Wear-resistant and Anti-corrosion material and preparation method therefor, and wear-resistant and Anti-corrosion plunger rod, and preparation method therefor and use thereof

Abstract

The present invention relates to the field of functional materials. Disclosed are a wear-resistant and anti-corrosion material and a preparation method therefor, and a wear-resistant and anti-corrosion plunger rod, and a preparation method therefor and the use thereof. The surface of the wear-resistant and anti-corrosion material comprises a wear-resistant and anti-corrosion coating, wherein the wear-resistant and anti-corrosion coating sequentially comprise an Si interface layer, a nano TiCN layer and a nano SiC layer from the inner interface of the coating to the outer surface of the coating. The wear-resistant and anti-corrosion material and the wear-resistant and anti-corrosion plunger rod provided in the present invention have excellent wear resistance and anti-corrosion property.

Description

Wear-resistant and corrosion-resistant materials and their preparation methods, wear-resistant and corrosion-resistant plunger rods and their preparation methods and applications

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202411574671.9, filed on November 6, 2024, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of functional materials, specifically to a wear-resistant and corrosion-resistant material and its preparation method, and a wear-resistant and corrosion-resistant plunger rod and its preparation method and application. Background Technology

[0004] The plunger rod is a key component of the plunger pump and an important tool in oil and gas fields. It extracts crude oil through reciprocating motion within the pump. The operating environment of plunger pumps is typically a multiphase medium consisting of solid particles, crude oil, inorganic salts, and high-pH water. In such environments, the plunger rod is highly susceptible to wear and corrosion, leading to failure and maintenance, severely impacting production efficiency. Therefore, improving the wear and corrosion resistance of the plunger rod in multiphase flow corrosive and abrasive environments has become a crucial issue for the efficient and stable operation of oil and gas fields. Currently, the main methods to improve the wear and corrosion resistance of plunger rods are electroplated chromium coating (CN209067455U), sprayed nickel-based coating (CN102211194A, CN201288658Y), laser cladding alloy coating (CN104862697B), and optimized structural design (CN220319800U). However, these methods still have obvious drawbacks. For example, electroplated chromium coatings pollute the environment and have poor wear resistance; sprayed nickel-based coatings have high porosity and high stress, making them prone to corrosion and wear; and laser cladding alloy coatings have high surface roughness and high wear rate. As a result, the wear and corrosion resistance of plunger rods is still limited, affecting the production efficiency and safety of oil and gas fields. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem that the wear resistance and corrosion resistance of plunger rods in the solid-liquid-gas three-phase medium environment of oil and gas field wells are seriously insufficient. This invention provides a wear-resistant and corrosion-resistant material and its preparation method, as well as a wear-resistant and corrosion-resistant plunger rod and its preparation method and application. The wear-resistant and corrosion-resistant material and the wear-resistant and corrosion-resistant plunger rod have good wear resistance and corrosion resistance.

[0006] To achieve the above objectives, the present invention provides a wear-resistant and corrosion-resistant material, the surface of which includes a wear-resistant and corrosion-resistant coating; wherein, the wear-resistant and corrosion-resistant coating consists of a Si interface layer, a nano-TiCN layer, and a nano-SiC layer sequentially from the inner interface to the outer surface of the coating.

[0007] A second aspect of the present invention provides a wear-resistant and corrosion-resistant plunger rod, the wear-resistant and corrosion-resistant plunger rod comprising a plunger rod substrate and a wear-resistant and corrosion-resistant coating formed on the surface of the plunger rod substrate, the wear-resistant and corrosion-resistant coating being the aforementioned wear-resistant and corrosion-resistant coating of the present invention.

[0008] The third aspect of the present invention provides a method for preparing a wear-resistant and corrosion-resistant material, the method comprising: sequentially forming a Si interface layer, a nano-TiCN layer and a nano-SiC layer on the surface of a substrate.

[0009] The fourth aspect of the present invention provides a wear-resistant and corrosion-resistant material prepared by the preparation method described in the present invention.

[0010] The fifth aspect of this invention provides a method for preparing a wear-resistant and corrosion-resistant plunger rod, which is carried out in accordance with the method for preparing wear-resistant and corrosion-resistant materials described in this invention.

[0011] The sixth aspect of the present invention provides a wear-resistant and corrosion-resistant plunger rod prepared by the preparation method described in the present invention.

[0012] The seventh aspect of this invention provides the application of the wear-resistant and corrosion-resistant plunger rod described herein in the field of plunger pumps.

