Corrosion-resistant amorphous alloy based on stainless steel and method for manufacturing the same

Abstract

This invention provides a corrosion-resistant amorphous alloy based on stainless steel and its preparation method. The method uses stainless steel as the main raw material, adding only small amounts of low-melting-point and low-cost FeB, FeP, or graphite, and sequentially employs induction melting and single-roll quenching techniques (or gas atomization) to directly obtain the corrosion-resistant amorphous alloy. Compared with conventional preparation processes, this corrosion-resistant iron-based amorphous alloy based on stainless steel, while fully utilizing stainless steel resources, eliminates the need for adding high-purity elemental metals (such as high-melting-point metals like Cr and Mo) and alloying raw materials for the difficult remelting and alloying process. This makes it easy to melt and form, and the cost is low. Moreover, the amorphized product exhibits significantly improved corrosion resistance and wear resistance compared to stainless steel.

Description

Technical Field

[0001] This invention relates to the field of corrosion-resistant amorphous alloy technology, and in particular to a corrosion-resistant amorphous alloy based on stainless steel and its preparation method. Background Technology

[0002] Corrosion, as the most important factor affecting the long-term performance of materials, is not only a materials science issue but also an economic and safety issue. According to statistics, the economic losses caused by corrosion globally each year far exceed the total losses caused by any other natural disaster. Traditional corrosion-resistant metallic materials are mainly crystalline alloys, such as stainless steel and nickel-based alloys, which are widely used in various fields. In recent years, iron-based amorphous alloys have been developed. These are formed through rapid solidification technology, where atoms do not have time to rearrange. Their internal atoms are randomly arranged, without grain boundaries, dislocations, or compositional segregation, resulting in extremely high corrosion resistance and wear resistance. For example, SAM2×5 (Fe 49.7 Cr 17.7 Mn 1.9 Mo 7.4 W 1.6 B 15.2 C 3.8 Si 2.4 (at.%) and SAM1651 (Fe 48 Mo 14 Cr 15 Y2C 15 B6 (at.%) amorphous alloys exhibit excellent corrosion resistance in NaCl and aqua regia, far superior to stainless steel. However, the preparation of these corrosion-resistant iron-based amorphous alloys typically requires remelting and alloying with high-purity elemental metals and alloy raw materials to avoid impurity-induced surface crystallization. Furthermore, high levels of corrosion-resistant elements such as Cr and Mo are required, leading to complex alloy smelting processes, high energy consumption, and high costs for large-scale applications.

[0003] Patent CN106636979B discloses a Cr-Fe-Ni based bulk amorphous alloy with excellent corrosion resistance and its preparation method. The method involves arc melting Fe, Cr, Ni, Mo, C, B and FeP alloys with a purity greater than 99.5wt% 3-5 times to obtain a master alloy ingot with uniform composition. Then, amorphous alloy rods are obtained by copper mold spray casting process. The manufacturing process is complex and costly.

[0004] The article "Thermal Stability and Corrosion Resistance of Iron-Based Amorphous Powder Core Wire Based on 430 Stainless Steel" reports a formulation for designing an alloy using stainless steel powder coating. 430 stainless steel is selected as the alloy's outer layer, and metal powder composed of Fe, Mo, Y, FeC, and FeB is added to the outer layer. Plate-shaped FeCrMnCBY bulk amorphous powder core wire is then prepared using arc melting and copper mold suction casting, exhibiting excellent corrosion resistance. However, this method requires the addition of high-melting-point metal powders such as Mo and Y, resulting in high cost and difficult melting. Arc melting is therefore necessary to prepare the amorphous alloy.

[0005] In view of this, it is necessary to design a corrosion-resistant amorphous alloy based on stainless steel and its preparation method to solve the above problems. Summary of the Invention

[0006] To address the shortcomings of the prior art, the present invention aims to provide a corrosion-resistant amorphous alloy based on stainless steel and its preparation method. By adding a small amount of FeB, FeP or graphite to the alloy, the corrosion-resistant amorphous alloy can be directly prepared using induction melting and single-roll quenching technology (or gas atomization method).

