A graphene-modified titanium alloy oil drill pipe wear-resistant belt and its preparation method

Abstract

The present invention belongs to the field of material processing and specifically discloses a graphene-modified titanium alloy oil drill pipe wear-resistant belt and a preparation method thereof. Specifically, the method comprises the following steps: removing oil stains from the surface of a titanium alloy drill pipe joint substrate and performing a grinding process; utilizing the principle of selective oxidation of aluminum and vanadium under ultra-low oxygen partial pressure, and under the protection of a mixed gas of argon and oxygen and a mixed gas of ultra-low partial pressure oxygen, a graphene-reinforced titanium-based double-layer composite wear-resistant belt is prepared on the titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process, thereby achieving in-situ generation of Al2O3 and V2O5 nano-reinforced particles of Al, V and O. While ensuring the bonding strength of the wear-resistant belt, the hardness, wear resistance and toughness of the cladding coating are greatly improved, while also combining the corrosion resistance of the Ti alloy and the self-lubricating properties of graphene. The wear-resistant belt is suitable for drilling and production of ultra-deep oil and gas, and improves the wear resistance and service life of the drill pipe.

Description

Technical Field

[0001] The invention belongs to the field of material processing, and particularly relates to a graphene-modified titanium alloy oil drill pipe wear-resistant belt and a preparation method thereof. Background Art

[0002] With the exploration and development of deep oil and gas, conventional alloy steel drill pipes have high density and heavy drill string overhang, resulting in high drilling loads; and due to the poor corrosion resistance of conventional steel drill pipes such as hydrogen sulfide stress corrosion, drill string failures are frequent, seriously affecting drilling efficiency and safety.

[0003] Titanium alloy drill pipe is suitable for ultra-deep well drilling due to its high strength, low density, low structural stress, fatigue resistance, and corrosion resistance. However, during the drilling process, the drill pipe comes into direct contact with the wellbore wall, causing rapid wear and tear, which significantly increases the cost of oilfield production. Currently, the main method used is surfacing welding, where a wear-resistant tape with a thickness of at least 2mm is deposited on the surface of the drill pipe joint to effectively protect it. The wear-resistant strip material for traditional steel drill pipe is generally high-hardness alloy steel. However, due to the significant difference in physical properties between steel and titanium alloy, existing high-hardness alloy steel wear-resistant strip materials and wear-resistant strip preparation methods are not suitable for titanium alloy drill pipe. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a graphene-modified titanium alloy oil drill pipe wear-resistant belt and a preparation method thereof, so as to solve the problem of excessive wear rate caused by using titanium alloy drill pipe for drilling during the drilling process.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides a method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt, comprising:

[0007] S1: Degreasing the surface of the titanium alloy drill pipe joint base and performing grinding;

[0008] S2: Under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture, an ultra-high-speed laser cladding process is used to clad the bonding base layer on the surface of the titanium alloy drill pipe joint substrate. The raw materials used for the bonding base layer are a mixture of Ti6Al4V titanium alloy powder and TiO2-bRGO;

[0009] S3: Under the protection of a mixed gas of argon and oxygen and a mixed gas of ultra-low partial pressure oxygen, an ultra-high-speed laser cladding process is used to clad a wear-resistant surface layer on the bonding base layer. The raw materials used for the wear-resistant surface layer are a mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder; a graphene-modified titanium alloy oil drill pipe double-layer composite structure wear-resistant belt is prepared.

[0010] Furthermore, in S1, grinding is performed to a roughness of 10 μm ≤ Ra ≤ 25 μm and an ovality ≤ 0.5%;

[0011] The thickness of the bonding bottom layer in S2 is 0.6 mm to 0.7 mm;

[0012] The ultra-high-speed laser cladding process parameters in S2 are: laser power 2400-2500W, spot diameter 1.5-1.8mm, scanning linear speed 35-45m / min, overlap rate 30-45%, and powder feeding rate 18-20g / min;

[0013] The wear-resistant surface cladding thickness in S3 is 1.4 mm to 1.6 mm;

[0014] The ultra-high-speed laser cladding process parameters in S3 are: laser power 2600-2700W, spot diameter 1.6-1.9mm, scanning linear speed 40-50m / min, overlap rate 40-55%, powder feeding rate 25-30g / min; the wear-resistant surface layer is formed in two passes, and the thickness of a single pass is 0.7mm-0.8mm.

