A corrosion-resistant nickel alloy and its preparation method and application

Abstract

The present invention belongs to the technical field of alloys, and specifically relates to a corrosion-resistant nickel alloy and a preparation method and application thereof. The composition of the nickel alloy includes: Ni: 52~56wt%, Mo: 2~4wt%, Mn: 0.9~1.1wt%, Ce: 0.5~1.0wt%; Sm: 0.5~1.0wt%, Ca: 0.2~0.4wt%, and the balance is copper. The nickel alloy of the present invention significantly improves the corrosion resistance of the nickel alloy through the interaction between the components by adding modified metals Mo, Mn, Ce, Sm and Ca during the preparation process, and has better mechanical properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of alloys, and more specifically, relates to a corrosion-resistant nickel alloy and a preparation method and application thereof. Background Art

[0002] Pure nickel has good resistance to chemically active halogen gases and their hydrides, resistance to caustic media such as NaOH, KOH and resistance to reducing media corrosion, as well as good mechanical properties. It has been widely used as a corrosion-resistant metal material. However, since pure nickel's resistance to reducing acid media is still insufficient, it is not resistant to oxidizing acids and high-temperature oxidation, sulfidation and other corrosion, therefore, nickel-based corrosion-resistant alloys developed by adding Cr, Mo, W, Cu, Si and other elements with good corrosion resistance, oxidation resistance, sulfidation and other characteristics to pure nickel alone or in combination, not only maintain the good properties of nickel, but also have the good properties of alloying components.

[0003] The main Ni-based corrosion-resistant alloys in industry include Ni-Cu series, Ni-Cr series, Ni-Mo series, Ni-Cr-Mo series, etc. Among them, Ni-Cu alloy is the earliest developed Ni-based corrosion-resistant alloy. Ni and Cu can form a continuous solid solution. It has many advantages of both Ni and Cu. It is more corrosion-resistant than Cu in oxidizing media and more corrosion-resistant than Ni in reducing media.

[0004] In nickel alloys, the addition of Mo enhances the stability of the passivation film on the alloy surface, prolongs the incubation period of possible pitting corrosion, and combines with Cl ions in the medium to form an insoluble chloride salt film covering the material surface, thereby inhibiting the generation and development of pitting corrosion.

[0005] Adding Mn can form a denser corrosion product film on the alloy surface, thereby improving the corrosion resistance of the alloy. Adding rare earth and alkaline earth metals to nickel-based alloys can also improve the corrosion resistance of nickel-based alloys.

[0006] CN113403500A discloses a high-strength, high-elasticity, corrosion-resistant, high-nickel-manganese white copper alloy, which is composed of 35-45wt% Ni, 5-15wt% Zn, 3.01-5wt% Mn, 0.0001-0.1wt% P by weight, and the remainder is Cu and inevitable impurities. By adding elements such as Mn and P to the zinc white copper matrix, due to the effects of Ni, Mn and P, it forms a strong elastic interaction with the Cu matrix, thereby obtaining a high-performance nickel-manganese white copper alloy with higher strength, better corrosion resistance and excellent elasticity. Ni, Mn and P form a Ni-Mn-P ternary compound, and through the elastic interaction of this compound with the Cu matrix, the strengthening effect on the alloy is achieved, and finally the product has excellent tensile strength, elastic modulus, corrosion resistance and other comprehensive properties. The obtained alloy can achieve an elastic modulus of more than 152GPa, and has excellent corrosion resistance, and can be applied to eyeglass accessories, electromagnetic shielding components and heat dissipation components.

[0007] CN102925753A A nickel-copper alloy with high strength and high corrosion resistance and a manufacturing method thereof, the technical key points of which are: it includes electrolytic copper and electrolytic nickel as main components, adding a small amount of manganese, iron, silicon, metal magnesium, metal titanium, and impurities ≤ 0.5%. The above components are sequentially loaded into a smelting furnace through steps, and then melted, stirred, slag removed, refined, cast and formed to form a nickel-copper alloy product. The finished product has a tensile strength of 670-720Rm / MPa and an elongation of 6-7.5, which is more than 15% higher than the strength of the current domestic nickel-copper alloy, and the corrosion resistance is nearly 2 times higher. The obtained nickel-copper alloy has the characteristics of wide application and long service life, and can be used to produce plates, strips, tubes, rods, wires, and forgings. It is used in shipbuilding, chemical industry, machinery manufacturing, aerospace, electronics and other industries. In addition, the manufacturing method changes the original vacuum casting process, adopts a semi-continuous smelting method, and reduces production costs.