[0007] To achieve the above objectives, the present invention provides a method for preparing a corrosion-resistant amorphous alloy based on stainless steel, comprising the following steps:

[0008] S1. After adding ferroalloys or graphite to stainless steel in a predetermined proportion and smelting, a master alloy is obtained.

[0009] The ferroalloy includes one or more of FeB and FeP;

[0010] S2. The master alloy is subjected to a predetermined treatment to obtain a corrosion-resistant amorphous alloy based on stainless steel; the predetermined treatment methods include single-roll quenching and gas atomization.

[0011] Further, in step S1, the stainless steel includes one of 430 stainless steel, 304 stainless steel, and 316L stainless steel; preferably, the stainless steel is 316L stainless steel.

[0012] Furthermore, in step S1, the melting process includes induction melting.

[0013] Further, in step S1, the mass fraction of B in FeB is 17.43 wt.%, and the mass fraction of P in FeP is 23.48 wt.%.

[0014] The predetermined proportions are as follows: FeB accounts for 5.8–44.1 wt.% of the total mass of the stainless steel and FeB; FeP accounts for 12.1–51.9 wt.% of the total mass of the stainless steel and FeP; graphite accounts for 1.1–5.1 wt.% of the total mass of the stainless steel and graphite; the total mass of FeB and FeP accounts for 18.0–57.3 wt.% of the total mass of the stainless steel, FeB, and FeP, wherein the mass ratio of FeB to FeP is 0.5; the total mass of FeB and graphite accounts for 6.9–24.3 wt.% of the total mass of the stainless steel, FeB, and graphite, wherein the mass ratio of FeB to graphite is 4.0; and the total mass of FeP and graphite accounts for 18.6–59.2 wt.% of the total mass of the stainless steel, FeP, and graphite, wherein the mass ratio of FeB to graphite is 4.0. The mass ratio of graphite is 8.6; the total mass of FeB, FeP, and graphite accounts for 24.4 to 78.4 wt.% of the total mass of stainless steel, FeB, FeP, and graphite, wherein the mass ratio of FeB, FeP, and graphite is 4:8:1; preferably, in the predetermined ratio, the mass ratio of stainless steel to FeB is 63.8:36.2; the mass ratio of stainless steel to FeP is 67.0:33.0; the mass ratio of stainless steel to graphite is 86.5:13.5; the mass ratio of stainless steel to FeB and FeP is 63.1:12.1:24.8; the mass ratio of stainless steel to FeB and graphite is 84.2:12.1:3.7; the mass ratio of stainless steel to FeP and graphite is 63.1:24.8:2.4; and the mass ratio of stainless steel to FeB, FeP, and graphite is 68.3:5.8:24.8:1.1.

[0015] Furthermore, in step S2, when using the single-roller spin quenching method, the linear speed of the copper roller is set to 20-40 m / s to obtain a corrosion-resistant amorphous alloy strip.

[0016] Furthermore, in step S2, when using the gas atomization method, a flow rate of 15–25 m³ / h is selected. 3 Using nitrogen gas at a rate of / h, and setting the atomization temperature to 1550~1700℃ and the pressure to 5~6MPa, corrosion-resistant amorphous alloy powder is obtained.

[0017] Furthermore, the thickness of the corrosion-resistant amorphous alloy strip is 25–50 μm.

[0018] Furthermore, the particle size of the corrosion-resistant amorphous alloy powder is 20–100 μm.

[0019] The present invention also provides a corrosion-resistant amorphous alloy prepared by the aforementioned preparation method; the corrosion-resistant amorphous alloy has an Fe composition. a Cr b Ni cMo d B e P f C g M.

[0020] Furthermore, the corrosion-resistant amorphous alloy Fe a Cr b Ni c Mo d B e P f C g The atomic percentages of each element in M ​​are: 68.4 wt.% ≤ a ≤ 80.8 wt.%, 8.8 wt.% ≤ b ≤ 15.4 wt.%, 0 ≤ c ≤ 10.9 wt.%, 0 ≤ d ≤ 2.2 wt.%, 0 ≤ e ≤ 7.7 wt.%, 0 ≤ f ≤ 12.2 wt.%, and 0 ≤ g ≤ 5.1 wt.%, where M is one or more of Mn, Si, Al, and S, and the atomic percentages of each element are Mn < 0.9 wt.%, Si < 0.5 wt.%, Al < 0.01 wt.%, and S < 0.01 wt.%.