[0013] In this invention, the silicon interface layer on the substrate surface can improve the hardness and strength of the plunger rod substrate, alleviate the thermal expansion coefficient mismatch between the nano-TiCN layer and the substrate, and enhance the film-substrate bonding strength while reducing interfacial stress. The nano-TiCN layer is composed of nano-TiCN grains, enabling it to form a strong interfacial bond with the silicon interface layer on the substrate surface, thereby improving its bonding force with the silicon interface layer and its barrier ability against corrosive media. The nano-SiC layer is composed of nano-SiC grains, resulting in good bonding with the nano-TiCN layer. Simultaneously, the nano-SiC particles have higher hardness and a lower coefficient of friction, further enhancing the wear resistance of the coating. Based on this, the composite coating formed by the silicon interface layer, nano-TiCN layer, and nano-SiC layer possesses excellent properties such as high hardness, strong bonding, low wear, and high corrosion resistance. It can significantly improve the surface hardness of wear-resistant and corrosion-resistant materials, the density of wear-resistant and corrosion-resistant coatings, and the ability to block the penetration of corrosive media, while reducing the wear rate, thereby improving its wear resistance and corrosion resistance. Attached Figure Description

[0014] Figure 1 is a schematic diagram of the wear-resistant and corrosion-resistant plunger rod structure prepared in Example 1;

[0015] Figure 2 is a cross-sectional SEM image of the wear-resistant and corrosion-resistant coating on the surface of the wear-resistant and corrosion-resistant plunger rod prepared in Example 1;

[0016] Figure 3 is a SEM image of the nano-TiCN layer in the wear-resistant and corrosion-resistant coating on the surface of the wear-resistant and corrosion-resistant plunger rod prepared in Example 1;

[0017] Figure 4 is an SEM image of the nano-SiC layer in the wear-resistant and corrosion-resistant coating on the surface of the wear-resistant and corrosion-resistant plunger rod prepared in Example 1.

[0018] Figure 5 is a test diagram of the adhesion of the wear-resistant and corrosion-resistant coating on the surface of the wear-resistant and corrosion-resistant plunger rod prepared in Example 1;

[0019] Figure 6 is a test diagram of the average friction coefficient of the wear-resistant and corrosion-resistant coating on the surface of the wear-resistant and corrosion-resistant plunger rod prepared in Example 1;

[0020] Figure 7 is a test diagram of the average wear rate of the wear-resistant and corrosion-resistant coatings on the surface of the wear-resistant and corrosion-resistant plunger rods prepared in Example 1 and Example 15;

[0021] Figure 8 is a test diagram of the average corrosion rate of the wear-resistant and corrosion-resistant coatings on the surface of the wear-resistant and corrosion-resistant plunger rods prepared in Examples 1 and 15. Detailed Implementation

[0022] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0023] The present invention provides a wear-resistant and corrosion-resistant material, the surface of which includes a wear-resistant and corrosion-resistant coating; wherein, the wear-resistant and corrosion-resistant coating consists of a Si interface layer, a nano TiCN layer and a nano SiC layer from the inner interface to the outer surface of the coating.

[0024] In this invention, the thickness of the Si interface layer can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the thickness of the Si interface layer is 0.5 to 1 μm.

[0025] In this invention, the thickness of the nano-TiCN layer can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the thickness of the nano-TiCN layer is 15 to 20 μm.

[0026] In this invention, the thickness of the nano-SiC layer can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the thickness of the nano-SiC layer is 12 to 18 μm.

[0027] In the nano-TiCN layer of the present invention, the nano-TiCN grain size can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the nano-TiCN grain size is 100-200 nm, preferably 100-150 nm.

[0028] In the nano-SiC layer of the present invention, the nano-SiC grain size can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the nano-SiC grain size is 50-150 nm.

[0029] In this invention, the base material of the wear-resistant and corrosion-resistant material can be selected from a wide range of materials, and commonly used materials can be applied to this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the base material of the wear-resistant and corrosion-resistant material is one or more of carbon steel, stainless steel, corrosion-resistant alloy, and ceramic.

[0030] In this invention, the range of matrix types for wear-resistant and corrosion-resistant materials is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the matrix of the wear-resistant and corrosion-resistant material is one or more of the following: plunger rod, ceramic, carbon-based material, corrosion-resistant alloy, and steel.

[0031] According to a preferred embodiment of the present invention, the wear-resistant and corrosion-resistant coating is formed on the inner and / or outer surface of the substrate.

[0032] In this invention, the bonding strength of the wear-resistant and anti-corrosion coating can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the bonding strength between the layers of the wear-resistant and anti-corrosion coating is 30 to 60 N, preferably 40 to 55 N.

[0033] In this invention, the average friction coefficient of the wear-resistant and corrosion-resistant coating can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the average friction coefficient of the wear-resistant and corrosion-resistant coating is 0.1 to 0.5, preferably 0.15 to 0.35.

[0034] In this invention, the average wear rate of the wear-resistant and anti-corrosion coating can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the average wear rate of the wear-resistant and anti-corrosion coating is 1×10⁻⁶. -7 ~40×10 -7 mm 3 N -1 m -1 Preferably 1.1×10 -7 ~4×10-7 mm 3 N -1 m -1 .

[0035] In this invention, the average corrosion rate of the wear-resistant and anti-corrosion coating can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the average corrosion rate of the wear-resistant and anti-corrosion coating is 0.003 to 0.08 mm / a, preferably 0.003 to 0.03 mm / a.

[0036] The present invention provides a wear-resistant and corrosion-resistant plunger rod, which includes a plunger rod substrate and a wear-resistant and corrosion-resistant coating formed on the surface of the plunger rod substrate, wherein the wear-resistant and corrosion-resistant coating is the aforementioned wear-resistant and corrosion-resistant coating of the present invention.

[0037] Wear-resistant and corrosion-resistant materials with the aforementioned characteristics can achieve the purpose of this invention. There are no special requirements for their preparation methods. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the preparation method of the wear-resistant and corrosion-resistant material includes: sequentially forming a Si interface layer, a nano TiCN layer and a nano SiC layer on the surface of a substrate.

