JPH08120376A - Heater substrate made of nickel-base heat resistant alloy and heater member using the same - Google Patents

Abstract

PURPOSE: To improve the oxidation resistance and mechanical strength of a heater substrate, simultaneously to impart excellent cold workability thereto and to produce a heater substrate having a complicated shape by specifying the compsn. of an Ni-base heat resistant alloy. CONSTITUTION: This heater substrate has an alloy compsn. contg., by weight, 2 to 10% Al, 0.1 to 4% Si and 0.01 to 0.5% C, furthermore contg. one or >=two kinds selected from among 0.0001 to 0.5% Y, 0.0001 to 0.3% La and 0.0001 to 0.3% Ce, and the balance Ni with inevitable impurities. This compsn. is preferably further incorporated with one or >= two kinds selected from among 0.1 to 2% Mn, 0.5 to 20% Co and 0.5 to 40% Fe. Furthermore, <=15% in total of one or >= two kinds selected from among the groups of 0.1 to 5% Ti, 0.1 to 10% Mo, 0.1 to 10% W, 0.1 to 10% Ta, 0.1 to 10% Nb and 0.1 to 10% Hf are preferably added thereto.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heater base made of a Ni-base heat-resistant alloy, which is preferably used in a high temperature oxidizing atmosphere, and a heater member using the same.

[0002]

2. Description of the Related Art FIG. 2 is a longitudinal sectional view showing an example of a conventional tubular heater member used in a high temperature oxidizing atmosphere. In the drawing, 1 is a heater base and 2 is an outer surface of the heater base 1. 1a is an insulating layer, 3 is the insulating layer 2
It is a heating resistance layer formed on the top. The heater base 1 is made of a heat-resistant alloy such as stainless steel such as SUS304 or SUS310S, a Ni-based alloy such as Inconel 600 (Ni-16Cr-8Fe), or the like. These heat-resistant alloys contain Cr in an amount of 16 to 25% by weight in order to enhance oxidation resistance and mechanical strength. This Cr reacts with oxygen in an oxidizing atmosphere, and the surface of the heat-resistant alloy contains Cr. Oxidation resistance is obtained by forming a protective film made of ₂ O ₃ . Further, since Cr has a solid solution strengthening effect, the mechanical strength of the heat resistant alloy is also improved.

The insulating layer 2 is made of an electrically insulating ceramic such as Al ₂ O ₃ (alumina). The heating resistance layer 3 is made of conductive ceramics such as SiC (silicon carbide).

[0004]

By the way, in the heat-resistant alloy used for the conventional heater substrate 1, it is necessary to contain Cr in an amount of 16% by weight or more in order to sufficiently improve the oxidation resistance and the mechanical strength. However, such a large amount of Cr
The alloy containing Al has the drawback of being inferior in cold workability. For example, when it is desired to manufacture a heater member having a complicated shape to match the outer shape of an object to be heated, or a heater member having a complicated shape, it is necessary to manufacture the heater base 1 that matches the shape. Since it is poor in properties, it is very difficult to manufacture the heater substrate 1 having a complicated shape, and there is a problem in that some heaters cannot be manufactured depending on the shape and the like.

Further, when the conventional heater member is heated to 600 ° C. or higher, oxygen enters between the heater base 1 and the insulating layer 2 due to diffusion, and oxide scale is generated between the heater base 1 and the insulating layer 2. Will occur and grow,
There is a problem that the insulating layer 2 is easily separated from the heater substrate 1 when the heating is repeated. Therefore, there is a problem that the performance as a heater member is deteriorated and the heater member becomes unusable in some cases.

The present invention has been made in view of the above circumstances, is excellent in cold workability, and therefore a heater member having a complicated shape can be easily manufactured, and further, an insulating layer is formed on the heater member. It is an object of the present invention to provide a heater base made of a Ni-base heat-resistant alloy, and a heater member using the same, in which the insulating layer is not likely to be peeled off from the heater base even when repeatedly heated to 600 ° C. or higher after forming.