[0015] Furthermore, the proportion of TiO2-bRGO in the mixture of Ti6Al4V titanium alloy powder and TiO2-bRGO in the bonding bottom layer raw materials is 1wt% to 3wt%.

[0016] Furthermore, in the mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder in the wear-resistant surface raw material, the proportion of TiO2-bRGO is 3wt% to 5wt%, and the proportion of micro-nano TiC powder is 4wt% to 7wt%.

[0017] Furthermore, when the high-speed laser cladding process is used to prepare the bonding base layer, the mixed atmosphere of argon and oxygen is protected, the oxygen content is 0.1-0.2 ppm, and the gas flow rate is 21-25 L / min; when the high-speed laser cladding process is used to prepare the wear-resistant surface layer, the mixed atmosphere of argon and oxygen is protected, the oxygen content is 0.3-0.5 ppm, and the gas flow rate is 21-25 L / min.

[0018] Furthermore, the TiO2-bRGO is TiO2-modified partially reduced graphene oxide, the partially reduced graphene oxide has 1 to 5 layers, a sheet size of 1 μm to 7 μm, and a reduction degree of 60% to 70%.

[0019] Furthermore, the preparation method of the TiO2-bRGO comprises:

[0020] First, 20wt% α-titanic acid and 5wt% partially reduced graphene oxide were dissolved in distilled water; and the dispersion was prepared by ultrasonication at an ultrasonic frequency of 8kHz to 10kHz for 100min to 120min; the dispersion was dried at 150℃ to 180℃ for 2h, then placed in a vacuum ball mill for 1.5 to 2 hours, and dried for 0.5 to 2 hours to prepare a TiO2-bRGO powder material with a particle size of 0.1μm to 3μm.

[0021] Furthermore, in the micro-nano TiC powder, the nano powder ratio is 10wt% to 15wt%, the nano TiC particle size is 50nm to 100nm, the micron TiC particle size is 0.1μm to 0.5μm, and the powder purity is greater than 99.5%;

[0022] The Ti6Al4V titanium alloy powder has a particle size of 60 μm to 150 μm, a D50 of 80 to 100 μm, and a fluidity of 35 s / 100 g or less and 40 s / 100 g or less.

[0023] On the other hand, the present invention provides a graphene-modified titanium alloy oil drill pipe wear-resistant belt, which is prepared according to any one of the above-mentioned methods for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt.

[0024] Furthermore, the surface hardness of the wear-resistant belt is 56-62HRC; the wear rate is ≤0.3μm / h and the friction coefficient is 0.29-0.43 in a simulated drilling environment; the corrosion rate is ≤0.025mm / a in a high-temperature, high-pressure, high-salt, and high-acid corrosion environment.

[0025] The present invention has at least the following beneficial effects:

[0026] 1. The present invention utilizes the principle of selective oxidation of aluminum and vanadium under ultra-low oxygen partial pressure. Under the protection of a mixed gas of argon and oxygen and a mixed gas of ultra-low partial pressure oxygen, an ultra-high-speed laser cladding process is used to prepare a graphene-reinforced titanium-based double-layer composite wear-resistant belt on a titanium alloy drill pipe joint substrate. This achieves in-situ generation of Al2O3 and V2O5 nano-reinforced particles of Al, V, and O. While ensuring the bonding strength of the wear-resistant belt, the hardness, wear resistance, and toughness of the cladding coating are greatly improved. At the same time, it combines the corrosion resistance of Ti alloy and the self-lubricating properties of graphene. It is suitable for drilling and production of ultra-deep oil and gas, and improves the wear resistance and service life of the drill pipe.