[0038] According to a preferred embodiment of the present invention, the method for forming the Si interface layer is hot-wire chemical vapor deposition.

[0039] According to a preferred embodiment of the present invention, the method for forming the nano-TiCN layer is high-vacuum chemical vapor deposition.

[0040] According to a preferred embodiment of the present invention, the method for forming the nano-SiC layer is high-vacuum chemical vapor deposition.

[0041] In this invention, the preparation method of the wear-resistant and corrosion-resistant material further includes a substrate cleaning step S1): the substrate surface is cleaned by high-energy plasma under vacuum conditions.

[0042] In this invention, the vacuum degree in step S1) has a wide selectable range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the vacuum degree in step S1) is 1×10⁻⁶. -4 ~5×10 -4 Pa.

[0043] In this invention, there are no special requirements for the high-energy plasma in step S1). The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the high-energy plasma in step S1) is one or more of Ar, H2, and SiH4, preferably Ar.

[0044] In this invention, there are no special requirements for the cleaning time in step S1). The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the cleaning time in step S1) is 20 to 40 minutes.

[0045] In this invention, there are no special requirements for the cleaning method of the substrate surface in step S1). Those skilled in the art can clean it according to actual needs. For example, the cleaning steps may include: first grinding the substrate surface to remove impurities, then sandblasting and polishing the substrate surface, then ultrasonically cleaning it with alcohol, and then drying it after cleaning.

[0046] In this invention, the preparation method of the wear-resistant and corrosion-resistant material includes step S2, which involves forming a Si interface layer on the substrate surface using hot-wire chemical vapor deposition.

[0047] In this invention, the range of Si source types that can be selected in step S2) is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the Si source in step S2) is one or more of SiH4, dichlorosilane, and tetramethylsilane.

[0048] In this invention, the vacuum degree in step S2) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the vacuum degree in step S2) is 1×10⁻⁶. -4 ~5×10 -4 Pa.

[0049] In this invention, the hot wire bias voltage in step S2) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the hot wire bias voltage in step S2) is 0.1 to 2.5 kV, preferably 0.4 to 1.5 kV.

[0050] In this invention, the silicon infiltration temperature in step S2) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the silicon infiltration temperature in step S2) is 30 to 200°C, preferably 80 to 120°C.

[0051] In this invention, the silicon infiltration time in step S2) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the silicon infiltration time in step S2) is 0.2 to 4 hours, preferably 2 to 4 hours.

[0052] This invention utilizes hot-wire chemical vapor deposition (CVD) under vacuum conditions. A silicon source is introduced into the tube, and the substrate temperature is controlled at a low temperature by a cooling device. Silicon plasma is generated through high-temperature pyrolysis of the hot wire, and the surface of the plunger is subjected to vacuum cryogenic silicon infiltration to prepare a silicon interface layer. Compared to conventional ion-diffusion silicon infiltration processes, this invention employs hot-wire CVD to prepare the Si interface layer, offering advantages such as lower stress and stronger adhesion.

[0053] In the preparation method of the wear-resistant and corrosion-resistant material of the present invention, step S3) of forming a nano-TiCN layer by high-vacuum chemical vapor deposition includes:

[0054] (a) Place the substrate with the Si interface layer into a vacuum chamber, evacuate the vacuum chamber, and then introduce gas.

[0055] (b) The vacuum chamber is heated, and then a TiCN precursor-containing gas source is introduced for chemical vapor deposition;

[0056] (c) After deposition is complete, stop the gas supply and cool down.

[0057] In this invention, the vacuum degree in step (a) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the vacuum degree in step (a) is 5 × 10⁻⁶. -4 ~5×10 -3 Pa. The aforementioned vacuum environment is a high vacuum environment. Using the aforementioned high-vacuum chemical vapor deposition method is beneficial for controlling grain size and forming high-purity, high-density, and low-defect coatings. In contrast, conventional chemical vapor deposition techniques for preparing TiCN coatings typically require deposition pressures greater than 20,000 Pa, which easily introduces defects and impurities, reducing crystallinity and density. Compared to existing technologies, the solution adopted in this invention has significant advantages.

[0058] According to a preferred embodiment of the present invention, the gas in step (a) is a mixture of a reducing gas and an inert gas. The flow rate ratio of the reducing gas to the inert gas is not particularly required and can be selected according to actual needs. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the flow rate ratio of the reducing gas to the inert gas is 1 to 3:1. In step (a) of the present invention, there are no special requirements for the reducing gas and the inert gas; they can be selected according to actual needs. For example, the reducing gas can be hydrogen, and the inert gas can be argon.

[0059] In this invention, the gas flow rate in step (a) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the gas flow rate in step (a) is 200 to 400 sccm.

[0060] In this invention, the deposition temperature in step (b) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the deposition temperature in step (b) is 600-800°C, preferably 680-720°C.

[0061] In this invention, the deposition pressure in step (b) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the deposition pressure in step (b) is 30 to 120 Pa, preferably 60 to 110 Pa.

[0062] In this invention, the deposition time in step (b) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the deposition time in step (b) is 2 to 5 hours.