[0007]

In order to solve the above problems, the present invention employs the following Ni-based heat-resistant alloy heater base and a heater member using the same. That is, the Ni-based heat-resistant alloy heater base according to claim 1 has an Al: 2 to
10% by weight, Si: 0.1 to 4% by weight, C: 0.01 to
0.5% by weight and Y: 0.0001-
0.5% by weight, La: 0.0001 to 0.3% by weight, C
e: One or two or more selected from 0.0001 to 0.3% by weight is contained, and the balance is Ni and inevitable impurities.

Here, Al and Si are limited as described above because their contents are Al: 2% by weight and S, respectively.
When i: less than 0.1% by weight, the oxidation resistance is insufficient, while the contents are Al: 10% by weight and Si: 4, respectively.
This is because the cold workability is deteriorated when the content exceeds the weight%. Further, C is limited as described above because the content is 0.
If it is less than 01% by weight, the desired mechanical strength cannot be obtained, while if it exceeds 0.5% by weight, the alloy becomes brittle. Further, Y, La, and Ce are limited as described above because the contents of Y, La, and Ce are 0.000 each.
If it is less than 1% by weight, the effect of improving the adhesion to the ceramic film formed on the surface by repeated heating cannot be obtained, while the content thereof is Y: 0.5% by weight, respectively.
This is because when La: 0.3 wt% and Ce: 0.3 wt% are exceeded, the adhesion to the ceramic film and the cold workability deteriorate.

The Ni-based heat-resistant alloy heater base according to claim 2 is the same as the Ni-based heat-resistant alloy heater base according to claim 1, further comprising Mn: 0.1 to 2 wt% and Co: 0.5.
˜20% by weight, Fe: 0.5 to 40% by weight, and one or more selected from them.

Here, the Mn is limited as described above, because if the content is less than 0.1% by weight, sufficient deoxidation cannot be achieved, while the content exceeds 2% by weight. And the oxidation resistance decreases. Further, Co is limited as described above because the desired mechanical strength cannot be obtained when the content thereof is less than 0.5% by weight, while the content thereof is 2
Even if it exceeds 0% by weight, the effect of further improving the strength cannot be obtained, which is uneconomical. Further, the reason why Fe is limited as described above is
This is because if the content is less than 0.5% by weight, the desired mechanical strength cannot be obtained, while if the content exceeds 40% by weight, the oxidation resistance decreases.

The Ni-based heat-resistant alloy heater base according to claim 3 is the same as the Ni-based heat-resistant alloy heater base according to claim 1, further comprising Ti: 0.1 to 5% by weight and Mo: 0.1.
-10 wt%, W: 0.1-10 wt%, Ta: 0.1
-10 wt%, Nb: 0.1-10 wt%, Hf: 0.
One kind or two or more kinds selected from 1 to 10% by weight is contained in a total amount of 15% by weight or less.

[0012] Ti, Mo, W, Ta, Nb and Hf have the action of improving the mechanical strength at high temperatures, so they can be contained if necessary, but the content of any of the components is If it is less than 0.1% by weight, the desired high temperature strength cannot be obtained, while if it exceeds 5% by weight for Ti and 10% by weight for each of Mo, W, Ta, Nb and Hf, the oxidation resistance decreases. Is.
When two or more of these components are contained, if the total content of the components exceeds 15% by weight, the oxidation resistance decreases, so the total content must be 15% by weight or less.

The Ni-based heat-resistant alloy heater base according to claim 4 is the same as the Ni-based heat-resistant alloy heater base according to claim 1, further comprising Mn: 0.1 to 2 wt% and Co: 0.5.
.About.20 wt%, Fe: 0.5 to 40 wt%, and one or more selected from Ti: 0.
1 to 5% by weight, Mo: 0.1 to 10% by weight, W: 0.1
-10 wt%, Ta: 0.1-10 wt%, Nb: 0.
1 to 10% by weight, Hf: 0.1 to 10% by weight, and one or more kinds selected from the total of 15% by weight or less.

