiO ₂ drying and firing process.

[Means for solving problems]

Therefore, as a result of detailed investigation of the discolored part of the fired electronic ceramic and the discolored part of TiO ₂ from the above viewpoints, the present inventors have found that the discolored part is due to the reaction between Cr and the ceramic in the tray material. I caught up.

Generally, heat-resistant alloys improve their oxidation resistance,
Basically Cr is added, but as a result of conducting research to develop a heat resistant alloy having good oxidation resistance without adding Cr from the above viewpoint, the result is% by weight (hereinafter% is% by weight). (1) Al: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or two or more thereof, and the balance of Ni and inevitable impurities in the composition (more than wt%), Ni-based alloy, (2) Ni-based of the above (1) Ni-based alloy having a composition containing Fe: 0.5 to 10%, (3) Ni-based alloy of (1) or (2) above, further Co: 0.5 to 20%, (4) Ni-base alloy having a composition containing (4) Ni-base alloy having a composition in which Mo: 0.1 to 10% is further added to the Ni-base alloy of (1) or (2) above, (5) Above (1) or (2) Ni-based alloy, which has a composition of Co: 0.5-20% and Mo: 0.1-10%, has extremely good oxidation resistance and does not contain Cr. When used as various members that come into contact with it in the calcination process and the firing process in the production of ceramic electronic parts, etc., there is little reaction and the ceramics that come into contact with the various members may be discolored. In addition, Ag-based paste used in the ceramic electrode firing process
We have obtained the knowledge that Ag-Pd alloy-based pastes are chemically extremely stable.

The present invention has been made based on the above findings, and the reason why the composition of the Ni-based alloy is limited as described above will be described below.

(A) Al The Al component has a function of forming Al ₂ O ₃ on the surface of the alloy and improving the chemical stability with respect to the ceramic electronic component, but if the content is less than 2%, the oxidation resistance is If the content is not sufficient and the content exceeds 10%, the hot workability is deteriorated. Therefore, the content is defined as 2 to 10%.

(B) Si The Si component has a deoxidizing effect, but more than that
Like Al, it has the effect of improving oxidation resistance. In particular, when the content of Cr is small, the effect is remarkable, and when the content is 1% or less, the oxidation resistance is not sufficient, while when the content exceeds 4%, the hot workability is deteriorated. Therefore, the content is determined to be over 1% to 4%.

(C) CC When the content of Cr is small, it has a function of forming a solid solution in the matrix to improve the strength, but if the content of Cr is less than 0.01%, the desired strength cannot be obtained. When the content exceeds 0.01, the alloy becomes brittle, so the content should be 0.01-
It was set at 0.5%.

(D) Y, La and Ce These components have the effect of improving the adhesion of the Al ₂ O ₃ protective coating formed on the alloy surface, but their contents are Y, La and Ce respectively. If it is less than 0.001%, the desired effect cannot be obtained, while if the content exceeds Y: 0.5%, La: 0.3%, and Ce: 0.3%, the hot workability and weldability deteriorate. Because you will
The content of Y: 0.001-0.5%, La: 0.001-0.3% and
Ce: 0.001 to 0.3% was set. In addition, Y: 0.005-0.1%, La:
0.01 to 0.12% and Ce: 0.01 to 0.12% are preferably contained.

(E) Since the Fe component is an inexpensive element, it is economically advantageous to increase the content thereof, but the content of Fe component is 0.
If it is less than 5%, the desired effect cannot be obtained, while the content is 1
If it exceeds 0%, the oxidation resistance will deteriorate, so the content was defined as 0.5-10%.

(F) Co The Co component has the action of forming a solid solution in the matrix to improve the strength, so it is contained as necessary when high strength is required, but if its content is less than 0.5%. It is economically disadvantageous because the desired strength-improving effect cannot be obtained, and on the other hand, even if the content exceeds 20%, no further strength-improving effect can be obtained. Therefore, its content is set to 0.5 to 20%.

(G) Mo Mo is added because it has the effect of improving high-temperature strength, but if its content is less than 0.1%, the desired high-temperature strength improving effect cannot be obtained, while its content exceeds 10%. When,
Since the oxidation resistance will deteriorate, the content of
Mo: 0.1-10%.

In the alloy of the present invention, B is used as an alloy component.
And if one or two of Zr is contained in the range of 0.001 to 0.1, the creep strength at high temperature will be improved,
Furthermore, one or two of Ca and Mg is added to 0.001 to 0.3.
When it is contained in the range of%, the hot workability can be improved by the deoxidizing and desulfurizing effect.

〔Example〕

Next, the alloy of the present invention will be specifically described by way of examples.

Using a normal vacuum induction melting furnace, melts each having the composition shown in Table 1 were prepared, and diameter: 60 mm x length:
Cast into a 200mm ingot, temperature this ingot: 11
While maintaining at 50 ℃ for 5 hours, hot forging is performed several times to form a slab with a thickness of 20mm, and after this slab is surface-polished, it is reheated to a temperature of 1150 ℃ for several times. The hot-rolled sheet is hot-rolled to a thickness of 2 mm, and the hot-rolled sheet is subsequently held at a temperature of 1100 ° C. for 10 minutes and then heat-treated under water cooling conditions to obtain the alloy sheet 1 of the present invention. .About.24 and comparative alloy sheet materials 1-2. Comparative alloy plate materials 3 to 5 are
Commercial thickness: A 2 mm plate was used.