[0063] According to a preferred embodiment of the present invention, the TiCN-containing precursor gas in step (b) includes Ti source gas, C source gas, N source gas and hydrogen.

[0064] In this invention, there are no special requirements for the type of Ti source gas in step (b). The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the Ti source gas in step (b) is one or more of titanium tetrachloride, titanium trichloride, and titanium dichloride, preferably titanium tetrachloride.

[0065] In this invention, there are no special requirements for the type of C source gas in step (b). The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the C source gas in step (b) is one or more of methane, ethane, ethylene, propylene, acetylene, and acetonitrile, preferably one or more of ethylene and acetonitrile.

[0066] In this invention, there are no special requirements for the type of N source gas in step (b). The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the N source gas in step (b) is one or more of nitrogen, ammonia, and acetonitrile, preferably one or more of nitrogen and acetonitrile.

[0067] In this invention, the flow rate of the Ti source gas in step (b) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the flow rate of the Ti source gas in step (b) is 50 to 300 sccm.

[0068] In this invention, the flow rate of the C source gas in step (b) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the flow rate of the C source gas in step (b) is 50 to 300 sccm.

[0069] In this invention, the flow rate of the N source gas in step (b) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the flow rate of the N source gas in step (b) is 50 to 300 sccm.

[0070] In this invention, the flow rate of hydrogen in step (b) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the flow rate of hydrogen in step (b) is 50 to 200 sccm.

[0071] By adopting the aforementioned preferred scheme, the nucleation size and final grain size of TiCN grains in the nano-TiCN layer can be adjusted by regulating the flow rate of the TiCN precursor gas, so as to form nano-TiCN grains.

[0072] In this invention, the cooling temperature in step (c) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the cooling temperature in step (c) is 400 to 600°C.

[0073] In the preparation method of the wear-resistant and corrosion-resistant material of the present invention, step S4) of forming a nano-SiC layer on the surface of the nano-TiCN layer by high vacuum chemical vapor deposition includes:

[0074] (d) Introduce reducing gas into the vacuum chamber and keep it warm;

[0075] (e) Introduce reactive gases for chemical vapor deposition.

[0076] In this invention, the reducing gas flow rate in step (d) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the reducing gas flow rate in step (d) is 100 to 300 sccm.

[0077] In this invention, the range of reducing gas types that can be selected in step (d) is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the reducing gas in step (d) is hydrogen.

[0078] In this invention, the heat preservation temperature in step (d) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the heat preservation temperature in step (d) is 400 to 600°C.

[0079] In this invention, the heat preservation time in step (d) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the heat preservation time in step (d) is 1 to 3 hours.

[0080] In step (e) of the present invention, before the chemical vapor deposition reaction begins, the reducing gas flow rate needs to be reduced. The range of reducing gas flow rate in step (e) is relatively wide. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the reducing gas flow rate in step (e) can be reduced to 100-200 sccm.

[0081] In this invention, the deposition temperature in step (e) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the deposition temperature in step (e) is 800-1100°C, preferably 900-1000°C.

[0082] In this invention, the deposition pressure in step (e) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the deposition pressure in step (e) is 10 to 110 Pa, preferably 40 to 60 Pa.

[0083] In this invention, the deposition time in step (e) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the deposition time in step (e) is 0.5 to 2 hours.

[0084] According to a preferred embodiment of the present invention, the reaction gas in step (e) includes a reducing gas, a silicon carbide source gas, and an inert gas. In step (e) of the present invention, there are no special requirements for the reducing gas, silicon carbide source gas, and inert gas; they can be selected according to actual needs. For example, the reducing gas can be hydrogen, the silicon carbide source gas can be trichloromethylsilane, and the inert gas can be argon.

[0085] In this invention, the flow rate of the reducing gas in the reaction gas in step (e) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the flow rate of the reducing gas in the reaction gas in step (e) is 100 to 150 sccm.

[0086] In this invention, the flow rate of the carbon-silicon source gas in the reaction gas in step (e) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the flow rate of the carbon-silicon source gas in the reaction gas in step (e) is 100 to 150 sccm.

[0087] In this invention, the flow rate of the inert gas in the reaction gas in step (e) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the flow rate of the inert gas in the reaction gas in step (e) is 50 to 200 sccm.

[0088] In this invention, step S4) further includes: after the deposition is completed, stopping the introduction of all gases except the inert gas, and allowing the temperature to drop naturally to room temperature.

[0089] In this invention, the inert gas flow rate after deposition in step S4) has a wide selectable range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the inert gas flow rate after deposition in step S4) is adjusted to 100-200 sccm.

[0090] In this invention, the chemical vapor deposition process involves heating and cooling. There are no special requirements for the heating rate and cooling rate, which can be selected according to actual needs, and will not be elaborated here.

[0091] This invention provides a wear-resistant and corrosion-resistant material prepared by the method described herein. This material exhibits good wear-resistant and corrosion-resistant coating density, high surface hardness, and excellent barrier properties against corrosive media penetration, demonstrating superior wear resistance and corrosion resistance.

[0092] This invention provides a method for preparing a wear-resistant and corrosion-resistant plunger rod. The method for preparing the wear-resistant and corrosion-resistant plunger rod can be carried out according to the method for preparing wear-resistant and corrosion-resistant materials described in this invention, and will not be repeated here.