According to a fifth aspect of the present invention, there is provided a heater member, wherein an insulating layer containing ZrO ₂ (zirconia) as a main component is provided on one main surface of the Ni-based heat-resistant alloy heater substrate according to any one of the first to fourth aspects. The heating resistance layers are sequentially laminated, and the value of the thermal expansion coefficient of the insulating layer is set to a value between the thermal expansion coefficient of the heater base and the thermal expansion coefficient of the heating resistance layer.

[0015]

In the heater base made of the Ni-base heat-resistant alloy according to claim 1 of the present invention, Al: 2 to 10% by weight, Si: 0.1 to 4
Wt%, C: 0.01 to 0.5 wt%, Y: 0.0001 to 0.5 wt%, La: 0.00
01 to 0.3% by weight, Ce: 0.0001 to 0.3% by weight, and one or two or more selected from the rest, and Ni and unavoidable impurities in the balance, so that even if Cr is not included, acid resistance can be improved. The chemical conversion property and the mechanical strength are sufficiently enhanced, the workability in the cold working is improved, and the heater substrate having a complicated shape is easily manufactured. In addition, the heater base is 60
When repeatedly heated to 0 ° C. or higher, oxide scale is not generated between the heater base and the insulating layer, and there is no possibility of peeling.

According to the heater base made of the Ni-base heat-resistant alloy according to claim 2, the heater base made of the Ni-base heat-resistant alloy according to claim 1 is further provided with Mn: 0.1 to 2% by weight and Co: 0.5 to.
By containing one or more selected from 20% by weight and Fe: 0.5 to 40% by weight, the mechanical strength is further enhanced.

In the heater base made of the Ni-base heat-resistant alloy according to claim 3, the Ni-base heat-resistant alloy heater base according to claim 1 is further provided with Ti: 0.1 to 5% by weight and Mo: 0.1 to 0.1% by weight.
10% by weight, W: 0.1 to 10% by weight, Ta: 0.1
10% by weight, Nb: 0.1 to 10% by weight, Hf: 0.1
By containing one kind or two or more kinds selected from 10% by weight to 15% by weight or less in total, the mechanical strength at high temperature is improved.

In the heater base made of the Ni-base heat-resistant alloy according to claim 4, the heater base made of the Ni-base heat-resistant alloy according to claim 1 is further provided with Mn: 0.1 to 2% by weight and Co: 0.5 to.
20% by weight, Fe: 0.5-40% by weight, and one or more selected from Ti: 0.1
~ 5 wt%, Mo: 0.1-10 wt%, W: 0.1
10% by weight, Ta: 0.1 to 10% by weight, Nb: 0.1
-10 wt%, Hf: 0.1-10 wt% selected from 1 or 2 or more in total, by containing 15 wt% or less in total, the mechanical strength is further increased, the mechanical strength at high temperature is improved. To do.

A heater member according to a fifth aspect of the present invention is a heater base made of a Ni-base heat-resistant alloy according to any one of the first to fourth aspects, wherein an insulating layer containing ZrO ₂ as a main component and a heating resistance layer are provided on one main surface. Are sequentially laminated, and the value of the thermal expansion coefficient of the insulating layer is
By setting the value between the coefficient of thermal expansion of the heater base and the coefficient of thermal expansion of the heating resistance layer, the heater member is heated to 600 ° C.
Even when the heating is repeatedly performed as described above, there is no possibility that oxide scale is generated between the heater base and the insulating layer, and the adhesion between them is improved. Therefore, there is no risk of the insulating layer peeling off from the heater substrate. As a result, the performance as a heater member is maintained and the life can be extended.

