Metal material with high strength and excellent antibacterial property and preparation method thereof

Abstract

The invention discloses a metal material with high strength and excellent antibacterial performance and a preparation method of the metal material, and belongs to the technical field of metal materials, the metal material comprises Fe2CrNi S < 0.2 > T < 0.1 > Cux, and x is 0.4-0.5. The preparation method comprises the following steps that S1, according to the proportion of alloy elements, an iron elementary substance, a chromium elementary substance, a nickel elementary substance, a silicon elementary substance, a titanium elementary substance and a copper elementary substance are matched, and a smelting raw material is obtained; s2, the prepared smelting raw materials are put into a vacuum arc furnace or a vacuum induction smelting furnace, smelting is carried out under the inert protective atmosphere, the smelting raw materials are sucked and cast into a copper mold, and an alloy ingot is formed; and S3, alloy ingots obtained through smelting are treated through a mechanical-heat treatment process, and the final metal material is obtained. According to the metal material with the high strength and the excellent antibacterial property, the mechanical property is obviously enhanced, the excellent antibacterial and antifouling properties are achieved, and attachment of bacteria and microorganisms on the surface of a ship can be reduced.

Description

Technical Field

[0001] The invention relates to the technical field of metal materials, and in particular to a metal material with high strength and excellent antibacterial properties and a preparation method thereof. Background Art

[0002] Engineering materials will be more or less affected by the attachment and influence of different kinds of microorganisms during their service. Accidents such as pipeline leakage caused by microbial corrosion, damage to seawater injection devices, and failure of deep-sea tsunami warning systems have caused irreparable losses to people's production and life. Copper and copper alloys are widely used in marine engineering because of their resistance to seawater corrosion, resistance to marine biological corrosion, and antibacterial and antifouling properties.

[0003] However, copper has low hardness and poor wear resistance. Copper alloy parts such as propellers and impellers are in direct contact with seawater during operation. They are subject to the dual effects of gravel scouring and seawater corrosion, and are prone to wear, corrosion, cracks and other defects, which seriously affect the safety of ship navigation. High entropy alloys have lattice distortion effect in structure, high entropy effect in thermodynamics, slow diffusion effect in dynamics, and cocktail effect in performance, which make high entropy alloys have higher strength, hardness and wear resistance. These are excellent properties that traditional alloys cannot have at the same time.

[0004] Therefore, designing a high-entropy alloy metal material with excellent mechanical strength and antibacterial properties is one of the keys to whether high-entropy alloys can be used on a large scale in marine environments. Summary of the invention

[0005] The purpose of the present invention is to provide a metal material with high strength and excellent antibacterial properties and a preparation method thereof, so as to solve the above problems.

[0006] To achieve the above object, the present invention provides a metal material with high strength and excellent antibacterial properties, the metal material composition is Fe 2 CrNiS i 0.2 T i 0.1 Cu x ,in:

[0007] The atomic percentage of each element in the alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:x; and x is 0.4-0.5.

[0008] A method for preparing a metal material with high strength and excellent antibacterial properties comprises the following steps:

[0009] S1. According to the ratio of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed to obtain a smelting raw material;

[0010] S2, placing the prepared smelting raw materials into a vacuum arc furnace or a vacuum induction melting furnace, melting them under an inert protective atmosphere and suction casting them into a copper mold to form an alloy ingot;

[0011] S3. The alloy ingot obtained by smelting is subjected to a mechanical-heat treatment process to obtain a final metal material.

[0012] Preferably, in a method for preparing a metal material with high strength and excellent antibacterial properties, the mass percentage purity of each single element in step S1 is not less than 99.9%.

[0013] Preferably, in a method for preparing a metal material with high strength and excellent antibacterial properties, in step S2, in order to ensure uniform alloy composition, the smelting process needs to be repeated more than 4 times.

[0014] Preferably, in a method for preparing a metal material with high strength and excellent antibacterial properties, the size of the alloy ingot formed by smelting and suction casting into a copper mold in step S2 is 10×10×50 mm 3 .