[0008] CN106048438A discloses a corrosion-resistant copper-nickel alloy steel and its application in drilling drill pipes, wherein the chemical composition and mass percentage are: carbon 0.35-0.45%, silicon 1.3-1.7%, manganese 0.8-1.4%, nickel 1.2-1.8%, tungsten 2.1-2.5%, phosphorus 0.01-0.03%, sulfur 0.03-0.05%, molybdenum 0.02-0.06%, chromium 0.35-0.55%, rubidium 0.08-0.12%, rhenium 0.09-0.13%, aluminum 0.01-0.03%, niobium and cobalt 0.04-0.06% in total, the mass percentage of niobium and cobalt is 3-5:1, and the rest is iron. The copper-nickel alloy steel provided by the invention has high corrosion resistance and is suitable for preparing drilling drill pipes.

[0009] That is, it can be known from the above content that the corrosion resistance of nickel-copper alloy can be improved by adding other metals. The present invention provides a corrosion-resistant nickel alloy, which has excellent corrosion resistance and mechanical properties based on appropriate amount of added components. Summary of the invention

[0010] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the prior art and provide a corrosion-resistant nickel alloy and its preparation method and application. The composition of the nickel alloy includes: Ni: 52~56wt%, Mo: 2~4wt%, Mn: 0.9~1.1wt%, Ce: 0.5~1.0wt%; Sm: 0.5~1.0wt%, Ca: 0.2~0.4wt%, and the balance is copper. The nickel alloy of the present invention significantly improves the corrosion resistance of the nickel alloy through the interaction between the components by adding modified metals Mo, Mn, Ce, Sm and Ca during the preparation process, and has better mechanical properties.

[0011] The object of the present invention is to provide a corrosion-resistant nickel alloy.

[0012] Another object of the present invention is to provide a method for preparing the corrosion-resistant nickel alloy.

[0013] Another object of the present invention is to provide an application of the corrosion-resistant nickel alloy.

[0014] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0015] A corrosion-resistant nickel alloy, the composition of the nickel alloy comprising:

[0016] Ni: 52~56wt%, Mo: 2~4wt%, Mn: 0.9~1.1wt%, Ce: 0.5~1.0wt%; Sm: 0.5~1.0wt%, Ca: 0.2~0.4wt%, the balance is copper;

[0017] Preferably, the composition of the nickel alloy includes: Ni: 54wt%, Mo: 3wt%, Mn: 1wt%, Ce: 0.8wt%, Sm: 0.7wt%, Ca: 0.3wt%, and the balance is copper.

[0018] Based on the above-mentioned method for preparing a corrosion-resistant nickel alloy, the preparation method comprises the following steps:

[0019] (1) Weigh the metal powder raw materials according to the composition ratio of the alloy, transfer them into a ball mill filled with stainless steel grinding balls, add ethanol, introduce nitrogen, seal, and then ball mill. The milled powder is taken out and sintered in a spark plasma sintering furnace;

[0020] (2) The sintered sample is wrapped in a stainless steel sleeve, and then the sample is hot rolled at 900-1000°C, and the final rolling temperature is 700°C;

[0021] (3) The hot-rolled alloy is heat treated under the protection of high-purity argon gas and then air-cooled to room temperature to obtain a corrosion-resistant nickel alloy.

[0022] Preferably, in step (1), in the ball mill, the ball-to-material ratio is 12:1; and the amount of ethanol used is 1-3 wt% of the total amount of the metal powder raw material.

[0023] Further preferably, in step (1), the ball milling is performed at a rotation speed of 400-500 rpm for 50-70 hours.

[0024] Further preferably, in step (1), the sintering current type is a direct current pulse current, the sintering atmosphere is a vacuum, the sintering temperature is 1000-1100° C., and the holding time is 10-20 min.

[0025] More preferably, in step (1), the sintering pressure is 30-40 MPa, and the heating rate is 30-50° C. / min.

[0026] Preferably, in step (2), the rolling deformation is 70-80%.

[0027] Preferably, in step (3), the heat treatment is performed at 900-1000° C. for 20-30 hours.

[0028] Based on the above, a corrosion-resistant nickel alloy is used in structural components in the chemical processing industry.

[0029] The present invention has the following beneficial effects:

[0030] The present invention adds appropriate amounts of Mo, Mn, Ce, Sm and Ca into the nickel-copper alloy, which can form a strong interaction with the base material, realize the strengthening of the alloy, and realize that the final nickel-copper alloy has comprehensive properties such as excellent mechanical properties and corrosion resistance. DETAILED DESCRIPTION

[0031] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0032] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0033] Example 1

[0034] A corrosion-resistant nickel alloy, the composition of the nickel alloy comprising:

[0035] Ni: 56wt%, Mo: 2wt%, Mn: 1.1wt%, Ce: 0.5wt%; Sm: 1.0wt%, Ca: 0.2wt%, the balance is copper;