[0020]

1 is a longitudinal sectional view showing a tubular heater member according to an embodiment of the present invention. In the drawing, 11 is a heater base, and 12 is an outer surface (one main surface) 11a of the heater base 11. The insulating layer 13 containing ZrO ₂ as a main component is a heating resistor layer formed on the insulating layer 12. The value of the coefficient of thermal expansion of the insulating layer 12 is set so as to take a value between the coefficient of thermal expansion of the heater base 11 and the coefficient of thermal expansion of the heating resistance layer 13.

The heater substrate 11 contains Al: 2 to 10% by weight, Si: 0.1 to 4% by weight, C: 0.01 to 0.5% by weight, and Y: 0.0001 to 0.5. % By weight, La: 0.0001 to 0.3% by weight, Ce: 0.0
One or two or more selected from 001 to 0.3% by weight is contained, and the balance is Ni and inevitable impurities, and the coefficient of thermal expansion thereof is 12 to 18 × 10 ⁻⁶ deg ⁻¹ .

The insulating layer 12 has good adhesion to the heater base 11, and is unlikely to generate oxide scale with the heater base 11. For example, ZrO ₂ such as monoclinic crystal, or ZrO ₂ −. _{6~10mol% Y 2 O 3, ZrO} 2 -11
_{~15mol% CaO, ZrO 2 -7~15mol%} M
Stabilization or partial stabilization of divalent or trivalent metal oxide such as gO or ZrO ₂ such as Y ₂ O ₃ (yttria), MgO (magnesia) or CaO (calcia) in a solid solution of about 3 to 15 mol%. Zirconia or the like is preferably used. The thermal expansion coefficient of ZrO ₂ is 7 to 10 × 10 ⁻⁶ deg ⁻¹ , and the thermal expansion coefficient of the stabilized zirconia is, for example, yttria-added stabilized zirconia (ZrO ₂ -8 mol% Y ₂
In the case of O ₃ ), it is about 8.10 × 10 ^-6 deg ^-1 .

The heating resistance layer 13 has good adhesion to the insulating layer 12, and is made of, for example, a conductive ceramic such as SiC. The coefficient of thermal expansion of SiC is 5.12 to 5.8 × 10 ⁻⁶ deg ⁻¹ .

The composition of the heater substrate 11 is the same as the above composition except that Mn: 0.1 to 2% by weight and Co: 0.5 to.
20% by weight, Fe: 1 to 2 or more selected from 0.5 to 40% by weight, and / or Ti:
0.1 to 5% by weight, Mo: 0.1 to 10% by weight, W:
0.1 to 10% by weight, Ta: 0.1 to 10% by weight, N
b: 0.1 to 10% by weight, Hf: 0.1 to 10% by weight, and one or more kinds selected from the total may be contained in an amount of 15% by weight or less.

Tables 1 and 2 show the respective test results of the cold workability and the peeling resistance by repeated heating when the composition of the heater substrate 11 is variously changed. Here, the heater substrate 11 having a component composition within the range of the present invention is an example (No. 1 to No. 25), and the one having a component composition outside the range of the present invention is a comparative example (No. 26).
-No. 36). Table 3 shows a conventional example (No.
37-No. 39) shows the results of similar tests.

In the cold workability test, widths of 20 mm and lengths of 100 mm were obtained from each of the plate materials having the component compositions shown in Tables 1 to 3.
A test piece having a thickness of 2 mm was prepared, the surface of each test piece was polished with # 800 emery polishing paper, and then a bending test (bending radius 0 mm, 180 ° bending) was performed at room temperature. The presence or absence of cracks was examined. In the peeling resistance test by repeated heating, from each of the plate materials having the component compositions shown in Tables 1 to 3, width 20 mm x length 100 mm x thickness 0.
A test piece having a size of 2 mm is prepared, and the surface of each test piece is subjected to bright annealing to form a glossy surface.
A 0 μm ZrO ₂ insulating layer was formed. Then, each of these test pieces is heated at 900 ° C. for 30 minutes in the atmosphere for 30 minutes and then air-cooled, which is repeated 20 times, and then Z
Bending test (bending radius 4 mm, 180 ° bending) was performed at room temperature with the rO ₂ insulating layer as the convex side, and Zr of each test piece was measured.
The presence or absence of cracking, peeling, and rising of the O ₂ insulating layer was examined.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