[0015] Preferably, a method for preparing a metal material with high strength and excellent antibacterial properties, the mechanical-heat treatment process in step S3 specifically includes: cold rolling the alloy ingot at room temperature using a rolling mill, and the thickness of the rectangular sample after rolling is reduced by 80%; after rolling, a temperature-controlled heater is used to keep the temperature at 1200°C for 1 hour, and then a temperature-controlled heater is used to keep the temperature at 600°C for 1 hour to obtain the final alloy material.

[0016] Therefore, the present invention adopts the above-mentioned metal material with high strength and excellent antibacterial properties and its preparation method, which has the following beneficial effects:

[0017] (1) Changing the mechanical-thermal processing parameters resulted in the preparation of a metal alloy with high mechanical properties (high ultimate tensile strength). Mechanical property tests showed that the alloy metal material prepared by this method had a yield strength of 1494 MPa, an ultimate tensile strength of 1502 MPa, and an elongation of 58% at room temperature (298K), and significantly enhanced mechanical properties.

[0018] (2) The alloy metal material is based on the FeCrNiSiTi system, and the Cu element is added; compared with the FeCrNiSiTi system alloy without the Cu element, the alloy material of the present application not only has a high ultimate tensile strength, but also has excellent antibacterial and antifouling properties (>99%), which can reduce the attachment of bacteria and microorganisms on the surface of the ship, thereby extending the service life of the alloy material.

[0019] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 XRD results of the metal materials prepared in Example 1 and Example 5 of the metal material with high strength and excellent antibacterial performance and the preparation method thereof of the present invention;

[0021] Figure 2 The SEM morphology of the metal material prepared in Examples 1 to 4 of the metal material with high strength and excellent antibacterial performance and the preparation method thereof of the present invention;

[0022] Figure 3 The tensile stress-strain curves of the metal materials prepared in Examples 1 to 4 of the metal material with high strength and excellent antibacterial properties and the preparation method thereof of the present invention;

[0023] Figure 4 The tensile stress-strain curves of the metal materials prepared in Examples 5 to 8 of the metal material with high strength and excellent antibacterial properties and the preparation method thereof of the present invention;

[0024] Figure 5 The antibacterial test culture dish of the metal material prepared in Examples 1 to 8 of the metal material with high strength and excellent antibacterial performance and the preparation method thereof of the present invention. DETAILED DESCRIPTION

[0025] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The singular forms "a", "said" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings, and "multiple" generally includes at least two.

[0027] It should also be noted that the term "includes", "comprising" or any other variation thereof is intended to cover non-exclusive inclusion, so that a commodity or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such commodity or device. In the absence of more restrictions, the elements defined by the sentence "comprising a ..." do not exclude the existence of other identical elements in the commodity or device including the elements.

[0028] The present invention provides a metal material with high strength and excellent antibacterial properties, wherein the metal material comprises Fe 2 CrN i S i 0.2 T i 0.1 Cu x ,in:

[0029] The atomic percentage of each element in the alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:x; and x is 0.4-0.5.

[0030] The method for preparing the above-mentioned metal material with high strength and excellent antibacterial properties comprises the following steps:

[0031] S1. According to the ratio of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed to obtain a smelting raw material;

[0032] S2, placing the prepared smelting raw materials into a vacuum arc furnace or a vacuum induction melting furnace, melting them under an inert protective atmosphere and suction casting them into a copper mold to form an alloy ingot;

[0033] S3. The alloy ingot obtained by smelting is subjected to a mechanical-heat treatment process to obtain a final metal material.

[0034] To further optimize the above technical solution, the mass percentage purity of each single element in step S1 is not less than 99.9%.

[0035] To further optimize the above technical solution, in step S2, in order to ensure uniform alloy composition, the smelting process needs to be repeated more than 4 times.

[0036] To further optimize the above technical solution, the size of the alloy ingot formed by the smelting and suction casting into the copper mold in step S2 is 10×10×50 mm. 3 .

[0037] To further optimize the above technical solution, the mechanical-heat treatment process in step S3 specifically includes: cold rolling the alloy ingot at room temperature using a rolling mill, and the thickness of the rectangular sample after rolling is reduced by 80%; after rolling, the temperature is kept at 1200°C for 1 hour using a temperature-controlled heater, and then the temperature is kept at 600°C for 1 hour using a temperature-controlled heater to obtain the final alloy material.

