JPS63297533A - High corrosion resistant amorphous nickel alloy for high temperature concentrated sulfuric acid - Google Patents

Abstract

PURPOSE:To produce an amorphous nickel alloy having high corrosion resistance to high temp. concd. sulfuric acid by incorporating a specific amt. of Ta into Ni. CONSTITUTION:The amorphous nickel alloy contg., by atom., 25-65% Ta and the balance consisting substantially of Ni is prepd.; or the amorphous nickel alloy contg. 10-40% Ta, total 25-50% of one or two kinds between Cr and Mo with Ta and the balance consisting substantially of Ni is prepd. Said alloy forms a stable protective film and exhibits high corrosion resistance in a severe corrosive environment such as high temp. concd. sulfuric acid having poor oxidizing power.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a highly corrosion-resistant amorphous nickel alloy suitable as a corrosion-resistant material in harsh corrosive environments such as high-temperature concentrated sulfuric acid.

Prior Art Currently, Hastelloy C and the like are used as structural materials for high-temperature concentrated sulfuric acid plants, but even these materials do not have sufficient corrosion resistance in highly corrosive environments such as high-temperature concentrated sulfuric acid.

On the other hand, the present inventors have previously discovered a highly corrosion-resistant amorphous nickel-based alloy that is resistant to pitting corrosion, crevice corrosion, and general corrosion, and has filed an application as Japanese Patent Application No. 132290/1983. This consists of the following four inventions.

(1) 5-40 at.% Cr and 15-35 at.%
A highly corrosion-resistant amorphous nickel-based alloy that is resistant to pitting corrosion, crevice corrosion, and general corrosion, and is resistant to harsh corrosive environments.

(2) 5-40 at.% Cr and 15-35 at.%
containing P of 3 atomic % or less, A1 of 3 atomic % or less, Mo of 10 atomic % or less, and one or more types of Fe of less than 40 atomic % (the total of rSPSA1, Mo, and Fe is less than 60 atomic %). A highly corrosion-resistant amorphous nickel-based alloy that is resistant to pitting corrosion, crevice corrosion, and general corrosion, with the remainder essentially consisting of Ni.

(3) C15iS containing 5 to 40 atom% of Cr and 5 to 35 atom% of P, and further containing 20 atom% or less of each
Contains one or more types of B in a total of 15 to 35 atomic percent of PSC, Si, and B, with the remainder substantially consisting of Ni, and is resistant to pitting corrosion, crevice corrosion, and general corrosion that can withstand severe corrosive environments. Highly corrosion-resistant amorphous nickel-based alloy.

(4) C1Si containing 5 to 40 atomic % of Cr and 5 to 35 atomic % of P, and further 20 atomic % or less of each,
Contains one or more types of B in a total of 15 to 35 at% of PlCSSilB, and 3 at% or less^111
Contains one or more types of Mo140 at% less than 0 at%, Fe, Cr5P, C,5iSB, Al,
The total content of Mo and Fe is less than 60 atomic %, and the remainder is substantially X.
A highly corrosion-resistant amorphous nickel-based alloy that is resistant to pitting corrosion, crevice corrosion, and general corrosion, and is resistant to harsh corrosive environments.

Furthermore, the present inventors have discovered a highly corrosion-resistant amorphous nickel alloy that can be used in harsh corrosive environments containing boiling concentrated nitric acid or oxidizing agents, and have filed a patent application for a highly corrosion-resistant amorphous nickel alloy comprising the following four inventions. A patent application was filed as No. 1986-51036.

(1) Contains 15-80 atomic% of Ta, the remainder being essentially Ni
Highly corrosion resistant amorphous alloy.

(2) Contains Ta and one or more elements selected from the group consisting of Ti5Zr, Nb, and W, with the remainder consisting essentially of Ni, with a Ta content of 10 atomic % or more, One or more elements selected from Ta
A highly corrosion-resistant amorphous alloy having a total content of 15 to 80 atomic %.