[0036] A method for preparing a corrosion-resistant nickel alloy comprises the following steps:

[0037] (1) Weigh the metal powder raw material according to the composition ratio of the alloy, transfer it into a ball mill filled with stainless steel grinding balls, and the ball-to-material ratio is 12:1; add ethanol at 3wt% of the raw material weight, pass nitrogen, seal it, and then ball mill it at 500rpm for 50h. The powder after ball milling is taken out and sintered in a spark plasma sintering furnace. The sintering current type is DC pulse current, the sintering atmosphere is vacuum, the sintering temperature is 1100℃, the holding time is 10min, the sintering pressure is 40MPa, and the heating rate is 50℃ / min;

[0038] (2) The sintered sample was wrapped in a stainless steel sleeve, and the sample was hot rolled at 1000°C, the final rolling temperature was 700°C, and the rolling deformation was 80%;

[0039] (3) The hot-rolled alloy was heat treated at 1000°C for 20 h under the protection of high-purity argon gas and then air-cooled to room temperature to obtain a corrosion-resistant nickel alloy.

[0040] Example 2

[0041] A corrosion-resistant nickel alloy, the composition of the nickel alloy comprising:

[0042] Ni: 52wt%, Mo: 4wt%, Mn: 0.9wt%, Ce: 1.0wt%; Sm: 0.5wt%, Ca: 0.4wt%, the balance is copper;

[0043] A method for preparing a corrosion-resistant nickel alloy comprises the following steps:

[0044] (1) Weigh the metal powder raw material according to the composition ratio of the alloy, transfer it into a ball mill filled with stainless steel grinding balls, and the ball-to-material ratio is 12:1; add ethanol at 1wt% of the raw material weight, pass nitrogen, seal it, and then ball mill it at 400rpm for 70h. The powder after ball milling is taken out and sintered in a spark plasma sintering furnace. The sintering current type is DC pulse current, the sintering atmosphere is vacuum, the sintering temperature is 1000℃, the holding time is 20min, the sintering pressure is 30MPa, and the heating rate is 30℃ / min;

[0045] (2) The sintered sample was wrapped in a stainless steel sleeve, and the sample was hot rolled at 900°C, the final rolling temperature was 700°C, and the rolling deformation was 70%;

[0046] (3) The hot-rolled alloy was heat treated at 900°C for 30 h under the protection of high-purity argon gas and then air-cooled to room temperature to obtain a corrosion-resistant nickel alloy.

[0047] Example 3

[0048] A corrosion-resistant nickel alloy, the composition of the nickel alloy comprising:

[0049] Ni: 54wt%, Mo: 3wt%, Mn: 1wt%, Ce: 0.8wt%; Sm: 0.7wt%, Ca: 0.3wt%, and the balance is copper.

[0050] A method for preparing a corrosion-resistant nickel alloy comprises the following steps:

[0051] (1) Weigh the metal powder raw material according to the composition ratio of the alloy, transfer it into a ball mill filled with stainless steel grinding balls, and the ball-to-material ratio is 12:1; add ethanol at 2wt% of the raw material weight, pass nitrogen, seal it, and then ball mill it at 450rpm for 60h. The powder after ball milling is taken out and sintered in a spark plasma sintering furnace. The sintering current type is DC pulse current, the sintering atmosphere is vacuum, the sintering temperature is 1050℃, the holding time is 16min, the sintering pressure is 35MPa, and the heating rate is 40℃ / min;

[0052] (2) The sintered sample was wrapped in a stainless steel sleeve, and the sample was hot rolled at 950°C, the final rolling temperature was 700°C, and the rolling deformation was 75%;

[0053] (3) The hot-rolled alloy was heat treated at 950°C for 26 h under the protection of high-purity argon gas and then air-cooled to room temperature to obtain a corrosion-resistant nickel alloy.

[0054] Comparative Example 1

[0055] Comparative Example 1 is substantially the same as Example 3, except that the composition of the nickel alloy includes:

[0056] Ni: 54wt%, Mo: 4wt%, Ce: 0.8wt%; Sm: 0.7wt%, Ca: 0.3wt%, and the balance is copper.

[0057] Comparative Example 2

[0058] Comparative Example 2 is substantially the same as Example 3, except that the composition of the nickel alloy includes:

[0059] Ni: 54wt%, Mo: 3wt%, Mn: 1.8wt%; Sm: 0.7wt%, Ca: 0.3wt%, and the balance is copper.

[0060] Comparative Example 3

[0061] Comparative Example 3 is substantially the same as Example 3, except that the composition of the nickel alloy includes:

[0062] Ni: 54wt%, Mo: 3wt%, Mn: 1wt%, Ce: 1.5wt%, Ca: 0.3wt%, and the balance is copper.