As is clear from Tables 1 to 3, in the present examples (No. 1 to No. 25), cold workability,
While the peel resistance by repeated heating is good, in Comparative Examples (No. 26 to No. 36), cold workability or peel resistance by repeated heating is poor, and there is no good both. . Moreover, the conventional example (No. 37-
No. Also in 39), neither of them is good as in the comparative example. Therefore, the effectiveness of this example was clarified.

As described above, according to the heater substrate of the above embodiment, the oxidation resistance and the mechanical strength can be sufficiently enhanced, the workability in cold working can be improved, and the complicated shape can be obtained. The heater base can be easily manufactured. Further, even when the heater base is repeatedly heated to 600 ° C. or higher, oxide scale does not occur between the heater base and the insulating layer, and there is no possibility of peeling.

Further, ZrO is formed on one main surface of the heater base.
An insulating layer containing ₂ as a main component and a heating resistance layer are sequentially laminated, and the value of the thermal expansion coefficient of the insulating layer is set to a value between the thermal expansion coefficient of the heater base and the thermal expansion coefficient of the heating resistance layer. So
Even when the heater member is repeatedly heated to 600 ° C. or higher, it is possible to prevent oxide scale from being generated between the heater base and the insulating layer, and to improve the adhesion between them. It is possible to prevent the insulating layer from peeling off from the heater substrate. Therefore, the performance of the heater member can be maintained for a long period of time, and the life of the heater member can be extended.

The heating resistance layer 13 is the insulating layer 12
Any material that has good adhesion with and does not peel off, such as ceramics having conductivity such as MoSi ₂ (molybdenum disilicide), heat-resistant alloys for heating elements such as Ni-based alloys or Fe-based alloys, and the like are used. May be.

In the above embodiment, the insulating layer 12 and the heating resistance layer 13 are formed on the outer surface 11a of the tubular heater substrate 11.
The heater base 1 has a structure in which
It suffices that the insulating layer 12 and the heating resistance layer 13 are sequentially laminated on one main surface of the first substrate 1. For example, the insulating layer 12 and the heating resistance layer 13 are sequentially laminated on the inner surface 11b of the heater base 11, or a flat plate. An insulating layer on the surface of the heater body
It is possible to change into various shapes according to the application, such as a structure in which heating resistor layers are sequentially laminated.

[0035]

As described above, according to the heater base made of the Ni-base heat-resistant alloy according to claim 1 of the present invention, Al: 2 to
10% by weight, Si: 0.1 to 4% by weight, C: 0.01 to
0.5% by weight and Y: 0.0001-
0.5% by weight, La: 0.0001 to 0.3% by weight, C
e: One or two or more selected from 0.0001 to 0.3% by weight is contained, and the balance is Ni and unavoidable impurities. Therefore, sufficient oxidation resistance and mechanical strength can be obtained without Cr. Therefore, the workability in cold working can be improved, and a heater substrate having a complicated shape can be easily manufactured. In addition, the heater base is 60
Even if it is repeatedly heated to 0 ° C. or more, there is no possibility that oxide scale will occur on the surface of the heater substrate, and when the insulating layer is formed on one main surface of the heater substrate, prevention of peeling of this insulating layer You can

According to the heater base made of the Ni-base heat-resistant alloy according to claim 2, Mn: 0.1 to 2% by weight, Co:
Since one or more selected from 0.5 to 20% by weight and Fe: 0.5 to 40% by weight is contained, the mechanical strength can be further increased.