[0021] The beneficial effects of this invention are:

[0022] This invention provides a method for preparing a corrosion-resistant amorphous alloy based on stainless steel. Using stainless steel as the main raw material, with only a small amount of low-melting-point and low-cost FeB, FeP, or FeC alloys added, the corrosion-resistant amorphous alloy is directly prepared by sequentially employing induction melting and single-roll quenching technology (or gas atomization method). Compared with conventional corrosion-resistant amorphous alloy preparation processes, this method fully utilizes stainless steel resources and avoids the addition of high-melting-point metals such as Cr and Mo. It is easy to melt and form, and has low cost. The amorphized product exhibits significantly improved corrosion resistance and wear resistance compared to stainless steel. Attached Figure Description

[0023] Figure 1 The images show the XRD patterns of the corrosion-resistant amorphous alloy strip prepared in Example 1 and the stainless steel alloy strip prepared in Comparative Example 1.

[0024] Figure 2 The corrosion polarization curves are shown for the corrosion-resistant amorphous alloy strip prepared in Example 1 and the stainless steel alloy strip prepared in Comparative Example 1.

[0025] Figure 3 Wear tests and friction coefficient diagrams were performed on the corrosion-resistant amorphous alloy strip prepared in Example 1 and the stainless steel alloy strip prepared in Comparative Example 1. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0027] It should also be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and / or processing steps closely related to the present invention are shown in the accompanying drawings, while other details that are not closely related to the present invention are omitted.

[0028] Additionally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0029] A method for preparing a corrosion-resistant amorphous alloy based on stainless steel includes the following steps:

[0030] S1. After adding ferroalloys or graphite to stainless steel in a predetermined proportion and smelting, a master alloy is obtained.

[0031] The stainless steel includes one of 430 stainless steel, 304 stainless steel, and 316L stainless steel; preferably, the stainless steel is 316L stainless steel; the ferroalloy includes one or more of FeB and FeP; the mass fraction of B in FeB is 17.43 wt.%, and the mass fraction of P in FeP is 23.48 wt.%; the smelting method includes induction melting;

[0032] The predetermined proportions are as follows: FeB accounts for 5.8–44.1 wt.% of the total mass of the stainless steel and FeB; FeP accounts for 12.1–51.9 wt.% of the total mass of the stainless steel and FeP; graphite accounts for 1.1–5.1 wt.% of the total mass of the stainless steel and graphite; the total mass of FeB and FeP accounts for 18.0–57.3 wt.% of the total mass of the stainless steel, FeB, and FeP, wherein the mass ratio of FeB to FeP is 0.5; the total mass of FeB and graphite accounts for 6.9–24.3 wt.% of the total mass of the stainless steel, FeB, and graphite, wherein the mass ratio of FeB to graphite is 4.0; and the total mass of FeP and graphite accounts for 18.6–59.2 wt.% of the total mass of the stainless steel, FeP, and graphite, wherein the mass ratio of FeB to graphite is 4.0. The mass ratio of graphite is 8.6; the total mass of FeB, FeP, and graphite accounts for 24.4 to 78.4 wt.% of the total mass of stainless steel, FeB, FeP, and graphite, wherein the mass ratio of FeB, FeP, and graphite is 4:8:1; preferably, in the predetermined ratio, the mass ratio of stainless steel to FeB is 63.8:36.2; the mass ratio of stainless steel to FeP is 67.0:33.0; the mass ratio of stainless steel to graphite is 86.5:13.5; the mass ratio of stainless steel to FeB and FeP is 63.1:12.1:24.8; the mass ratio of stainless steel to FeB and graphite is 84.2:12.1:3.7; the mass ratio of stainless steel to FeP and graphite is 63.1:24.8:2.4; and the mass ratio of stainless steel to FeB, FeP, and graphite is 68.3:5.8:24.8:1.1.

