JP2014080675A - Ni-BASED ALLOY EXCELLENT IN HOT FORGING PROPERTY, HIGH TEMPERATURE OXIDATION RESISTANCE AND HIGH TEMPERATURE HALOGEN GAS CORROSION PROPERTY AND MEMBER USING Ni-BASED ALLOY - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a Ni-based alloy excellent in hot forging property, high temperature oxidation resistance and high temperature halogen gas corrosion property, suitable as a constituent material of a firing tray of a chip capacitor, a firing tray of a lithium battery positive electrode substance, a CVD device member, a PVD device member, an LCD device member and a semiconductor equipment member.SOLUTION: There is provided a Ni-based alloy excellent in hot forging property, high temperature oxidation resistance and high temperature halogen gas corrosion property, containing, by wt.%, Al: 2.0 to 5.0%, Si: 0.1 to 2.5%, Cr: 0.8 to 4.0%, Mn: 0.1 to 1.5%, B: 0.001 to 0.01%, Zr: 0.001 to 0.1% and the balance Ni with inevitable impurities.

Description

The present invention relates to a Ni-based alloy excellent in hot forgeability, high-temperature oxidation resistance and high-temperature halogen gas corrosiveness, and a member using this Ni-based alloy, particularly a chip capacitor firing tray, a lithium battery positive electrode material The present invention relates to a baking tray, a CVD device member, a PVD device member, an LCD device member, and a semiconductor manufacturing device member.

In general, a member such as a tray used in an oxidation furnace or a firing furnace uses a Ni-based alloy having excellent high-temperature oxidation resistance in order to prevent mixing of oxide scale generated from the member into a product.
As such a Ni-based alloy excellent in high-temperature oxidation resistance, for example, as shown in Patent Document 1, Al: 3.6 to 4.4% by mass% (hereinafter,% represents mass%) Further, if necessary, one or more of Si: 0.1-2.5%, Cr: 0.8-4.0%, Mn: 0.1-1.5% A Ni-based alloy with a balance of Ni and inevitable impurities and excellent in high-temperature oxidation resistance used as fins and tubes for high-temperature heat exchangers has been proposed.

  In Patent Document 2, Al: 0.05 to 2.5%, Si: 0.3 to 2.5%, Cr: 0.5 to 3.0%, Mn: 0.5 to 1.8 In addition, a Ni-based alloy excellent in heat resistance and corrosion resistance has been proposed in which Si / Cr <1.1 or less, with the balance being Ni and inevitable impurities.

  Furthermore, Patent Document 3 includes Al: 3.1-4.3%, Si: 0.5-1.5%, Cr: 1-2%, Mn: 0.45-0.65%, Mg and A Ni-based alloy for a spark plug electrode material is proposed that contains 0.005 to 0.05% of Ca or two of Ca, the balance being Ni and inevitable impurities, and excellent in high-temperature strength and spark wear resistance. .

Pure nickel with a Ni-Al layer formed on the surface of a CVD device member, a PVD device member, an LCD device member, and a semiconductor manufacturing device member, which is excellent in plasma resistance by halogen-based gas and corrosion resistance to film formation and cleaning. Alternatively, a Ni-based alloy member is used.
As such a member excellent in high-temperature halogen gas corrosivity, for example, as shown in Patent Document 4, the material of the base material is pure nickel or a Ni—Cr—Fe alloy, and a Ni—Al alloy layer is formed on the surface thereof. A formed film forming treatment device member has been proposed.

Japanese Patent No. 3814822 JP-A-2-163336 Japanese Patent No. 3206119 JP 2012-219369 A

In recent years, there has been a demand for large jig members that are excellent in high-temperature oxidation resistance and are used in applications such as jigs for manufacturing semiconductor products. However, since the Ni-based alloys shown as Patent Documents 1 to 3 are not sufficient in hot forgeability or high-temperature oxidation resistance, Ni-based alloys for applications requiring hot forgeability and high-temperature oxidation resistance are required. As a result, it did not have satisfactory characteristics.
Further, in applications such as semiconductor manufacturing apparatus members, further corrosion resistance against halogen gas has been required even in parts and movable parts where high dimensional accuracy is required. However, the member for a film formation processing apparatus shown as the above-mentioned Patent Document 4 is difficult to achieve high dimensional accuracy because the film formation processing is performed after the base material is machined, and the film is microscopic in the movable part. However, it has not been provided with satisfactory characteristics at such sites because it can be destroyed and become a source for generating particles.