These inventive alloy sheet materials 1 to 24 and comparative alloy sheet material 1
The following tests were carried out for Nos. 5 to 5 for the purpose of evaluating the chemical stability of ceramic electronic parts.

(A) Oxidation resistance test A test piece having dimensions of length: 20 mm × width: 30 mm × thickness: 2 mm was used to prepare the above alloy sheet materials 1 to 24 of the present invention and comparative alloy sheet materials 1 to 1 above.
Each of the test pieces was cut out from No. 5, and each surface was polished with # 150 emery paper and then degreased.

Put each of the above test pieces into an alumina crucible and heat them in an electric furnace in the atmosphere at a temperature of 1150 ° C. for 20 hours and then let them naturally cool to room temperature as one cycle, and repeat this for 25 cycles. The amount of thinning was measured by observing the cross section of the sample under a microscope. The test results are shown in Table 1.

(B) is a kind of discoloration test piezoceramic (Pb, St) (Ti, Zr) those printed with Ag-Pb paste sintered chip O _3,
Test pieces prepared from the above-described alloy sheet materials 1 to 24 of the present invention and comparative alloy sheet materials 1 to 5 having dimensions of length: 50 mm × width: 100 mm × thickness: 2 mm (similar to the oxidation resistance test, polished with # 150 emery paper. It was placed on the surface of the container) and kept in the air at a temperature of 850 ° C. for 2 hours, and then air-cooled to room temperature.

This was performed 20 times as one cycle, and the presence or absence of discoloration on the chip side of the contact surface between the chip and the test piece was visually observed, and the results are also shown in Table 1.

〔The invention's effect〕

From the results shown in Table 1, the alloy sheet materials 1 to 24 of the present invention
Is a comparative alloy sheet material 1 to 5 which does not discolor the contact surface of the ceramic constituting the electronic component and has excellent oxidation resistance at the same time, but which does not satisfy the component composition conditions of the present invention.
It is also understood that all of them have poor oxidation resistance due to the large amount of oxidation thinning, and that the comparative alloy plate materials 4 to 5 containing Cr in particular discolor the contact surface of the ceramic.

As described above, when the Ni-based heat-resistant alloy of the present invention is used as a lining material or a container of a rotary kiln used in a calcination process or a firing process of a ceramic electronic component, or as a tray, it has an excellent effect. .

Claims (8)

(57) [Claims] 1. Al: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or more of them are contained, and the rest has a composition consisting of Ni and unavoidable impurities (above weight%) in the calcination and firing process of ceramic electronic parts. Ni-based heat-resistant alloy suitable for use as various contacting members. 2. Aluminium: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or more of them are contained, and further, Co: 0.5 to 20% is contained, and the balance is composed of Ni and inevitable impurities (above weight%). A Ni-base heat-resistant alloy suitable for use as various members that come into contact with ceramic electronic parts during calcination and firing processes. 3. Aluminium: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or more of them are contained, and Mo: 0.1-10% is further contained, and the balance is composed of Ni and unavoidable impurities (above weight%). A Ni-base heat-resistant alloy suitable for use as various members that come into contact with ceramic electronic parts during calcination and firing processes. 4. Aluminium: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or more of them are contained, and further, Co: 0.5 to 20%, Mo: 0.1 to 10% are contained, and the balance is composed of Ni and inevitable impurities (above weight%) A Ni-base heat-resistant alloy suitable for use as various members that come into contact with a ceramic electronic component during calcination and firing steps. 5. Al: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or more of them are contained, Fe: 0.5 to 10% is further contained, and the balance is composed of Ni and unavoidable impurities (above weight%). A Ni-base heat-resistant alloy suitable for use as various members that come into contact with ceramic electronic parts during calcination and firing processes. 6. Aluminium: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or more of them are contained, Fe: 0.5-10% is further contained, Co: 0.5-20% is further contained, and the rest is Ni and inevitable impurities. A Ni-base heat-resistant alloy suitable for use as various members that come into contact with a ceramic electronic component during calcination and firing steps, characterized by having a composition (above wt%). 7. Aluminium: 2-10%, Si: more than 1% -4%, C: 0.01-0.5%, Y: 0.001-0.5%, La: 0.001-0.3%, Ce: 0.001- 0.3%, one or more of them are contained, Fe: 0.5-10% is further contained, Mo: 0.1-10% is further contained, and the rest is Ni and inevitable impurities. A Ni-base heat-resistant alloy suitable for use as various members that come into contact with a ceramic electronic component during calcination and firing steps, characterized by having a composition (above wt%). 8. Al: 2 to 10%, Si: more than 1% to 4%, C: 0.01 to 0.5%, Y: 0.001 to 0.5%, La: 0.001 to 0.3%, Ce: 0.001 to 0.3%, one or more of them are contained, Fe: 0.5-10% is further contained, Co: 0.5-20%, Mo: 0.1-10% is contained, and the rest Ni-based heat-resistant alloy suitable for use as various members that come into contact with calcination and firing steps of ceramic electronic parts, characterized in that is composed of Ni and inevitable impurities (above wt%).