Preparation method of nano copper sulfide coated ZrN ceramic resistant to sulfuration corrosion

Abstract

The embodiment of the invention provides a preparation method of sulfuration-corrosion-resistant nano copper sulfide coated ZrN ceramic. The preparation method comprises the following steps: providing nano copper powder, ZrN powder and high-purity carbon powder; filling sulfur oxide gas into the nano copper powder; respectively adding the ZrN powder and the high-purity carbon powder into the nano copper powder, and carrying out argon-filled ball-milling powder mixing and vacuumizing to obtain mixed powder; and carrying out vacuum pressure sintering on the mixed powder, and cooling to obtain the nano copper sulfide coated ZrN ceramic. The process for preparing the nano copper sulphide coated ZrN ceramic is simple, and the production cost per kilogram is only 45-56% of that of a stellite alloy, so that the production cost can be remarkably saved. The prepared nano copper sulfide coated ZrN ceramic is compact in structure, excellent in sulfuration corrosion resistance and obviously high in cost performance, and it is possible to replace currently-used expensive Stelforce alloy.

Description

Technical Field

[0001] This invention relates to a method for preparing nano-copper sulfide-coated ZrN ceramics resistant to sulfide corrosion. Background Technology

[0002] For materials used in coal-fired and oil and gas pipeline components, the "Stele" alloy coating is widely used both domestically and internationally to achieve ideal resistance to high-temperature sulfidation corrosion. However, due to its relatively high manufacturing cost, many users and researchers in China working under sulfidation-mediated corrosion conditions desire a material that is both cost-effective and performs well in service. Clearly, inventing a sulfidation-resistant nano-copper sulfide-coated ZrN ceramic to replace the "Stele" alloy has significant innovative value and engineering application implications. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing nano-copper sulfide-coated ZrN ceramics resistant to sulfide corrosion.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing sulfide-resistant copper sulfide-coated ZrN ceramics includes the following steps: (1) Pack nano copper powder with a purity of not less than 99% and a particle size of 50nm~200nm into a sealable ball mill jar, and fill it with sulfur oxide gas at a flow rate of 2ml / min and maintain it for 2min~5min, and then ball mill and mix the powder for 15min~30min. (2) Add 5 to 15 times the weight of nano copper powder, 100μm to 200μm ZrN powder and 10% of the weight of nano copper powder, and 99.9% pure high-purity carbon powder. After mixing the powder by argon ball milling for 2 to 10 hours, vacuum for 5 to 10 minutes. (3) The mixed powder is loaded into a graphite crucible and placed in a plasma-activated sintering furnace. Vacuum pressure sintering is carried out at 750℃~950℃ and held for 10min~50min. After sintering, the furnace is cooled to obtain nano-copper sulfide coated ZrN ceramic.

[0005] In the above process, the vacuum degree of the ball mill jar is <10. -1 Pa; the vacuum degree of the vacuum pressure sintering is <10 - 1 The pressure is 100MPa~500MPa. The heating rate of the vacuum pressure sintering is 2℃ / second~3℃ / second.

[0006] The present invention provides a simple process for preparing nano-copper sulfide-coated ZrN ceramics, with a production cost per kilogram that is only 45-56% of that of "Steyli" alloy, thus significantly reducing production costs. The resulting nano-copper sulfide-coated ZrN ceramics have a dense structure and excellent resistance to sulfide corrosion. For example, in a sulfide corrosion test at 650℃ (100 hours), under the same test conditions, its thickness reduction is significantly lower than that of "Steyli" material, demonstrating a significantly higher cost-performance ratio and making it a viable alternative to the currently used, more expensive "Steyli" alloy.