[0093] This invention provides a wear-resistant and corrosion-resistant plunger rod prepared by the preparation method described herein.

[0094] The wear-resistant and corrosion-resistant coating formed on the surface of a plunger rod in this invention consists of a Si interface layer, a nano-TiCN layer, and a nano-SiC layer. First, a Si interface layer is prepared on the plunger rod surface using a vacuum impregnation method, which improves and enhances the chemical compatibility between the plunger rod and the nano-TiCN layer on its surface. Simultaneously, the Si interface layer can alleviate the mismatch in thermal expansion coefficients between the plunger rod substrate and the nano-TiCN layer, reduce interfacial stress, and improve the bonding strength between the nano-TiCN layer and the plunger rod substrate, thus contributing to enhanced corrosion resistance. Second, a nano-TiCN layer is prepared using CVD and deposited on the surface of the Si interface layer. This corrosion-resistant layer enhances the barrier capability against solid-liquid-gas three-phase media, simultaneously improving the plunger rod's corrosion resistance and wear resistance. Finally, a nano-SiC layer is prepared on the surface of the corrosion-resistant layer using CVD. The nano-SiC layer provides excellent wear resistance, and the nano-SiC grains also exhibit good corrosion resistance, further reducing the plunger rod's friction coefficient while minimizing corrosion damage from solid-liquid-gas three-phase media in oil and gas field downhole tools, thereby improving the plunger rod's wear resistance and corrosion resistance. In summary, the wear-resistant and corrosion-resistant plunger rod provided by the present invention includes a plunger rod substrate and a wear-resistant and corrosion-resistant coating on its surface composed of a Si interface layer, a nano-TiCN layer, and a nano-SiC layer, which has excellent wear-resistant and corrosion-resistant properties.

[0095] This invention provides the application of the wear-resistant and corrosion-resistant plunger rod described herein in the field of plunger pumps. The wear-resistant and corrosion-resistant plunger rod provided by this invention consists of a plunger rod matrix, a Si interface layer, a nano-TiCN layer, and a nano-SiC layer. It exhibits a low coefficient of friction, low wear rate, and low average corrosion rate. Using it as a key component of a plunger pump in oil and gas field production can significantly improve the service life of the plunger rod and the production efficiency of oil and gas fields under harsh environments.

[0096] Example 1

[0097] (1) The plunger rod substrate is ground to remove impurities, sandblasted with quartz sand, polished, and then ultrasonically cleaned with alcohol. After cleaning, the plunger rod substrate is placed in an oven and dried at 100°C for 3 hours before being placed in a vacuum device.

[0098] (2) Evacuate the chamber to a vacuum level of 2×10⁻⁶. -4 Pa; Argon gas is then introduced, and a high-frequency pulse voltage is applied to form a high-energy argon plasma to clean the surface of the plunger rod substrate for 30 minutes.

[0099] (3) Formation of the silicon interface layer: After cleaning, maintain a vacuum level of 2×10 -4A bias voltage of 1 kV is applied to both ends of the hot wire. High-energy silicon plasma is generated by cracking the silicon source dichlorosilane through the metal wire, and then used to perform silicon diffusion treatment on the surface of the plunger rod substrate. During silicon diffusion, the substrate temperature is controlled by an external cooling device to maintain it at 100°C, and the silicon diffusion time is 3 hours.

[0100] (4) Place the plunger containing the silicon interface layer into the CVD apparatus and use a two-stage vacuum pump set to evacuate the CVD apparatus to 1×10⁻⁶. -3 Pa, then hydrogen and argon are simultaneously introduced, with a hydrogen flow rate of 200 sccm and an argon flow rate of 100 sccm. The furnace heating program is started, with the heating rate set to 5℃ / min and the deposition temperature set to 700℃;

[0101] (5) A nano-TiCN layer was prepared on the surface of a plunger containing a silicon interface layer by high-vacuum first chemical vapor deposition, including the following steps: the CVD heating device was heated to 400℃ at 4℃ / min and held for 1h, then heated to 700℃ at 6℃ / min, with a deposition pressure of 60Pa. Afterwards, a coating deposition process was initiated, introducing titanium tetrachloride, hydrogen, nitrogen, acetonitrile, and ethylene, with flow rates of 200sccm for titanium tetrachloride, 100sccm for acetonitrile, 150sccm for hydrogen, 100sccm for nitrogen, and 60sccm for ethylene. The deposition time was 5h, and the deposition pressure was adjusted to 6×10⁻⁶ by adjusting the pumping speed of the vacuum pump group. 1 Pa;

[0102] (6) After the first chemical vapor deposition in high vacuum is completed, the CVD device enters the controllable cooling mode, stops the introduction of all gases, and the cooling rate is 8℃ / min, cooling down to 400℃.

[0103] (7) When the temperature in the reaction chamber drops to 400℃, 200 sccm of hydrogen gas is introduced and kept warm for 3 hours.

[0104] (8) After the heat preservation process is completed, adjust the hydrogen flow rate to 100 sccm and start the heating program to heat the cavity to 950°C.