Therefore, the present inventor has solved this problem and developed a Ni-based alloy having hot forgeability superior to that of the prior art and having excellent high temperature oxidation resistance and high temperature halogen gas corrosion resistance. As a result of extensive research, Al: 2.0-5.0%, Si: 0.1-2.5%, Cr: 0.8-4.0%, Mn: 0.1% by weight ~ 1.5%, with respect to the Ni-based alloy having the component composition as described in Patent Document 1 with the balance being Ni and inevitable impurities, B: 0.001 to 0.01% and Zr: 0.001 By containing ˜0.1%, this Ni-based alloy not only shows high-temperature oxidation resistance equivalent to the Ni-based alloy described in Patent Document 1, but also has better hot forgeability. The result of research that shows excellent corrosion resistance to high-temperature halogen gas. It is.

The present invention has been made based on the above findings,
“(1) Al by weight%: 2.0-5.0%,
Si: 0.1 to 2.5%
Cr: 0.8-4.0%
Mn: 0.1 to 1.5%
B: 0.001 to 0.01%,
Zr: 0.001 to 0.1% is contained,
A Ni-based alloy excellent in hot forgeability, high-temperature oxidation resistance and high-temperature halogen gas corrosion resistance, the balance being Ni and inevitable impurities.
(2) Al: 3.6-4.2% by weight,
Si: 1.1 to 1.7%,
Cr: 1.6 to 2.3%,
Mn: 0.2 to 0.7%
B: 0.001 to 0.007%,
Zr: 0.001 to 0.06% is contained,
The Ni-based alloy having excellent hot forgeability, high-temperature oxidation resistance and high-temperature halogen gas corrosion resistance as described in (1) above, wherein the balance is Ni and inevitable impurities.
(3) A chip capacitor or a lithium battery positive electrode material firing tray, a CVD device member, a PVD device member, an LCD device member, and a semiconductor manufacturing device member made of the Ni-based alloy according to (1) or (2). "
It is characterized by.

  Next, the reason for limiting the numerical value of each component element in the alloy composition of the Ni-based alloy of the present invention will be described in detail.

Al:
Al forms an alumina coating on the surface of a Ni-based alloy, has the effect of improving high-temperature oxidation resistance and reducing the generation of oxide scale, and aluminum fluoride, which is highly protective particularly in a high-temperature fluorine-based gas environment. It is added because it has the effect of reducing the generation of particles by suppressing the generation of corrosive organisms, but if the content is less than 2.0%, a sufficient alumina coating or aluminum fluoride coating will not be formed On the other hand, if the desired effect cannot be obtained, and its content exceeds 5.0%, the hot workability is lowered due to the precipitation of the γ 'phase (Ni ₃ Al intermetallic compound) in the substrate. It is not preferable because it becomes difficult to do. Therefore, the Al content is determined to be 2.0 to 5.0%. The more preferable content of Al is 3.6 to 4.2%.

Si:
Si is added because it has an effect of improving high-temperature oxidation resistance. However, if its content is less than 0.1%, a desired improvement effect cannot be obtained in the above-described effect, while its content is 2.5%. If it exceeds 1, cracks are likely to occur during hot working, so the content was determined to be 0.1 to 2.5%. A more preferable Si content is 1.1 to 1.7%.

Cr:
Cr is added because it has an effect of improving heat resistance. However, if its content is less than 0.8%, the desired improvement effect cannot be obtained for the above-described effect, while its content exceeds 4.0%. Then, the high temperature strength tends to decrease, so the content was determined to be 0.8 to 4.0%. A more preferable Cr content is 1.6 to 2.3%.

Mn:
Mn is added because it has the effect of improving the high-temperature strength. However, if its content is less than 0.1%, a desired improvement effect cannot be obtained for the above-described effect, while its content exceeds 1.5%. And, since the high temperature oxidation resistance is lowered, the content is determined to be 0.1 to 1.5%. A more preferable Mn content is 0.2 to 0.7%.

B and Zr:
B and Zr have the effect of improving the hot forgeability of the Ni-based alloy by adding them together.
Speaking of the respective contents of B and Zr, if the content of B is less than 0.001%, a desired improvement effect cannot be obtained in the above action, while if the content exceeds 0.01%, Therefore, the B content is determined to be 0.001 to 0.01%. A more preferable content of B is 0.001 to 0.007%.
Zr also improves the hot forgeability of the Ni-based alloy. However, if the Zr content is less than 0.001%, a desired effect cannot be obtained in improving the hot forgeability, while the content is If the content exceeds 0.1%, the hot forgeability is reduced as in the case of addition of B, so the Zr content is determined to be 0.001 to 0.1%. A more preferable content of Zr is 0.001 to 0.06%.

In the present invention, B and Zr are respectively 0.001 to 0.01% and 0.001 to 0.1% (preferably 0.001 to 0.007% and 0.001 to 0.00, respectively. Within the range of 06%), both of them are added at the same time. However, when only one of them is added, or when either of them is added outside the scope of the present invention, the hot forgeability The improvement effect cannot be expected. This is presumably because the grain boundary breakage in hot forging is suppressed because the grain boundaries of the Ni-based alloy are strengthened by the simultaneous addition of B and Zr.