(3) Contains Ta, Fe and/or Co, and the remainder is substantially Ni, with a content of 15-80 at.% Ta, 75 at.% or less of Fe and/or Co, and 7 at.% Ni. A highly corrosion resistant amorphous alloy with a corrosion resistance of at least atomic percent.

(4) Contains Ta, one or more elements selected from the group consisting of Ti5Zr, Nb, and W, and Fe and/or Co, with the remainder substantially consisting of lfi, and the content is Ta and Ti. , Zt, Nb and W in a content of 15 to 80 atomic %, Ta is 10 atomic % or more, and Fe and/or Co is 75 atomic % or less A highly corrosion-resistant amorphous alloy containing 7 atomic % or more of Ni.

Furthermore, the present inventors have discovered a highly corrosion-resistant amorphous alloy that can be used in harsh corrosive environments such as boiling concentrated hydrochloric acid, and have published Japanese Patent Applications No. 172,860/1986 and Japanese Patent Application No. 1728/1982.
A patent application was filed as 61.

Japanese Patent Application No. 60-172860 consists of the following 16 inventions.

(1) A highly corrosion-resistant amorphous alloy containing 30 to 80 atomic % of Ta, with the balance essentially consisting of Ni.

(2) A highly corrosion-resistant amorphous alloy containing 12 atomic % or more of Ta, the total of Ta and Nb being 30-80 atomic %, and the remainder being substantially Ni.

(3) Contains 25 atom% or more of Ta, Ti, Z
One or more elements selected from the group r5Cr and T
A highly corrosion-resistant amorphous alloy in which the total amount of a and a is 30 to 80 atomic %, and the remainder is substantially made of Ni.

(4) Contains 12 atomic % or more of Ta, the total of Ta and Nb is 25 atomic % or more, and contains IFI or two or more elements selected from the group of Ti, Zr, and Cr, and Ta and N.
A highly corrosion-resistant amorphous alloy containing 30 to 80 atomic % in total with b and the remainder being substantially Ni.

(5) Highly corrosion-resistant amorphous alloy containing 30-80 atomic % or more of Ta and 2 atomic % or more of Ili, with the remainder substantially consisting of one or both of Fe and CO, making the total 100 atomic % .

(6) Contains 12 atomic % or more of Ta, the total of Ta and Nb is 30-80 atomic % or more, contains 2 atomic % or more of Ni, and the remainder is substantially one of Fe and CO. Or a highly corrosion-resistant amorphous alloy consisting of two types, the total of which is 100 atomic %.

(7) Contains 25 atomic% or more of Ta, Ti, Zr
The total of one or more elements selected from the 5CrO group and Ta is 30-80 atomic %, contains 2 atomic % or more of Ni, and the remainder is substantially one of Fe and CO. Or a highly corrosion-resistant amorphous alloy consisting of two types, the total of which is 100 atomic %.

(8) Contains 12 atomic % or more of Ta, the total of Ta and Lb is 25 atomic % or more, and contains II or two or more elements selected from the group of Ti, Zr, and Cr, and Ta and Nb.
and 3o-go atomic% in total, further containing 2 atomic% or more of Ni, and the remainder substantially consisting of one or two of Fe and Co, making the total 100 atomic%. Corrosion-resistant amorphous alloy.

(9) A highly corrosion-resistant amorphous alloy containing 20 atomic % or more and less than 80 atomic % of Ta and 7 atomic % or less of P, with the remainder substantially consisting of 20 atomic % or more of Ni, for a total of 100 atomic %.

(10) Contains 7 atomic % or more of Ta, the total of Ta and Wb is 20 atomic % or more and less than 80 atomic %, contains 7 atomic % or less of P, and the balance is substantially 20 atomic % or more of N.
A highly corrosion-resistant amorphous alloy consisting of i, with a total of 100 atomic %.

(11) Contains 15 atomic% or more of Ta, Ti%2r
, one or more elements selected from the group of Cr and T
The total with a is 20 atom % or more and less than 80 atom %, and 7
A highly corrosion-resistant amorphous alloy containing atomic percent or less of P, and the remainder being substantially Ni, for a total of 100 atom percent.