[0105] (9) When the temperature reaches 950℃, high-vacuum second chemical vapor deposition begins. A nano-SiC layer is prepared on the surface of the nano-TiCN layer prepared by high-vacuum first chemical vapor deposition. Hydrogen, trichloromethylsilane, and argon are introduced sequentially. The flow rates of hydrogen, trichloromethylsilane, and argon are 120 sccm and 60 sccm respectively. The deposition time is 2 hours. The deposition pressure is 50 Pa by adjusting the pumping speed of the vacuum pump group.

[0106] (10) After the high vacuum second chemical vapor deposition process is completed, the argon flow rate is increased to 100 sccm and other gases are stopped. The gas is allowed to cool naturally to room temperature to obtain a wear-resistant and corrosion-resistant plunger rod.

[0107] Figure 1 is a schematic diagram of the wear-resistant and corrosion-resistant plunger rod structure prepared in Example 1.

[0108] Figure 2 shows a cross-sectional SEM image of the wear-resistant and corrosion-resistant coating on the surface of a wear-resistant and corrosion-resistant plunger rod prepared in Example 1. The results in Figure 2 show that the Si interface layer and the plunger rod substrate, the Si interface layer and the nano-TiCN layer, and the nano-TiCN layer and the nano-SiC layer in the wear-resistant and corrosion-resistant coating on the plunger rod surface have dense and uniform structures. The thickness of the Si interface layer is approximately 0.5-1 μm, the thickness of the nano-TiCN layer is approximately 15-20 μm, and the thickness of the nano-SiC layer is approximately 12-18 μm.

[0109] Figure 3 shows a SEM image of the nano-TiCN layer in the wear-resistant and corrosion-resistant coating on the surface of a wear-resistant and corrosion-resistant plunger prepared in Example 1. The results in Figure 3 show that the TiCN grain size in the nano-TiCN layer is approximately 150 nm.

[0110] Figure 4 shows an SEM image of the nano-SiC layer in the wear-resistant and corrosion-resistant coating on the surface of a wear-resistant and corrosion-resistant plunger rod prepared in Example 1. The results in Figure 4 show that the SiC grain size in the nano-SiC layer is approximately 100 nm.

[0111] Figure 5 shows the adhesion test results of the wear-resistant and corrosion-resistant coating on the surface of a wear-resistant and corrosion-resistant plunger rod prepared in Example 1. The results in Figure 5 show that the adhesion of the wear-resistant and corrosion-resistant coating is 55 N.

[0112] Figure 6 shows the average friction coefficient test result of the wear-resistant and corrosion-resistant coating on the surface of the wear-resistant and corrosion-resistant plunger rod prepared in Example 1. The results in Figure 6 show that the average friction coefficient is 0.18.

[0113] Figure 7 shows the average wear rate test of the wear-resistant and corrosion-resistant coating on the surface of the wear-resistant and corrosion-resistant plunger rod prepared in Example 1. The results in Figure 7 show that the average wear rate is 1.2 × 10⁻⁶. -7 mm 3 N -1 m -1 .

[0114] Figure 8 shows the average corrosion rate test of the wear-resistant and corrosion-resistant coating on the surface of a wear-resistant and corrosion-resistant plunger rod prepared in Example 1. The results in Figure 8 show that the average corrosion rate is 0.0042 mm / a.

[0115] Example 2

[0116] The only difference compared to Example 1 is that in step (3), the hot wire voltage is 0.4 kV.

[0117] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 40 N, an average friction coefficient of 0.23, and an average wear rate of 3.4 × 10⁻⁶. -7 mm 3 N -1 m -1 The average corrosion rate is 0.016 mm / a.

[0118] Example 3

[0119] The only difference from Example 1 is that in step (3), the voltage applied to the hot wire is 2kV.

[0120] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 42 N, an average friction coefficient of 0.26, and an average wear rate of 3.3 × 10⁻⁶. -7 mm 3 N -1 m -1 The average corrosion rate is 0.014 mm / a.

[0121] Example 4

[0122] The only difference from Example 1 is that in step (3), the silicon infiltration time is 0.5h.

[0123] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 40 N, an average friction coefficient of 0.28, and an average wear rate of 1.8 × 10⁻⁶. -6 mm 3 N -1 m -1 The average corrosion rate is 0.021 mm / a.

[0124] Example 5

[0125] The only difference from Example 1 is that the substrate temperature in step (3) is 155°C.

[0126] The results show that the adhesion of the wear-resistant and anti-corrosion coating is 42 N, the average coefficient of friction is 0.31, and the average wear rate is 1.5 × 10⁻⁶. -6 mm 3 N -1 m -1 The average corrosion rate is 0.028 mm / a.

[0127] Example 6

[0128] The only difference from Example 1 is that the substrate temperature in step (3) is 45°C.

[0129] The results show that the adhesion of the wear-resistant and anti-corrosion coating is 31 N, the average coefficient of friction is 0.57, and the average wear rate is 1.5 × 10⁻⁶. -6 mm3 N -1 m -1 The average corrosion rate is 0.055 mm / a.

[0130] Example 7

[0131] The only difference from Example 1 is that the deposition temperature in step (5) is 630°C.

[0132] The results showed that the wear-resistant and anti-corrosion coating had an adhesion strength of 36 N, an average friction coefficient of 0.45, and an average wear rate of 2.8 × 10⁻⁶. -6 mm 3 N -1 m -1 The average corrosion rate is 0.051 mm / a.