[0063] Comparative Example 4

[0064] Comparative Example 4 is substantially the same as Example 3, except that the composition of the nickel alloy includes:

[0065] Ni: 54wt%, Mo: 3wt%, Mn: 1wt%, Ce: 0.8wt%; Sm: 1wt%, and the balance is copper.

[0066] Comparative Example 5

[0067] Comparative Example 5 is substantially the same as Example 3, except that the composition of the nickel alloy includes:

[0068] Ni: 54wt%, Mo: 3wt%, Mn: 1wt%, Ce: 0.8wt%; Sm: 0.7wt%, Ca: 0.1wt%, and the balance is copper.

[0069] Comparative Example 6

[0070] Comparative Example 6 is substantially the same as Example 3, except that the composition of the nickel alloy includes:

[0071] Ni: 54wt%, Mo: 3wt%, Mn: 1wt%, Ce: 0.8wt%; Sm: 0.7wt%, Ca: 0.5wt%, and the balance is copper.

[0072] The properties of the nickel alloys of Examples 1-3 and Comparative Examples 1-6 were tested. The specific test results are shown in Table 1:

[0073] Among them, the tensile strength is tested according to GB / T 228.1-2010 standard;

[0074] Corrosion resistance: According to the provisions of GB / T 10125-1997, the alloy was placed in a salt spray of 5wt% NaCl solution for 8 hours and then placed for 16 hours to measure the average corrosion rate and examine the corrosion resistance of the alloy.

[0075] Table 1:

[0076] Tensile strength (MPa) Corrosion resistance rate (mm / a) Example 1 550.6 0.014 Example 2 547.3 0.012 Example 3 552.8 0.009 Comparative Example 1 542.8 0.036 Comparative Example 2 543.4 0.029 Comparative Example 3 541.8 0.034 Comparative Example 4 544.2 0.023 Comparative Example 5 545.7 0.043 Comparative Example 6 545.1 0.052

[0077] It can be seen from Table 1 that the corrosion-resistant nickel alloy prepared by the present invention has excellent tensile strength and corrosion resistance, and within the appropriate content range, the synergistic effect between the components is relatively obvious, especially in terms of corrosion resistance, it has excellent corrosion resistance, excellent performance and good application prospects.

[0078] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a corrosion-resistant nickel alloy, characterized in that: The composition of the nickel alloy includes: Ni: 52~56wt%, Mo: 2~4wt%, Mn: 0.9~1.1wt%, Ce: 0.5~1.0wt%; Sm: 0.5~1.0wt%, Ca: 0.2~0.4wt%, the balance is copper; The preparation method comprises the following steps: (1) Weigh the metal powder raw materials according to the composition ratio of the alloy, transfer them into a ball mill filled with stainless steel grinding balls, add ethanol, introduce nitrogen, seal, and then perform ball milling. The milled powder is taken out and sintered in a spark plasma sintering furnace; (2) The sintered sample is wrapped in a stainless steel sleeve, and then the sample is hot rolled at 900-1000°C, and the final rolling temperature is 700°C; (3) heat treating the hot-rolled alloy under the protection of high-purity argon gas, and then air-cooling it to room temperature to obtain a corrosion-resistant nickel alloy; In step (3), the heat treatment is performed at 900-1000° C. for 20-30 hours.

2. The method for preparing a corrosion-resistant nickel alloy according to claim 1, characterized in that: The nickel alloy comprises: Ni: 54wt%, Mo: 3wt%, Mn: 1wt%, Ce: 0.8wt%, Sm: 0.7wt%, Ca: 0.3wt%, and the balance is copper.

3. The method for preparing a corrosion-resistant nickel alloy according to claim 1, characterized in that: In step (1), in the ball mill, the ball-to-material ratio is 12:1; the amount of ethanol used is 1-3 wt% of the total amount of the metal powder raw material.

4. The method for preparing a corrosion-resistant nickel alloy according to claim 1, characterized in that: In step (1), the ball milling is performed at a rotation speed of 400-500 rpm for 50-70 hours.

5. The method for preparing a corrosion-resistant nickel alloy according to claim 1, characterized in that: In step (1), the sintering current type is a direct current pulse current, the sintering atmosphere is a vacuum, the sintering temperature is 1000-1100°C, and the holding time is 10-20 minutes.

6. The method for preparing a corrosion-resistant nickel alloy according to claim 5, characterized in that: In step (1), the sintering pressure is 30-40 MPa, and the heating rate is 30-50°C / min.

7. The method for preparing a corrosion-resistant nickel alloy according to claim 1, characterized in that: In step (2), the rolling deformation is 70-80%.

8. Use of the corrosion-resistant nickel alloy prepared according to any of the above claims in structural parts in the chemical processing industry.