[0038] In order to more clearly and in detail introduce the metal material with high strength and excellent antibacterial properties and the preparation method thereof provided by the present invention, a description will be given below in conjunction with specific embodiments.

[0039] Embodiment 1

[0040] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.4 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.4. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0041] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0042] The XRD and SEM morphologies of the alloy materials were obtained. Figure 1 , Figure 2 As shown by Figure 1 It can be seen that it is an FCC phase. For the convenience of description, the sample prepared in Example 1 is named 1-Cu0.4.

[0043] Embodiment 2

[0044] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.4 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.4. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0045] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0046] Mechanical-heat treatment process: use UDIAN temperature control heater to keep the temperature at 1200℃ for 1 hour, and then use UDIAN temperature control heater to keep the temperature at 600℃ for 1 hour.

[0047] The SEM morphology of the alloy material is as follows: Figure 2 As shown, the alloy material has Cu precipitated phase. For the convenience of description, the sample prepared in Example 2 is named 2-Cu0.4.

[0048] Embodiment 3

[0049] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.4 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.4. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0050] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0051] Mechanical-heat treatment process: The bars were cold rolled at room temperature using a ZK-WS8A-3 asynchronous rolling mill, and the thickness of the rectangular specimens after rolling was reduced by 80%. Subsequently, the bars were kept at 1200°C for 1 hour using a UDIAN temperature-controlled heater, and finally kept at 600°C for 1 hour using a UDIAN temperature-controlled heater.

[0052] The SEM morphology of the alloy material is as follows: Figure 2 For the convenience of description, the sample prepared in Example 3 is named 3-Cu0.4.

[0053] Embodiment 4

[0054] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.4 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.4. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0055] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0056] Mechanical-heat treatment process: The UDIAN temperature-controlled heater was used to keep the temperature at 1200℃ for 1 hour, and then quenched with water to room temperature. The bars were cold-rolled at room temperature using a ZK-WS8A-3 asynchronous rolling mill, and the thickness of the rectangular specimens after rolling was reduced by 80%. Finally, the UDIAN temperature-controlled heater was used to keep the temperature at 600℃ for 1 hour.

[0057] The SEM morphology of the alloy material is as follows: Figure 2 As shown, the alloy material has Cu precipitated phase. For the convenience of description, the sample prepared in Example 4 is named 4-Cu0.4.

[0058] Embodiment 5

[0059] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.5 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.5. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0060] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0061] The XRD of the alloy material is obtained as Figure 1 For the convenience of description, the sample prepared in Example 5 is named 5-Cu0.5.

[0062] Embodiment 6

[0063] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.5 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.5. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0064] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0065] Mechanical-heat treatment process: use UDIAN temperature control heater to keep the temperature at 1200℃ for 1 hour, and then use UDIAN temperature control heater to keep the temperature at 600℃ for 1 hour.

[0066] For the convenience of description, the sample prepared in Example 6 is named 6-Cu0.5.

[0067] Embodiment 7

[0068] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.5 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.5. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0069] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0070] Mechanical-heat treatment process: The bars were cold rolled at room temperature using a ZK-WS8A-3 asynchronous rolling mill, and the thickness of the rectangular specimens after rolling was reduced by 80%. Subsequently, the bars were kept at 1200°C for 1 hour using a UDIAN temperature-controlled heater, and finally kept at 600°C for 1 hour using a UDIAN temperature-controlled heater.

[0071] For the convenience of description, the sample prepared in Example 7 is named 7-Cu0.5.

[0072] Embodiment 8

[0073] Fe 2 CrN iSi 0.2 Ti 0.1 Cu 0.5 The alloy element ratio of the high entropy alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:0.5. According to the proportion of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed, and the mass percentage purity of each element is not less than 99.9%.

[0074] The single element in the smelting raw material is placed in a vacuum arc furnace, then vacuumed, protected by argon, and evenly smelted 4 times to obtain an alloy ingot with a size of 10×10×50mm 3 .