(12) Contains 7 atomic % or more of Ta, the total of Ta and Nb is 16 atomic % or more, and Tiq lrs C
One or more elements selected from the group r, Ta and N
The total with b is 20 atomic % or more and less than 80 atomic %, and 7
A highly corrosion-resistant amorphous alloy containing atomic percent or less of P, and the remainder being substantially Ili for a total of 100 atom percent.

(13) Ta of 20 atomic % or more and less than 80 atomic %,
Contains 2 atomic % or more of Ni and 7 atomic % or less of P, and the total of the substantial balance of one or two of Fe and CO and Nf is 20 atomic % or more, and the total is 100 atomic %. A highly corrosion-resistant amorphous alloy.

(14) The total of Ta and Nb of 7 atomic % or more is 20
N at least 80 at%, but at least 2 at%
A highly corrosion-resistant amorphous alloy containing i and 7 atomic % or less of P, the substantial balance of one or both of Fe and Co, and Ni in a total of 20 atomic % or more, making the total 100 atomic %.

(15) Contains Ta with an original atomic weight of Is or more, Ti%zr
, one or more elements selected from the group of Cr and T
The total amount with a is 20 atomic % or more and less than 80 atomic %,
Contains 2 atomic % or more of Ni, 7 atomic % or less of P, and the total of the substantial balance of IN or two of Fe and CO and Ni is 20 atomic % or more, and the total is 100 atomic %. Corrosion-resistant amorphous alloy.

(16) Contains 7 atomic % or more of Ta, the total of Ta and Nb is a<ta atomic % or more, and contains Ti%Zr, C
One or two selected from the group r? Elements with i1 or higher and Ta
and Nb in an amount of 20 at% or more and less than 80 at%, and further contains 2 at% or more of Ni and 7 at% or less of P, with one or two of re and Co being the substantial remainder. N
A highly corrosion-resistant amorphous alloy in which the total amount of i and i is 20 atomic % or more, and the total is 100 atomic %.

Furthermore, Japanese Patent Application No. 172861/1986 consists of the following 16 inventions.

(1) 20-50 at% Ta and 10-23 at%
A highly corrosion-resistant amorphous alloy containing P and the remainder being substantially Ni.

(2) A highly corrosion-resistant amorphous alloy containing 7 atomic % or more of Ta, the total of Ta and Nb being 20-50 atomic %, and 10-23 atomic % of P with the remainder being substantially Ni.

(3) Contains 15 atomic % or more of Ta, Ti, Zr
and Cr, the total amount of Ta and one or more elements selected from the group of Cr is 20-50 at%,
A highly corrosion-resistant amorphous alloy containing 3 at.% of P and the remainder being substantially Ni.

(4) Contains 8 atomic % or more of Ta, the total of Ta and Nb is 16 atomic % or more, and Ta and Nb are combined with one or more elements selected from the group of Ti, lr and Cr. A highly corrosion-resistant amorphous alloy containing P in a total content of 20-50 atomic %, 10-23 atomic % P, and the remainder substantially Ni.

(5) 20-50 at% Ta and 10-23 at%
of P and 2 at % or more of Ni, with the substantial balance being F
Consists of one or two types of e and Co, totaling 100
Highly corrosion resistant amorphous alloy with atomic percent.

(6) Contains 7 atomic % or more of Ta, the total with Ta%Nb is 20-50 atomic %, and 10-23 atomic % of P
A highly corrosion-resistant amorphous alloy containing 2 atomic % or more of Ni, and the substantial balance consisting of one or both of Fe and Co, with a total of 100 atomic %.

(7) Contains 15 atomic % or more of Ta, the total of Ta and one or more elements selected from the group of Ti5Zr and Cr is 20-50 atomic %, and 10-23 atomic %
A highly corrosion-resistant amorphous alloy containing atomic % of P and 2 atomic % or more of Ni, with the substantial balance consisting of one or both of Fe and Co, with a total of 100 atomic %.