[0133] Example 8

[0134] The only difference from Example 1 is that the deposition temperature in step (5) is 760°C.

[0135] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 37 N, an average friction coefficient of 0.45, and an average wear rate of 2.9 × 10⁻⁶. -6 mm 3 N -1 m -1 The average corrosion rate is 0.053 mm / a.

[0136] Example 9

[0137] The only difference from Example 1 is that in step (5), the deposition pressure is 110 Pa.

[0138] The results show that the adhesion of the wear-resistant and anti-corrosion coating is 41 N, the average coefficient of friction is 0.34, and the average wear rate is 2.5 × 10⁻⁶. -7 mm 3 N -1 m -1 The average corrosion rate is 0.011 mm / a.

[0139] Example 10

[0140] The only difference from Example 1 is that in step (5), the deposition pressure is 45 Pa.

[0141] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 39 N, an average friction coefficient of 0.28, and an average wear rate of 3.6 × 10⁻⁶. -7 mm 3 N -1 m -1 The average corrosion rate is 0.051 mm / a.

[0142] Example 11

[0143] The only difference from Example 1 is that the deposition temperature in step (9) is 890°C.

[0144] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 42 N, an average friction coefficient of 0.31, and an average wear rate of 2.2 × 10⁻⁶. -6 mm 3 N -1 m -1 The average corrosion rate is 0.038 mm / a.

[0145] Example 12

[0146] The only difference from Example 1 is that the deposition temperature in step (9) is 1100°C.

[0147] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 41 N, an average friction coefficient of 0.32, and an average wear rate of 2.0 × 10⁻⁶. -6 mm 3 N -1 m -1 The average corrosion rate is 0.035 mm / a.

[0148] Example 13

[0149] The only difference from Example 1 is that in step (9), the deposition pressure is 110 Pa.

[0150] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 39 N, an average friction coefficient of 0.35, and an average wear rate of 2.7 × 10⁻⁶. -7 mm 3 N -1 m -1 The average corrosion rate is 0.028 mm / a.

[0151] Example 14

[0152] The only difference from Example 1 is that the deposition pressure in step (9) is 15 Pa.

[0153] The results show that the wear-resistant and anti-corrosion coating has an adhesion strength of 40 N, an average friction coefficient of 0.34, and an average wear rate of 2.6 × 10⁻⁶. -7 mm 3 N -1 m -1 The average corrosion rate is 0.027 mm / a.

[0154] Example 15

[0155] Compared with Example 8, the only difference is that in step (3), ordinary vacuum silicon diffusion treatment is used, and the silicon diffusion temperature is 500°C.

[0156] The results show that the adhesion of the wear-resistant and anti-corrosion coating is 36 N, the average coefficient of friction is 0.40, and the average wear rate is 35.5 × 10⁻⁶. -7 mm 3 N -1 m -1 The average corrosion rate is 0.071 mm / a.

[0157] Figures 7 and 8 show the average wear rate test diagram and the average corrosion rate test diagram of the wear-resistant and corrosion-resistant coating on the surface of the prepared wear-resistant and corrosion-resistant plunger rod.

[0158] The preferred embodiments of the present invention have been described above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A wear-resistant and corrosion-resistant material, characterized in that, The surface of the material includes a wear-resistant and corrosion-resistant coating; wherein, the wear-resistant and corrosion-resistant coating consists of a Si interface layer, a nano-TiCN layer, and a nano-SiC layer, sequentially from the inner interface to the outer surface of the coating.

2. The material according to claim 1, characterized in that, The thickness of the Si interface layer is 0.5–1 μm; and / or The thickness of the nano-TiCN layer is 15–20 μm; and / or The thickness of the nano-SiC layer is 12–18 μm.

3. The material according to claim 1 or 2, characterized in that, In the nano-TiCN layer, the nano-TiCN grain size is 100–200 nm; and / or In the nano-SiC layer, the size of the nano-SiC grains is 50–150 nm.

4. The material according to claim 3, characterized in that, In the nano-TiCN layer, the size of the nano-TiCN grains is 100-150 nm.

5. The material according to claim 1 or 2, characterized in that, The matrix material of the material is one or more of carbon steel, stainless steel, corrosion-resistant alloy, and ceramic; and / or The matrix of the material is one or more of the following: plunger rod, ceramic, carbon-based material, corrosion-resistant alloy, and steel. The wear-resistant and corrosion-resistant coating is formed on the inner and / or outer surface of the substrate.

6. The material according to claim 1 or 2, characterized in that, The bonding force between the layers of the wear-resistant and corrosion-resistant coating is 30-60N.

7. The material according to claim 1 or 2, characterized in that, The wear-resistant and corrosion-resistant coating has an average coefficient of friction of 0.1 to 0.5; and / or The average wear rate of the wear-resistant and corrosion-resistant coating is 1×10⁻⁶. -7 ~40×10 -7 mm 3 N -1 m -1 ; and / or The average corrosion rate of the wear-resistant and corrosion-resistant coating is 0.003 to 0.08 mm / a.

8. A wear-resistant and corrosion-resistant plunger rod, characterized in that, The wear-resistant and corrosion-resistant plunger rod includes a plunger rod substrate and a wear-resistant and corrosion-resistant coating formed on the surface of the plunger rod substrate, wherein the wear-resistant and corrosion-resistant coating is the wear-resistant and corrosion-resistant coating as described in any one of claims 1-7.