[0075] Mechanical-heat treatment process: The UDIAN temperature-controlled heater was used to keep the temperature at 1200℃ for 1 hour, and then quenched with water to room temperature. The bars were cold-rolled at room temperature using a ZK-WS8A-3 asynchronous rolling mill, and the thickness of the rectangular specimens after rolling was reduced by 80%. Finally, the UDIAN temperature-controlled heater was used to keep the temperature at 600℃ for 1 hour.

[0076] For the convenience of description, the sample prepared in Example 8 is named 8-Cu0.5.

[0077] The antibacterial properties of the metal materials obtained in Examples 1 to 8 were tested, and the data are shown in Table 1;

[0078] Table 1 Antibacterial properties of Examples 1 to 8

[0079]

[0080]

[0081] The yield strength, ultimate tensile strength, elongation and antibacterial properties of the metal materials obtained in Examples 1 to 8 were tested, and the data are shown in Table 2;

[0082] Table 2 Yield strength, ultimate tensile strength, elongation and antibacterial performance data of Examples 1 to 8

[0083]

[0084]

[0085] according to Figure 3 Combined with the processes of Examples 1 to 8 in Table 2, the yield strength, ultimate tensile strength and elongation can be obtained, and the yield strength of the alloy material can reach 1494MPa, the ultimate tensile strength can reach 1502MPa, and it has high mechanical properties. The elongation of the alloy material can reach 58%.

[0086] Combination Figure 4 From the bacterial situation in the culture dish and the colony count, dilution multiple, bacterial solution concentration and antibacterial rate of Examples 1 to 8 in Table 1, it can be seen that the alloy material of the present invention has excellent antibacterial performance (>99%).

[0087] Therefore, the present invention adopts a metal material with high strength and excellent antibacterial properties and a preparation method thereof of the above-mentioned structure, and obtains a metal alloy with high mechanical properties (having very high ultimate tensile strength) by changing the mechanical-thermal processing parameters. Mechanical property tests show that the alloy metal material prepared by this method has a yield strength of 1494MPa and an ultimate tensile strength of 1502MPa at room temperature (298K), and an elongation of 58%, and the mechanical properties are significantly enhanced. The alloy metal material is based on the FeCrNiSiTi system, and the Cu element is added; compared with the FeCrNiSiTi system alloy without the Cu element, the alloy material of the present application not only has a high ultimate tensile strength, but also has excellent antibacterial and antifouling properties (>99%), which can reduce the attachment of bacteria and microorganisms on the surface of the ship, thereby making the alloy material serve longer.

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A metal material with high strength and excellent antibacterial properties, characterized in that: The metal material composition is Fe2CrNiSi 0.2 Ti 0.1 Cu x ,in: The atomic percentage of each element in the alloy is Fe:Cr:Ni:Si:Ti:Cu=2:1:1:0.2:0.1:x; and x is 0.4-0.

5.

2. A method for preparing a metal material with high strength and excellent antibacterial properties as claimed in claim 1, characterized in that: The following steps are involved: S1. According to the ratio of alloy elements, iron, chromium, nickel, silicon, titanium and copper are mixed to obtain a smelting raw material; S2, placing the prepared smelting raw materials into a vacuum arc furnace or a vacuum induction melting furnace, melting them under an inert protective atmosphere and suction casting them into a copper mold to form an alloy ingot; S3. The alloy ingot obtained by smelting is subjected to a mechanical-heat treatment process to obtain a final metal material.

3. The method for preparing a metal material with high strength and excellent antibacterial properties according to claim 2, characterized in that: In step S2, in order to ensure uniform alloy composition, the smelting process needs to be repeated more than 4 times.

4. The method for preparing a metal material with high strength and excellent antibacterial properties according to claim 2, characterized in that: The size of the alloy ingot formed by the smelting and suction casting into the copper mold in step S2 is 10×10×50 mm 3 .

5. The method for preparing a metal material with high strength and excellent antibacterial properties according to claim 2, characterized in that: The mechanical-heat treatment process in step S3 specifically includes: cold rolling the alloy ingot at room temperature using a rolling mill, and the thickness of the rectangular sample after rolling is reduced by 80%; after rolling, the temperature is kept at 1200°C for 1 hour using a temperature-controlled heater, and then kept at 600°C for 1 hour using a temperature-controlled heater to obtain the final alloy material.

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