(8) Contains 8 atomic % or more of Ta, the total of Ta and Nb is 16 atomic % or more, and one or more elements selected from the group of Ti, Zr and Cr and Ta and N
The total with b is 20-50 at%, contains 10-23 at% of P and 2 at% or more of Ni, and the substantial balance consists of one or two of Fe and Go, and the total is 10-23 at% of P and 2 at% or more of Ni.
Highly corrosion resistant amorphous alloy with 0 atomic %.

(9) 11 containing 20-50 atomic % Ta and 0.05 atomic % or more P and selected from the group of B, Si and C
! Or a highly corrosion-resistant amorphous alloy in which the total of 2p1 or more and P is 1023 atomic %, and the remainder is substantially Ni.

(10) Contains 7 atomic % or more of Ta and 0.05 atomic % or more of P, the total of Ta and Nb is 20-50 atomic %, and tm or 2N or more selected from the group of B5Si and C A highly corrosion-resistant amorphous alloy in which the total amount of P and P is 10-23 atomic %, and the remainder is substantially Ni.

(11) Contains 15 atomic % or more of Ta and 0.05 atomic % or more of P, and the total of Ta and one or more elements selected from the group of Ti, Zr, and C is 20-5
0 atomic %, and the total of one or more selected from the group of B, Si and C and P is 10-23 atomic %, with the remainder being substantially Ni. Amorphous alloy.

(12) Contains 8 atomic % or more of Ta and 0.05 atomic % or more of P, the total of Ta and Nb is 16 atomic % or more, and one or two selected from the group of Ti, Zr, and Cr. The total of the above elements and Ta and Nb is 20-5
0 atomic %, and the total of one or more selected from the group of B, Si and C and P is 10-23 atomic %, with the remainder being substantially Ni. Amorphous alloy.

(13) Contains 20-50 at% Ta, 0.05 at% or more P, and 2 at% or more Ni, B, Si
The total of one or more elements selected from the group of
Highly corrosion resistant amorphous alloy with 0.00 atomic %.

(14) Contains 7 at% or more Ta, 0.05 at% or more P, and 2 at% or more N1, the total of Ta and Nb is 20-50 at%, and contains B5Si and C. One or more elements selected from the group and P
The total amount of
Highly corrosion resistant amorphous alloy with 0.00 atomic %.

(15) Ta of 15 at% or more, 0.05 at%
Contains P of 2 atomic % or more and Ni of 2 atomic % or more, Ti5Zr
and Cr, the total content of Ta and one or more elements selected from the group of Cr is 20-50 at%, and
, the total of one or more elements selected from the group of Si and C and P is 10-23 atomic %, and the substantial balance is composed of one or two of Fe and CO, and the total is 100 Highly corrosion resistant amorphous alloy with atomic percent.

(16) Contains 8 at% or more Ta, 0.05 at% or more P, and 2 at% or more Ni, the total of Ta and Wb is 16 at% or more, and contains Ti, Zr, and Cr.
one or more elements selected from the group of
The total amount of B5S and b is 20-50 atomic%, and
The total of one or more selected from the group of i and C and P is 10-23 atomic %, and the substantial balance is F.
Consists of one or two types of e and Co, totaling 100
Highly corrosion resistant amorphous alloy with atomic percent.

Furthermore, the present inventors have discovered that an amorphous nickel alloy with high corrosion resistance can be obtained even in harsh corrosive acids such as high-temperature concentrated phosphoric acid. did.

Japanese Patent Application No. 61-225435 consists of the following four inventions.

(1) 10-30 at% Mo and 15-23 at% P
A highly corrosion-resistant amorphous nickel alloy containing Ni and the remainder being substantially Ni.

(2) Contains 10-30 atomic% of Mo, and further contains B, S
A highly corrosion-resistant amorphous nickel alloy containing a total of 7 at % or less of any one or two types of i and 15 to 23 at % in total of P, with the balance substantially consisting of Ni.