9. A method for preparing the wear-resistant and corrosion-resistant material according to any one of claims 1-7, characterized in that, The method includes: sequentially forming a Si interface layer, a nano-TiCN layer, and a nano-SiC layer on the surface of a substrate.

10. The preparation method according to claim 9, characterized in that, The method for forming the Si interface layer is hot-wire chemical vapor deposition; and / or The method for forming the nano-TiCN layer is high-vacuum chemical vapor deposition; and / or The method for forming the nano-SiC layer is high-vacuum chemical vapor deposition.

11. The preparation method according to claim 9 or 10, characterized in that, The method also includes a substrate cleaning step S1): the substrate surface is cleaned by high-energy plasma under vacuum conditions.

12. The preparation method according to claim 11, characterized in that, In step S1), Vacuum degree is 1×10 -4 ~5×10 -4 Pa; and / or The high-energy plasma is one or more of Ar, H2, and SiH4; and / or The cleaning time is 20 to 40 minutes.

13. The preparation method according to claim 10, characterized in that, Step S2) of forming a Si interface layer on the substrate surface using hot-wire chemical vapor deposition includes: The Si source is one or more of SiH4, dichlorosilane, and tetramethylsilane; and / or Vacuum degree is 1×10 -4 ~5×10 -4 Pa; and / or The hot wire is biased at a voltage of 0.1–2.5 kV; and / or The silicon diffusion temperature is 30–200℃; and / or The silicon infiltration time is 0.2 to 4 hours.

14. The preparation method according to claim 10, characterized in that, Step S3) of forming the nano-TiCN layer using high-vacuum chemical vapor deposition includes: (a) Place the substrate with the Si interface layer into a vacuum chamber, evacuate the vacuum chamber, and then introduce gas. (b) The vacuum chamber is heated, and then a gas containing TiCN precursor is introduced for chemical vapor deposition; (c) After deposition is complete, stop the gas supply and cool down.

15. The preparation method according to claim 14, characterized in that, In step (a), The vacuum level is 5×10⁻⁶. -4 ~5×10 -3 Pa; and / or The gas is a mixture of reducing gas and inert gas, with a flow ratio of reducing gas to inert gas of 1 to 3:1; and / or The gas flow rate is 200–400 sccm.

16. The preparation method according to claim 14, characterized in that, In step (b), The deposition temperature is 600–800℃; and / or Deposition pressure is 30–120 Pa; and / or The deposition time is 2–5 hours; and / or The precursor gases include Ti source gas, C source gas, N source gas, and hydrogen.

17. The preparation method according to claim 16, characterized in that, In step (b), The Ti source gas is one or more of titanium tetrachloride, titanium trichloride, and titanium dichloride; and / or The C source gas is one or more of methane, ethane, ethylene, propylene, acetylene, and acetonitrile; and / or The N source gas is one or more of nitrogen, ammonia, and acetonitrile; and / or The flow rate of the Ti source gas is 50–300 sccm; and / or The flow rate of the C source gas is 50–300 sccm; and / or The flow rate of the N source gas is 50–300 sccm; and / or The flow rate of the hydrogen gas is 50–200 sccm.

18. The preparation method according to claim 14, characterized in that, In step (c), Cool down to 400-600℃.

19. The preparation method according to claim 9 or 10, characterized in that, Step S4) of forming a nano-SiC layer on the surface of a nano-TiCN layer by high-vacuum chemical vapor deposition includes: (d) Introduce reducing gas into the vacuum chamber and keep it warm; (e) Introduce reactive gases for chemical vapor deposition.

20. The preparation method according to claim 19, characterized in that, In step (d), The reducing gas flow rate is 100–300 sccm; and / or The reducing gas is hydrogen; and / or The insulation temperature is 400–600℃; and / or The heat preservation time is 1 to 3 hours.

21. The preparation method according to claim 19, characterized in that, In step (e), The deposition temperature is 800–1100℃; and / or Deposition pressure is 10–110 Pa; and / or The deposition time is 0.5 to 2 hours.

22. The preparation method according to claim 19, characterized in that, In step (e), The reactant gases include reducing gases, carbon-silicon source gases, and inert gases; and / or The flow rate of the reducing gas in the reaction gas is 100–150 sccm; and / or The flow rate of the carbon-silicon source gas in the reaction gas is 100–150 sccm; and / or The inert gas flow rate in the reaction gas is 50–200 sccm.

23. The preparation method according to claim 19, characterized in that, Step S4 also includes: After deposition, stop introducing any gas other than the inert gas and allow it to cool naturally to room temperature; the inert gas flow rate is adjusted to 100-200 sccm.

24. The wear-resistant and corrosion-resistant material prepared by the preparation method according to any one of claims 9-23.

25. A method for preparing the wear-resistant and corrosion-resistant plunger rod according to claim 8, characterized in that, The method is carried out according to the preparation method described in any one of claims 9-23.

26. The wear-resistant and corrosion-resistant plunger rod prepared by the preparation method according to claim 25.

27. The application of the wear-resistant and corrosion-resistant plunger rod according to any one of claims 8 and 26 in the field of plunger pumps.

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