The Ni-based alloy of the present invention having the above-described alloy component composition is excellent in high temperature oxidation resistance and high temperature halogen gas corrosion resistance, and has excellent hot forgeability. It can be used as a constituent member such as a baking tray of a lithium battery positive electrode material, a CVD device member, a PVD device member, an LCD device member, and a semiconductor manufacturing device member.
In addition to the above, the Ni-based alloy of the present invention includes a Ni-based alloy plate, tube, wire, cast material, forged material, and jigs and members processed and formed from these, members for oxidation furnaces, firing For various applications that require high-temperature oxidation resistance and hot forgeability, such as furnace members, silver tin firing process muffles, cemented carbide manufacturing process jigs, special powder (LED raw materials, etc.) firing process retorts, etc. It is of course possible to use it.

As described above, since the Ni-based alloy of the present invention has extremely excellent hot forgeability, high-temperature oxidation resistance and high-temperature halogen gas corrosion resistance, the firing tray of the chip capacitor made from the Ni-based alloy of the present invention The firing tray of the lithium battery positive electrode material has little generation of oxide scale, requires no maintenance, has a long life and can be reduced in cost, and is a CVD apparatus member and PVD apparatus manufactured from the Ni-based alloy of the present invention Since the generation of particles due to corrosion is suppressed even in halogen gas-based process environments, the members, LCD device members, and semiconductor manufacturing device members contribute to improving the yield of manufactured semiconductors and FPDs, and have excellent industrial effects. It is something that demonstrates.

  Examples of the present invention will be described below.

The raw materials are blended in a predetermined ratio, and these are vacuum melted and vacuum cast in a high frequency melting furnace, and have the alloy component composition shown in Table 1 and have a diameter of 300 mm. The ingot which consists of was produced.
Subsequently, hot forging was performed in a state where the ingot was heated to a temperature of 1200 ° C. to produce a plate-like body having a thickness of 25 mm and a width of 300 mm.
This hot-forged plate-like body was further hot-rolled at a temperature of 1200 ° C., processed into a hot-rolled plate having a width: 300 mm, and further subjected to a heat treatment for rapidly cooling the hot-rolled plate from 900 ° C. Thereafter, the oxide scale on the surface was removed, and a plate material having a thickness of 3 mm was finally produced.

For comparison, the raw materials were blended at a predetermined ratio, and these were vacuum-melted and vacuum-cast in a high-frequency melting furnace, had the alloy composition shown in Tables 2 and 3, and had a diameter of 300 mm. Ingots made of comparative Ni-base alloys 1 to 12 and conventional Ni-base alloy 1 were prepared.
The conventional Ni-based alloy 1 shown in Table 3 is a Ni-based alloy having the alloy component composition described in Patent Document 1. Similarly, the conventional Ni-based alloy 2 shown in Table 3 has a chemical composition of Cr: 15.5%, Fe: 9%, the balance Ni and inevitable impurities in weight% that has been used in many semiconductor manufacturing equipment. It is an alloy called so-called 600 alloy (UNS N06600).
About the ingot which consists of said comparative Ni base alloy 1-12 and the conventional Ni base alloy 1, the hot forging similar to this invention Ni base alloy 1-15, hot rolling, heat processing, and the oxide scale removal process were performed. Conventional Ni-based alloy 2 was purchased as a commercially available 3 mm plate.
In addition, about what generate | occur | produced the forge crack during hot forging, it described as "the crack generation during hot forging" in Table 2, Table 3.

Next, among the Ni-based alloys 1 to 15 of the present invention, the comparative Ni-based alloys 1 to 12 and the conventional Ni-based alloy 1, it is possible to produce a plate material having a thickness of 3 mm without generating forging cracks during hot forging. About what was made and the conventional Ni base alloy 2, the evaluation test of high temperature oxidation resistance was implemented as follows.
First, 50 × 25 × 3 mmt corrosion test pieces were produced from the plate material having a thickness of 3 mm produced as described above.
Next, the surfaces of these test pieces were polished to finally give a water-resistant emery paper # 400 finish.
Next, the polished sample was degreased by being kept in an ultrasonic vibration state in acetone for 5 minutes. Next, an exposure test at 750 ° C. × 30 hours was repeated 10 times for each corrosion test piece made of the Ni-based alloys 1 to 15 of the present invention, the comparative Ni-based alloys 1 to 12 and the conventional Ni-based alloys 1 and 2. The thickness of the oxide film was measured by observing the cross section of the corrosion test piece after the test with an optical microscope.