[0027] 2. The wear-resistant belt of the present invention has strong bonding strength and low internal residual stress, effectively inhibiting crack initiation in the wear-resistant belt. The laser energy density is uniform, heating is rapid, the heat-affected zone is small, the substrate melting depth is below 90μm, the mutual dilution effect between the parent material and the coating is small, and the residual stress is small. Compared with hardfacing or conventional laser cladding processes, it can more effectively inhibit the generation of cracks; the thickness of a single-layer cladding layer is controllable within the range of 600-800μm. The Ti6Al4V powder of the wear-resistant belt substrate powder is similar to the main composition of the titanium alloy drill pipe, easily fused, and has strong bonding strength. By adding / generating in situ different amounts of nano- and micron-reinforced particles in the bonding base layer and the wear-resistant surface layer, a composition gradient, strength gradient, and hardness gradient structure of the titanium alloy drill pipe joint / bonding base layer / wear-resistant surface layer is achieved. While ensuring high bonding strength between the wear-resistant belt and the base material, internal residual stress is reduced, effectively inhibiting crack initiation.

[0028] 3. The wear-resistant belt of the present invention has high strength, high toughness and high wear resistance. It cleverly utilizes the principle of selective oxidation of aluminum and vanadium under ultra-low oxygen partial pressure. Under the protection of a mixed gas of argon and oxygen and a mixed gas of ultra-low partial pressure oxygen, an ultra-high-speed laser cladding process is adopted to prepare a graphene-enhanced titanium-based double-layer composite wear-resistant belt on a titanium alloy drill pipe joint substrate, thereby realizing in-situ generation of Al2O3 and V2O5 nano-reinforcement particles from Al and V in the matrix material and O in the atmosphere, which can greatly improve the strength and hardness of the wear-resistant belt and has a high bonding strength with the matrix material. The in-situ generated Al2O3 and V2O5 nano-reinforcement particles and the added nano-TiC particles serve as heterogeneous nucleation points, which promote nucleation during the laser cladding process, refine the grains of the wear-resistant belt, and play a role in fine grain strengthening and toughening. The size gradient of the reinforcing phase inside the wear-resistant belt ranges from a few nanometers (V2O5, Al2O3), tens of nanometers (Al2O3 and V2O5, TiC) to micron level (TiO2-bRGO). The complementary advantages make the drill pipe joint wear-resistant belt have good resistance to impact wear, abrasion and adhesive wear during service. The addition of TiO2-bRGO makes the wear-resistant belt have the self-lubricating properties of graphene, improving its wear resistance. In addition, TiO2-bRGO with a particle size of 0.1μm to 3μm combines the excellent strength and toughness of graphene, which can prevent crack initiation, stop cracks, deflect cracks or bridge cracks in the wear-resistant belt, thereby greatly improving the strength, toughness and wear resistance of the wear-resistant belt.

[0029] 4. The present invention uses Ti6Al4V powder as the base material, so the wear-resistant belt has the excellent corrosion resistance of titanium alloy materials. Test results show that the wear-resistant belt material of the present invention has excellent corrosion resistance in high temperature, high pressure, high salt and high acid medium corrosion environment.

[0030] 5. The present invention utilizes the principle that TiO2 hydrate and partially reduced graphene oxide share "O" and the hydrophilic properties of both, and adopts α-titanic acid and partially reduced graphene oxide to react to form TiO2-bRGO, which solves the dispersion problem of graphene and solves the problem of uneven mixing during ball milling due to the light density of graphene.

[0031] 6. The present invention utilizes nano- and micron-sized oxide reinforcement particles. During the high-speed laser cladding process, the interface bonding force between the nano-reinforced particles and the Ti6Al4V matrix material is improved by sharing the principle of "O". Compared with ordinary wear-resistant belts, the toughness and wear resistance of the wear-resistant belts of the present invention are greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0033] In the attached figure:

[0034] Figure 1 The present invention is a schematic diagram of a process for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt. DETAILED DESCRIPTION

[0035] The present invention will be described in detail below with reference to the accompanying drawings and in combination with embodiments. It should be noted that, in the absence of conflict, the embodiments and features of the embodiments of the present invention can be combined with each other.