[0033] S2. The master alloy is subjected to a predetermined treatment to obtain a corrosion-resistant amorphous alloy; the predetermined treatment includes single-roll quenching and gas atomization; when using the single-roll quenching method, the linear speed of the copper roller is set to 20-40 m / s, and the thickness of the obtained corrosion-resistant amorphous alloy strip is 25-50 μm; when using the gas atomization method, the flow rate is selected to be 15-25 m³ / s. 3 With nitrogen gas at a flow rate of / h, the atomization temperature is set to 1550–1700℃ and the pressure to be 5–6MPa, the particle size of the obtained corrosion-resistant amorphous alloy powder is 20–100μm.

[0034] This design allows for full utilization of stainless steel resources and avoids the addition of high-melting-point metals such as Cr and Mo. It is easy to melt and form and has low cost. Compared with stainless steel, the amorphized product has significantly improved corrosion resistance and wear resistance.

[0035] The present invention also provides a corrosion-resistant amorphous alloy prepared by the aforementioned preparation method; the corrosion-resistant amorphous alloy has the composition of Fe. a Crb Ni c Mo d B e P f C g M.

[0036] The corrosion-resistant amorphous alloy Fe a Cr b Ni c Mo d B e P f C g The atomic percentages of each element in M ​​are: 68.4 wt.% ≤ a ≤ 80.8 wt.%, 8.8 wt.% ≤ b ≤ 15.4 wt.%, 0 ≤ c ≤ 10.9 wt.%, 0 ≤ d ≤ 2.2 wt.%, 0 ≤ e ≤ 7.7 wt.%, 0 ≤ f ≤ 12.2 wt.%, and 0 ≤ g ≤ 5.1 wt.%, where M is one or more of Mn, Si, Al, and S, and the atomic percentages of each element are Mn < 0.9 wt.%, Si < 0.5 wt.%, Al < 0.01 wt.%, and S < 0.01 wt.%.

[0037] The preparation method of the corrosion-resistant amorphous alloy based on stainless steel provided by the present invention will be specifically described below with reference to the embodiments:

[0038] Example 1

[0039] The stainless steel used in this embodiment is 316L stainless steel, and its specific composition is shown in Table 1.

[0040] Table 13. Composition of 1316L stainless steel (wt.%)

[0041]

[0042] This embodiment provides a corrosion-resistant amorphous alloy based on stainless steel and its preparation method, specifically including the following steps:

[0043] S1. Take 100g of 316L stainless steel and add 36.18g of FeB alloy (B content 17.43wt.%), then perform induction melting to obtain Fe. 73.5 Ni 7.4 Cr 11.9 Mo 1.5 Mn 0.7 Si 0.3 B 4.6 (wt.%) master alloy;

[0044] S2, regarding the Fe 73.5 Ni 7.4 Cr 11.9 Mo 1.5Mn 0.7 Si 0.3 B 4.6 The (wt.%) master alloy was processed using single-roll spin quenching technology to finally obtain corrosion-resistant amorphous alloy strip;

[0045] When using the single-roller spin quenching method, the speed of the copper roller is set to 30 m / s, and the thickness of the resulting corrosion-resistant amorphous alloy strip is approximately 30 μm.

[0046] Comparative Example 1

[0047] This comparative example provides a method for preparing stainless steel, specifically including the following steps:

[0048] S1. Take 10g of 316L stainless steel and process it using single-roll spin quenching technology to finally obtain stainless steel alloy strip.

[0049] When using the single-roller spin quenching method, the speed of the copper roller is set to 30 m / s, and the thickness of the resulting corrosion-resistant amorphous alloy strip is approximately 30 μm.

[0050] XRD analysis was performed on the corrosion-resistant amorphous alloy strip obtained in Example 1 and the stainless steel alloy strip obtained in Comparative Example 1, respectively. The results are as follows: Figure 1 As shown, the corrosion-resistant amorphous alloy strip in Example 1 exhibits a single diffuse scattering peak, which is significantly different from the obvious crystallization peak in the stainless steel alloy strip in Comparative Example 1, indicating that an amorphous alloy was prepared based on 316L stainless steel. The corrosion resistance (e.g., ...) of the corresponding alloy strips in Example 1 and Comparative Example 1 was also tested. Figure 2 (as shown) and abrasion resistance test (such as) Figure 3 As shown in the figure, it was found that the passivation range of the corrosion-resistant amorphous alloy strip prepared in Example 1 was significantly wider; moreover, the scratches after friction were shallow and the wear volume was small, indicating that the corrosion resistance and wear resistance of the amorphous alloy prepared based on stainless steel were significantly improved.