Further, for each test piece made of the inventive Ni-based alloys 1-15, comparative Ni-based alloys 1-12, and conventional Ni-based alloys 1 and 2 separately prepared by the same method, a gas exhaust port in the plasma CVD chamber was used. The amount of particles when attached in the vicinity and exposed to a high-temperature fluorine-based gas was compared. The test conditions are as follows. Plasma was generated for 60 seconds by applying high-frequency power of 750 W between the pressure in the chamber: 5 torr, cleaning gas: C ₂ F ₆ , and the electrodes. The number of particles was measured by a particle counter attached to a gas exhaust port near the test piece. At this time, the temperature in the chamber was maintained at 500 ° C. Evaluation was made by comparing the conventional Ni-based alloy 2 as 100%.
Tables 1 to 3 show the measurement results.

From the results shown in Tables 1 and 2, among the comparative Ni-base alloys 1 to 12 having an alloy composition deviating from the present invention, the comparative Ni-base alloys 2, 4, and 9 to 12 were subjected to hot forging. Since cracking occurred, the test did not reach the high temperature oxidation resistance evaluation test or high temperature halogen gas corrosion resistance evaluation test. Similarly, with respect to the comparative Ni-based alloy 7, since the occurrence of fine cracks was confirmed after hot forging, the high-temperature oxidation resistance evaluation test and the high-temperature halogen gas corrosion resistance evaluation test were not achieved.
In particular, the comparative Ni-based alloy 9 added with Zr alone, the comparative Ni-based alloy 11 added with B alone, and the comparative Ni-based alloys 10 and 12 in which either Zr or B is outside the scope of the present invention, Also, cracks occurred during hot forging and the hot forgeability was poor.
Further, the comparative Ni-base alloys 1 and 3 that were capable of hot forging both had a thick oxide film, and compared with the Ni-base alloys 1 to 15 of the present invention, high-temperature oxidation resistance. It was inferior to. Further, the comparative Ni-base alloys 5, 6, and 8 that were capable of hot forging all had high particle generation rates, and were inferior in high-temperature halogen gas corrosion resistance as compared with the Ni-base alloys 1 to 15 of the present invention. It was a thing.
Further, from the results shown in Tables 1 and 3, it can be seen that the Ni-based alloys 1 to 15 of the present invention are superior in hot forgeability compared to the conventional Ni-based alloy 1 which is a conventional material. In addition, since the conventional Ni-based alloy 1 also cracked during hot forging, it did not reach the high temperature oxidation resistance evaluation test. Further, it can be seen that the high temperature halogen gas corrosion resistance is superior to the conventional Ni-based alloy 2 which is a conventional material.
From the results shown in Tables 1 to 3, the Ni-based alloy of the present invention is particularly excellent in hot forgeability and high temperature resistance because the alloy components B and Zr are respectively added in predetermined amounts at the same time. It turns out that it is excellent in oxidation resistance and high temperature halogen corrosion resistance.

Since the Ni-based alloy of the present invention is excellent in hot forgeability and excellent in high temperature oxidation resistance and high temperature halogen gas corrosion resistance, a chip capacitor firing tray, a lithium battery positive electrode material firing tray, and a CVD apparatus It is suitable as a member constituting a member, a PVD device member, an LCD device member, and a semiconductor manufacturing device member.
In addition to this, among the Ni-base alloy plate, tube, wire, cast material, forged material, and jigs and members processed and formed from these, an oxidation furnace member, a firing furnace member, silver tin firing It can be applied as a structural member for various applications that require high-temperature oxidation resistance and hot forgeability, such as process muffles, cemented carbide manufacturing process jigs, and retorts for firing special powders (such as LED raw materials). Is possible.

Claims (3)

In weight% Al: 2.0-5.0%,
Si: 0.1 to 2.5%
Cr: 0.8-4.0%
Mn: 0.1 to 1.5%
B: 0.001 to 0.01%,
Zr: 0.001 to 0.1% is contained,
A Ni-based alloy excellent in hot forgeability, high-temperature oxidation resistance and high-temperature halogen gas corrosion resistance, the balance being Ni and inevitable impurities. Al: 3.6-4.2% by weight%
Si: 1.1 to 1.7%,
Cr: 1.6 to 2.3%,
Mn: 0.2 to 0.7%
B: 0.001 to 0.007%,
Zr: 0.001 to 0.06% is contained,
The Ni-based alloy having excellent hot forgeability, high-temperature oxidation resistance and high-temperature halogen gas corrosion resistance according to claim 1, wherein the balance is made of Ni and inevitable impurities. A chip capacitor, a firing tray of a lithium battery positive electrode material, a CVD device member, a PVD device member, an LCD device member, and a semiconductor manufacturing device member made of the Ni-based alloy according to claim 1.