According to the heater base made of the Ni-base heat-resistant alloy according to claim 3, further, Ti: 0.1 to 5% by weight and Mo:
0.1 to 10% by weight, W: 0.1 to 10% by weight, Ta:
0.1-10% by weight, Nb: 0.1-10% by weight, H
f: One or two or more selected from 0.1 to 10% by weight is contained in total of 15% by weight or less,
The mechanical strength at high temperature can be improved.

According to the heater base made of the Ni-base heat-resistant alloy according to claim 4, Mn: 0.1 to 2% by weight, Co:
0.5 to 20% by weight, Fe: 0.5 to 40% by weight, and one or more selected from
i: 0.1 to 5% by weight, Mo: 0.1 to 10% by weight,
W: 0.1 to 10% by weight, Ta: 0.1 to 10% by weight,
Nb: 0.1 to 10% by weight, Hf: 0.1 to 10% by weight
15% by weight in total of one or more selected from
Since it is contained below, the mechanical strength can be further increased and the mechanical strength at high temperature can be improved.

According to the heater member of claim 5, an insulating layer containing ZrO ₂ as a main component is provided on one main surface of the heater base made of the Ni-base heat-resistant alloy according to any one of claims 1 to 4.
Since the heating resistance layers are sequentially laminated and the value of the thermal expansion coefficient of the insulating layer is set to a value between the thermal expansion coefficient of the heater base and the thermal expansion coefficient of the heating resistance layer, the heater member is kept at 600 ° C. or higher. Even when it is repeatedly heated, the oxide scale can be prevented from being generated between the heater base and the insulating layer, the adhesion between them can be enhanced, and the insulating layer is separated from the heater base. Can be prevented. Therefore, the performance of the heater member can be maintained for a long period of time, and the life of the heater member can be extended.

[Brief description of drawings]

FIG. 1 is a vertical sectional view showing a heater member according to an embodiment of the present invention.

FIG. 2 is a vertical sectional view showing a conventional heater member.

[Explanation of symbols]

 11 Heater Base 12 Insulating Layer 13 Heating Resistance Layer

Claims (5)

[Claims] 1. Al: 2 to 10% by weight, Si: 0.1
4% by weight, C: 0.01 to 0.5% by weight, Y: 0.0001 to 0.5% by weight, La: 0.00
Ni-based heat-resistant alloys containing one or two or more selected from 01 to 0.3% by weight and Ce: 0.0001 to 0.3% by weight, and the balance consisting of Ni and inevitable impurities. Made heater base. 2. Mn: 0.1 to 2% by weight, C
The heater base made of a Ni-base heat-resistant alloy according to claim 1, further comprising one or more selected from o: 0.5 to 20% by weight and Fe: 0.5 to 40% by weight. 3. Further, Ti: 0.1 to 5% by weight, M
o: 0.1 to 10% by weight, W: 0.1 to 10% by weight, T
a: 0.1 to 10% by weight, Nb: 0.1 to 10% by weight,
Hf: 1 or 2 selected from 0.1 to 10% by weight
The heater base made of a Ni-base heat-resistant alloy according to claim 1, characterized in that a total of 15% by weight or more of at least one kind is contained. 4. Mn: 0.1 to 2% by weight, C
o: 0.5 to 20% by weight, Fe: 0.5 to 40% by weight, and one or more selected from
Ti: 0.1 to 5% by weight, Mo: 0.1 to 10% by weight,
W: 0.1 to 10% by weight, Ta: 0.1 to 10% by weight,
Nb: 0.1 to 10% by weight, Hf: 0.1 to 10% by weight
15% by weight in total of one or more selected from
The heater base made of a Ni-base heat-resistant alloy according to claim 1, characterized by containing the following: 5. An insulation layer containing ZrO ₂ as a main component and a heating resistance layer are sequentially laminated on one main surface of the heater base made of the Ni-base heat-resistant alloy according to claim 1, and the insulation is formed. A heater member, wherein the value of the coefficient of thermal expansion of the layer is a value between the coefficient of thermal expansion of the heater base and the coefficient of thermal expansion of the heating resistance layer.