[0007] This invention can prepare sulfide-resistant nano-copper sulfide-coated ZrN ceramics by generating nano-copper sulfide in situ during the material preparation process, and distributing it well between the ZrN ceramic grains after sintering. This effectively resists the erosion of sulfide media and is suitable for boilers and petrochemical pipelines that are resistant to sulfide corrosion. Attached Figure Description

[0008] Figure 1 This is a schematic flowchart of a method for preparing sulfide-resistant copper sulfide-coated ZrN ceramics according to an embodiment of the present invention. Figure 2 This is a photograph of the sulfide-resistant copper nano-copper coated ZrN ceramic prepared in Example 1 of the present invention. Detailed Implementation

[0009] like Figure 1 As shown, an embodiment of the present invention provides a method for preparing sulfide-resistant copper sulfide-coated ZrN ceramics, comprising: Step S1: Provide nano copper powder, ZrN powder, and high-purity carbon powder; Step S2: Infuse the nano-copper powder with sulfur oxide gas; Step S3: Add the ZrN powder and the high-purity carbon powder to the nano copper powder respectively, perform argon-filled ball milling and mixing, and then vacuum to obtain a mixed powder. Step S4: Vacuum pressure sintering is performed on the mixed powder, and the mixture is cooled to obtain nano-copper sulfide coated ZrN ceramic.

[0010] Example 1: (1) Pack 99.9% pure copper nanoparticles with a particle size of 200 nm into a sealable ball mill jar, and fill with sulfur oxide gas at a flow rate of 2 ml / min and maintain for 5 minutes, and then ball mill and mix the powder for 30 minutes. (2) Add 5 times the amount of 200μm ZrN powder and 10% of the weight of 99.9% high-purity carbon powder to the nano copper powder respectively, and mix them by argon ball milling for 10 hours, and then vacuum for 10 minutes. (3) The mixed powder is loaded into a graphite crucible and placed in a plasma-activated sintering furnace. Vacuum pressure sintering is carried out at 750°C and the temperature is maintained for 10 minutes. After sintering, the furnace is cooled to obtain nano-copper sulfide coated ZrN ceramic.

[0011] In the above process, the vacuum degree of the ball mill jar is 10. -2 Pa; the vacuum degree of the vacuum pressure sintering is 10. - 2 The pressure is 500 MPa. The heating rate of the vacuum pressure sintering is 2 °C / second. Figure 2 The image shown is a photograph of the sulfide-resistant nano-copper sulfide-coated ZrN ceramic prepared in this embodiment.

[0012] In this embodiment, the nano-copper sulfide-coated ZrN ceramic sample (φ100mm×100mm) and the "Stailly" alloy (φ100mm×100mm) were simultaneously placed in a sulfide medium simulated erosion test chamber for testing at 650℃ for 100 hours. After the test, the samples were ultrasonically cleaned in acetone and then dried. The change in height after damage was measured using vernier calipers. The reduction in sample height before and after the test is shown in Table 1. The data in the table show that the material prepared in this invention exhibits significantly improved resistance to sulfide media, more than doubling its performance.

[0013] Table 1

[0014] Example 2: The process in this embodiment is the same as in embodiment 1, except that some process parameters are different: The copper powder used had a particle size of 50 nm. Sulfur oxide gas was introduced and maintained for 2 minutes. After gas introduction, the ball milling time was 15 minutes. In addition to adding carbon powder of the same weight and purity as in the example, 100 μm ZrN powder with 10 times the amount of nano copper powder was added. After argon ball milling and mixing for 2 hours, vacuum was applied for 5 minutes. Vacuum pressure sintering was carried out at 950°C and held for 30 minutes to obtain nano copper sulfide coated ZrN ceramic.

[0015] The vacuum degree of the ball mill jar is 10. -2 Pa; the vacuum degree of the vacuum pressure sintering is 10. -3 The sintering holding pressure is 300 MPa. The heating rate of the vacuum pressure sintering is 3 °C / second.

[0016] The reduction in height of the obtained nano-copper sulfide-coated ZrN ceramic sample (φ100mm×100mm) and the Steyr alloy sample (φ100mm×100mm) under the same test conditions as in Example 1 is shown in Table 2. The data in the table show that the material of the present invention has significantly better resistance to sulfide corrosion than the "Steyr" alloy.