(3) Contains 10-30 atom% Mo, 30-40 atom% Cr, further contains 8-20 atom% P, and the balance is substantially N.
A highly corrosion-resistant amorphous nickel alloy consisting of i.

(4) Contains 10-30 atom% of Mo, 30-40 atom% of Cr, and further contains 8-20 atom% of one or two of B and Si in total of 7 atom% or less and P. A highly corrosion-resistant amorphous nickel alloy consisting essentially of Ni.

Japanese Patent Application No. 61-225436 consists of the following seven inventions.

(1) Contains 20-60 atomic% of Ta, with the remainder being substantially Ni
Highly corrosion resistant amorphous nickel alloy.

(2) Taf&-1-25 atomic% and P 15-23
A highly corrosion-resistant amorphous nickel alloy containing atomic% of nickel and the remainder being substantially nickel.

(3) Contains 1-25 atom% of Ta, and further contains 15-23 atom% of P in total of 7 atom% or less of any one or two of B and Si, and the remainder consists essentially of Ni. Highly corrosion resistant amorphous nickel alloy.

(4) 10-40 at% Cr and 15-23 at% P
A highly corrosion-resistant amorphous nickel alloy containing Ni and the remainder being substantially Ni.

(5) Contains 10-40 atom% of Cr and further contains B and Si
A highly corrosion-resistant amorphous nickel alloy containing a total of 7 at % or less of any one or two of the above and 15 to 23 at % of P in total, with the balance substantially consisting of Ni.

(6) The total of Ta of 20 at% or less and Cr is 10-4
A highly corrosion-resistant amorphous nickel alloy containing 0 atomic %, 15-23 atomic % P, and the remainder substantially Ni.

(7) The total of Ta of 20 at% or less and Cr is 10-4
A highly corrosion-resistant amorphous nickel alloy containing 0 atomic %, a total of 7 atomic % or less of any one or two of B and Si, and 15 to 23 atomic % in total of P, with the balance substantially consisting of Ni.

Problems to be solved by the invention High-temperature concentrated sulfuric acid does not have the high oxidizing power of high-temperature concentrated nitric acid, so it is difficult to form a stable passive film, and although it does not have the same effect of destroying the passive film as high-temperature hydrochloric acid, sulfate ions Because it has a film-destroying effect similar to that of chlorine ions, it is more corrosive than concentrated phosphoric acid at the same temperature, and there are few ordinary metal materials that can withstand use. There is a need for various new metal materials that can withstand use in such a corrosive environment.

Means for Solving the Problems The object of the present invention is to use a method that is non-oxidizing and does not passivate metals, like high-temperature concentrated sulfuric acid, and that can withstand extremely harsh corrosive environments that have a film-destroying effect. Our goal is to provide alloys.

Normally, alloys are crystallized in the solid state, but if you apply a method that prevents the formation of long-period regularity in the atomic arrangement during the solid state process, such as by limiting the alloy composition and solidifying by ultra-rapid cooling from the molten state, the crystal structure An amorphous structure resembling that of a liquid is obtained, and such an alloy is called an amorphous alloy.

Amorphous alloys are mostly homogeneous single-phase supersaturated solid solution alloys that have significantly higher strength than conventional practical metals and exhibit various properties, including unusually high corrosion resistance, depending on their composition. The present inventors conducted research to utilize the characteristics of such amorphous alloys and found that they are susceptible to pitting corrosion, crevice corrosion, and general corrosion even in highly corrosive aqueous solutions such as strong acids or aqueous solutions containing high concentrations of chlorine ions. They discovered a highly corrosion-resistant amorphous nickel-based alloy that could be used in harsh corrosive environments that contain boiling concentrated nitric acid or oxidizing agents. He discovered this and filed a patent application as Japanese Patent Application No. 60-51036, and furthermore,
A highly corrosion-resistant amorphous alloy that can be used in harsh corrosive environments such as boiling concentrated hydrochloric acid was discovered, and patent application No. 80-17286 was filed.
No. 0 and Japanese Patent Application No. 172861/1983. Next, the present inventors discovered an amorphous nickel alloy with high corrosion resistance that can withstand high-temperature concentrated phosphoric acid.
No. 5435 was filed.