[0051] Example 2

[0052] Example 2 provides a corrosion-resistant amorphous alloy based on stainless steel and its preparation method. The difference between Example 1 and Example 2 lies in the alloy added in step S1. This example uses an FeP alloy, with 32.98 g of FeP alloy (P content 23.48 wt.%) added, ultimately yielding Fe... 71.8 Ni 7.6 Cr 12.2 Mo 1.5 Mn 0.8 Si 0.3 P 5.8 (wt.%) Master alloy. The remaining steps are the same as in Example 1 and will not be repeated here. The remaining steps and parameters are the same as in Example 1 and will not be repeated here.

[0053] Finally, the corrosion resistance of the stainless steel-based corrosion-resistant amorphous alloy prepared in Example 2 was tested, and its corrosion resistance was significantly better than that of 316L stainless steel.

[0054] In summary, this invention provides a corrosion-resistant amorphous alloy based on stainless steel and its preparation method. Using stainless steel as the main raw material, with only a small amount of low-melting-point and low-cost FeB, FeP, or FeC alloys added, the corrosion-resistant amorphous alloy can be directly obtained using induction melting and single-roll quenching technology (or gas atomization). Compared with conventional corrosion-resistant amorphous alloy preparation processes, this corrosion-resistant iron-based amorphous alloy, prepared based on the compositional characteristics of stainless steel, fully utilizes stainless steel resources without requiring the use of high-purity metallic elements (such as high-melting-point metals like Cr and Mo) and alloy raw materials for difficult remelting and alloying, and avoids the addition of these materials. It is thus easy to melt and form, and the cost is low. Moreover, the amorphized product exhibits significantly improved corrosion resistance and wear resistance compared to stainless steel.

[0055] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a corrosion-resistant amorphous alloy based on stainless steel, characterized in that, The corrosion-resistant amorphous alloy is composed of Fe. a Cr b Ni c Mo d B e P f C g M; wherein the mass percentage of each element is: 68.4wt.%≤a≤80.8wt.%, 8.8wt.%≤b≤15.4wt.%, 0≤c≤10.9wt.%, 0≤d≤2.2wt.%, 0≤e≤7.7wt.%, 0≤f≤12.2wt.%, 0≤g≤5.1wt.%; M is one or more of Mn, Si, Al, and S, and the mass percentage of each element is Mn<0.9wt.%, Si<0.5wt.%, Al<0.01wt.%, S<0.01wt.%. The preparation method includes the following steps: S1. After adding ferroalloy to stainless steel in a predetermined ratio and smelting it, a master alloy is obtained. The ferroalloy is FeB or FeP; The stainless steel is 316L stainless steel; The FeB contains 17.43 wt.% B, and the FeP contains 23.48 wt.% P. The predetermined proportions are as follows: FeB accounts for 5.8~44.1 wt.% of the total mass of the stainless steel and FeB; and FeP accounts for 12.1~51.9 wt.% of the total mass of the stainless steel and FeP. S2. The master alloy is processed by single-roller spin quenching, with the linear speed of the copper roller set to 20~40m / s, to obtain a corrosion-resistant amorphous alloy.

2. The method for preparing a corrosion-resistant amorphous alloy based on stainless steel according to claim 1, characterized in that: In step S1, the melting process includes induction melting.

3. The method for preparing the corrosion-resistant amorphous alloy based on stainless steel according to claim 1, characterized in that: In the predetermined ratio, the mass ratio of stainless steel to FeB is 63.8:36.2; the mass ratio of stainless steel to FeP is 67.0:33.

0.

4. The method for preparing a corrosion-resistant amorphous alloy based on stainless steel according to claim 1, characterized in that: The thickness of the corrosion-resistant amorphous alloy is 25~50μm.

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