[0017] Table 2

[0018] Example 3: The process in this embodiment is the same as in embodiment 1, except that some process parameters are different: The copper powder used had a purity of 99% and a particle size of 100 nm. Sulfur oxide gas was introduced and maintained for 3 minutes, followed by ball milling for 25 minutes. In addition to adding carbon powder of the same weight and purity as in the example, 150 μm ZrN powder with 15 times the amount of nano copper powder was added. After argon ball milling for 8 hours, vacuum was applied for 7 minutes. Vacuum pressure sintering was performed at 850 °C and held for 50 minutes to obtain nano copper sulfide coated ZrN ceramic.

[0019] The vacuum degree of the ball mill jar is 10. -3 Pa; the vacuum degree of the vacuum pressure sintering is 10. -2 The sintering holding pressure is 500 MPa. The heating rate of the vacuum pressure sintering is 2 °C / second.

[0020] The reduction in height of the obtained nano-copper sulfide-coated ZrN ceramic sample (φ100mm×100mm) and the Steyr alloy sample (φ100mm×100mm) under the same test conditions as in Example 1 is shown in Table 3. The data in the table show that the material of the present invention has better resistance to sulfide corrosion than the Steyr alloy.

[0021] Table 3

[0022] It is understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of this disclosure, and this disclosure is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and substance of this disclosure, and these modifications and improvements are also considered to be within the scope of protection of this disclosure.

Claims

1. A method for preparing sulfide-resistant nano-copper sulfide-coated ZrN ceramics, characterized in that, The method includes: We offer nano copper powder, ZrN powder, and high-purity carbon powder. Sulfur oxide gas is introduced into the nano-copper powder; The ZrN powder and the high-purity carbon powder were respectively added to the nano copper powder, and the mixture was mixed by argon ball milling and vacuumed to obtain a mixed powder. The mixed powder was subjected to vacuum pressure sintering and cooled to obtain nano-copper sulfide-coated ZrN ceramic.

2. The method according to claim 1, characterized in that, The purity of the nano-copper powder is not less than 99%, and the particle size is 50nm~200nm.

3. The method according to claim 2, characterized in that, The step of filling the nano-copper powder with sulfur oxide gas includes: The nano-copper powder is loaded into a sealable ball mill jar; Sulfur oxide gas was introduced into the ball mill jar at a flow rate of 2 ml / min and maintained for 2 min to 5 min. Ball mill the powder for 15 to 30 minutes.

4. The method according to claim 3, characterized in that, The step of adding the ZrN powder and the high-purity carbon powder to the nano-copper powder includes: ZrN powder with a weight of 5 to 15 times that of the nano copper powder and a particle size of 10 μm to 200 μm, and high-purity carbon powder with a weight of 10% of the nano copper powder and a purity of 99.9%, are respectively added to the nano copper powder.

5. The method according to claim 4, characterized in that, The process of argon-filled ball milling and powder mixing includes: Perform argon-filled ball milling and powder mixing for 2 to 10 hours.

6. The method according to claim 5, characterized in that, The vacuuming process lasts for 5 to 10 minutes.

7. The method according to claim 6, characterized in that, After vacuuming, the vacuum level of the ball mill jar is less than 10. - 1 Pa.

8. The method according to any one of claims 1 to 7, characterized in that, The process of vacuum pressure sintering and cooling the mixed powder to obtain nano-copper sulfide-coated ZrN ceramics includes: The mixed powder was loaded into a graphite crucible and placed in a plasma-activated sintering furnace. Vacuum pressure sintering was carried out at 750℃~950℃ and held for 10min~50min. After sintering, the furnace was cooled to obtain nano-copper sulfide coated ZrN ceramic.

9. The method according to claim 8, characterized in that, The vacuum degree of the vacuum pressure sintering is less than 10. -1 Pa, with a pressure of 100MPa~500MPa.

10. The method according to claim 9, characterized in that, The heating rate of the vacuum pressure sintering is 2℃ / second to 3℃ / second.

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