Furthermore, as a result of continuing research on the corrosion resistance of amorphous alloys, the present inventors have developed an amorphous alloy that exhibits high corrosion resistance due to a combination of certain elements even in high-temperature concentrated sulfuric acid, where a passive film is difficult to form and the film is easily destroyed. A nickel alloy was discovered and the present invention was achieved.

The present invention consists of the first to eighth inventions shown in claims 1 to 8, and the constituent elements and contents of these first to eighth inventions are shown in Table 1 below. Show rate.

Function: Amorphous alloys obtained by various methods for producing amorphous alloys, such as ultra-rapid solidification of molten alloys having the above composition or sputter deposition, are single-phase alloys in which the above-mentioned elements are uniformly dissolved in solid solution. Therefore, the amorphous nickel alloy of the present invention produces a protective film that is extremely uniform and guarantees high corrosion resistance.

High temperature'a that makes it difficult to form a passive film and easily destroys the film
Since metallic materials easily dissolve in sulfuric acid solutions, in order to use metallic materials in such an environment, it is necessary to provide the metallic materials with the ability to form a stable protective film. This is achieved by creating an alloy containing the required amount of effective elements. However, in the case of crystalline metals, adding a large amount of various alloying elements often results in a multiphase structure with different chemical properties, and it may not be possible to achieve the desired corrosion resistance.

Moreover, the occurrence of chemical non-uniformity is rather detrimental to corrosion resistance.

In contrast, the amorphous nickel alloy of the present invention is a homogeneous solid solution and uniformly contains the necessary amount of effective elements that can form a stable protective film. , exhibits sufficiently high corrosion resistance.

In other words, the conditions that a metal material must have that can withstand high-temperature concentrated sulfuric acid, where it is difficult to form a passive film and the film is easily destroyed, are as follows:
The material has a high ability to form a protective film that is stable even in such environments and is uniformly formed on the material. This is achieved with the alloy composition of the present invention, and the fact that the alloy develops an amorphous structure makes it possible to create alloys with complex compositions as single-phase solid solutions, ensuring uniform protective coating formation. .

Next, the reason for limiting the composition of each component in the present invention will be described.

Ni is an element that forms the basis of the alloy of the present invention, and is an element that forms an amorphous structure when a predetermined amount of Ta or at least one of Mo and Cr coexists with Ta, and P, B5Si, etc. Elements that form an amorphous structure even when they coexist with metalloids. Furthermore, L is an element that assists the action of TaSMo and Cr, which are responsible for corrosion resistance.

Ta, Mo, and Cr are all elements that form a protective film and provide corrosion resistance. Among these, the total of Ta or Ta and either Cr and Mo or two types is 25
-50 atomic %, a metal-metal alloy of these and Ni can form an amorphous structure. The total amount is 25-50 at.%.

P is an effective element that helps form a protective film of Ta, Mo, Cr, etc. Further, if a Ni alloy contains a sufficient amount of metalloid elements, it will form an amorphous structure as a metal-metalloid alloy. However, adding an excessive amount of metalloid elements can actually prevent the formation of an amorphous structure.

Therefore, in order to produce an amorphous structure, the upper limit of the metalloid elements in the third, fourth, sixth and seventh terms of the present invention is set at 23 at %. Also, the amount of Mo in the alloy is 1
0-30 atomic%, not as much N as metal-metal alloys
In the case of an i metalloid alloy, it is desirable to contain 15 atomic % or more of the metalloid to form an amorphous structure. Therefore, in the fourth and seventh terms of the present invention, the lower limit of the metalloid element is 15 at %.

On the other hand, as a metal-metal alloy, it does not become amorphous, but like an amorphous metal-metal alloy, it contains a large amount of Mo,
When Cr and Ta are included, an amorphous structure is created by adding a small amount of metalloid elements, so the lower limit of the metalloid elements is 8 at % in the third, fifth, sixth and eighth terms of the present invention. do. Furthermore, when a large amount of metal elements are included as in Items 5 and 8 of the present invention, it is rather difficult for the metal-metalloid alloy to become amorphous, so the upper limit of the metalloid element must be kept at 15 at %. On the other hand, B and Si are also effective elements for forming an amorphous structure along with P, but since P is necessary for an amorphous metal-metalloid alloy to ensure corrosion resistance, The content of one or both of B and Si that substitutes P is 7 atomic % or less.

Ta is an extremely effective element for forming a passive film that guarantees corrosion resistance, and the composition range that guarantees the formation of an amorphous structure is set at 25 to 65 at % in Item 1 of the present invention. Similarly, when containing 10-40 at% of Ta, Ct
The total of one or two of Mo and Ta is 2
If the content is 5 to 50 atomic %, an amorphous structure will result, so in the second aspect of the present invention, the total of one or both of Cr and No and Ta is set to 25 to 50 atomic %.

Mo is an element that guarantees corrosion resistance, and sufficient corrosion resistance can be obtained by containing 10 to 30 at % of Mo in the amorphous metal-metalloid alloys as in Items 4 and 7 of the present invention. On the other hand, items 5 and 8 of the present invention
In the case of an alloy that is similar to a metal-metal alloy with a small amount of metalloid elements added, it is necessary to add enough metal elements to form an amorphous structure, and it is possible to form an amorphous structure while ensuring corrosion resistance. In order to achieve this, it is necessary to contain a total of 45 to 70 atom % of any one or both of Cr and Mo.

Moreover, the amorphous nickel alloy of the present invention is 10 atomic %
Even if the following Nb and W and 5 atomic % or less of Ti1Zr are included, the object of the present invention is not hindered.

The amorphous alloy of the present invention can be produced by various methods that are already widely used, including methods of ultra-rapidly solidifying a liquid alloy, various methods of forming an amorphous alloy through a gas phase, and methods of forming a solid long material by ion implantation. Any method for producing an amorphous alloy, such as a method for destroying a periodic structure, may be used.

- As an example, an apparatus for producing the amorphous alloy of the present invention is shown in FIG. The area surrounded by dotted lines is evacuated and then filled with inert gas. In the figure, 2 is a quartz tube with a vertical nozzle 3 at its lower end, and through an inlet I provided at the upper end of this quartz tube 2, raw material 4 and an inert gas for preventing oxidation of the raw material can be introduced. can. Said sample 4
A heating furnace 5 is installed around the quartz tube 2 to heat it.

A high speed rotating roll 7 is placed vertically below the nozzle 3 and is rotated by a motor 6. To produce an amorphous alloy, a raw material 4 having a predetermined composition is placed in a quartz tube 2, the apparatus is first evacuated to about 10@-5 Torr, and then filled with inert gas. Next, the raw material 4 is heated and melted in the heating furnace 5, and the molten metal is heated to 1000 m
Roll 7 rotating at high speed at 10000 r, p, m
This is done by injecting pressurized inert gas onto the outer peripheral surface of the By this method, for example, a thickness of 0.1
The amorphous alloy of the present invention can be obtained as a long thin plate with a width of 10xx and a length of about r/1 m.

Example Raw material metals were mixed to have the compositions shown in Table 2, and raw material alloys were produced in an argon arc melting furnace. By remelting these alloys in an argon atmosphere and ultra-rapidly solidifying them using the single roll method shown in FIG.
01-0.051℃, width 1-322, length 3-20+
An amorphous alloy thin plate of y was obtained.

The formation of an amorphous structure was confirmed by X-ray diffraction. The surface of these alloy samples was covered with silicon carbide paper.
Polished to No. 00 in cyclohexane.

Next, an alloy sample of a predetermined length was cut out, immersed in a solution of about 80% H2SO at 100°C for 7 to 10 days, and its weight before and after immersion was measured using a microbalance.

The results obtained are shown in Table 3.

Table 2 Alloy composition (atomic %) Invention No. Sample No. Ni Ta Mo C
r P Si B invention No. sample! to N
i Ta Mo Cr P Si B30
63 15 1.5 5
28 32 38 3015+, 0
3 4 Table 3 Example of corrosion rate (g/hx') of the alloy of the present invention in 80% sulfuric acid solution at 100°C Sample No.

1 0.0083 2 0.0056 3 0.0031 4 0.0019 5 0.0010 6 0.0101 7 0.0035 8 0.0023 9 0.0020 10 0.0005 11 0.0057 12 0.0015 13 0.0010 14 0.0211 15 0.0193 16 0.0200 17 0.0225 Sample No.

18 0.0015 19 0.0013 20 0.0225 21 0.0171 22 0.0153 23 0.0167 24 0.0155 25 0.0129 26 0.0233 27 0.031g 28 0.0027 29 0.0224 3 0 0 .0152 31 0.0144 32 0.0173 33 0.0164 The corrosion rate of the amorphous alloy of the present invention is extremely low. Furthermore, after the alloy of the present invention was subjected to an immersion test, the alloy surface was analyzed using X-ray photoelectron spectroscopy.
It has been found that a protective film of hydrated oxide or hydrated oxyhydroxide containing mM r and Mo is formed, which is responsible for the high corrosion resistance of the alloy of the present invention.

Effects of the Invention As detailed above, the amorphous nickel alloy of the present invention is a highly corrosion-resistant alloy that forms a stable protective film and does not corrode even in highly corrosive environments such as high-temperature a-sulfuric acid, which has poor oxidizing power. .

Furthermore, since any of the amorphous alloy production techniques that are already widely used can be applied to the production of the alloy of the present invention, there is no need for special equipment, and the alloy of the present invention has excellent practicality. .

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of an apparatus for producing the amorphous alloy of the present invention. ■ = Raw material inlet, 2: Quartz tube, 3: Nozzle section, 4: Raw material, 5: Heating furnace, 6: Motor, 7: High speed rotating roll.

Claims (8)

[Claims] (1) Contains 25-65 atomic% of Ta, the remainder being essentially Ni
A highly corrosion-resistant amorphous nickel alloy for high-temperature concentrated sulfuric acid. (2) 10-40 atomic % of Ta and 25-50 atomic % of one or both of Cr and Mo in total amount with Ta
A highly corrosion-resistant amorphous nickel alloy for high-temperature concentrated sulfuric acid, the remainder of which is essentially Ni. (3) The total amount of Ta of 1 atomic % or more and Mo with Ta is 1
A highly corrosion-resistant amorphous nickel alloy for use in high-temperature concentrated sulfuric acid, containing 0 to 40 atomic %, further containing 8 to 23 atomic % of P, and the remainder consisting essentially of Ni. (4) 10-30 at% Mo and 15-23 at% P
A highly corrosion-resistant amorphous nickel alloy for high-temperature concentrated sulfuric acid, the remainder of which is essentially Ni. (5) Either one or two of Cr and Mo are added to 45-
70 atom% and 8-15 atom% of P, the remainder being substantially N.
A highly corrosion-resistant amorphous nickel alloy for high-temperature sulfuric acid consisting of i. (6) The total amount of Ta of 1 atomic % or more and Mo with Ta is 1
A highly corrosion-resistant amorphous material for high-temperature concentrated sulfuric acid containing 0 to 40 at%, further comprising 7 at% or less of any one or two of B and Si, and P in total of 8 to 23 at%, the remainder being essentially Ni. Nickel alloy. (7) Contains 10-30 at% of Mo, and further contains 7 at% or less of any one or two of B and Si and P in total of 1
A highly corrosion-resistant amorphous nickel alloy for use in high-temperature concentrated sulfuric acid, containing 5 to 23 atomic % and the remainder being substantially Ni. (8) Either one or two of Cr and Mo are added to 45-
Highly corrosion-resistant amorphous nickel for high-temperature concentrated sulfuric acid containing 70 at% and further 7 at% or less of any one or two of B and Si and P in total of 8-15 at%, the balance being essentially Ni. alloy.