[0036] The following detailed description is an exemplary description and is intended to provide further detailed description of the present invention. Unless otherwise indicated, all technical terms used in the present invention have the same meaning as those generally understood by those skilled in the art to which the present invention belongs. The terms used in the present invention are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention.

[0037] like Figure 1 As shown, a method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt comprises:

[0038] S1: The surface of the titanium alloy drill pipe joint substrate is degreased and ground to a roughness of 10μm≤Ra≤25μm and an ovality of ≤0.5%;

[0039] S2: Under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture, an ultra-high-speed laser cladding process is used to clad the bonding base layer on the surface of the titanium alloy drill pipe joint substrate. The bonding base layer cladding thickness is 0.6mm to 0.7mm. The ultra-high-speed laser cladding process parameters are: laser power 2400-2500W, spot diameter 1.5-1.8mm, scanning linear speed 35-45m / min, overlap rate 30-45%, and powder feeding rate 18-20g / min;

[0040] S3: Under the protection of a mixed gas of argon and oxygen and a mixed gas of ultra-low partial pressure oxygen, an ultra-high-speed laser cladding process is used to clad the wear-resistant surface layer on the bonding base layer, and the cladding thickness of the wear-resistant surface layer is 1.4mm~1.6mm; the ultra-high-speed laser cladding process parameters are: laser power 2600~2700W, spot diameter 1.6~1.9mm, scanning line speed 40~50m / min, overlap rate 40~55%, and powder feeding rate 25~30g / min; the wear-resistant surface layer is formed in two times, and the thickness of a single pass is 0.7mm~0.8mm, and a double-layer composite structure wear-resistant belt of graphene-modified titanium alloy oil drill pipe is prepared.

[0041] The raw materials for the bonding bottom layer are a mixture of Ti6Al4V titanium alloy powder and TiO2-modified partially reduced graphene oxide (hereinafter referred to as TiO2-bRGO). The mixture is placed in a vacuum ball mill and vacuum ball milled for 4 to 5 hours, and then dried for 1 to 1.5 hours. The proportion of TiO2-bRGO is 1wt% to 3wt%.

[0042] The raw materials for the wear-resistant surface layer are a mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder. The mixture is placed in a vacuum ball mill and vacuum milled for 5 to 6 hours, and then dried for 1 to 1.5 hours. The proportion of TiO2-bRGO is 3wt% to 5wt%, and the proportion of micro-nano TiC powder is 4wt% to 7wt%.

[0043] Utilizing the principle of selective oxidation of aluminum and vanadium under ultra-low oxygen partial pressure, and under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture, an ultra-high-speed laser cladding process is used to form a graphene-modified titanium alloy drill pipe wear-resistant belt on the titanium alloy drill pipe joint substrate, achieving in-situ generation of Al2O3 and V2O5 nano-reinforced particles of Al, V, and O.

[0044] When the high-speed laser cladding process is used to prepare the bonding base layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.1-0.2ppm and the gas flow rate is 21-25L / min; when the high-speed laser cladding process is used to prepare the wear-resistant surface layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.3-0.5ppm and the gas flow rate is 21-25L / min.

[0045] Among them, the characteristics of TiO2-bRGO are as follows:

[0046] The partially reduced graphene oxide has 1 to 5 layers, a sheet size of 1 μm to 7 μm, a reduction degree of 60% to 70%, and is rich in functional groups such as hydroxyl groups;

[0047] TiO2-bRGO was prepared by utilizing the principle that TiO2 hydrate and partially reduced graphene oxide share "O".

[0048] The preparation method of TiO2-bRGO includes:

[0049] First, 20wt% α-titanic acid and 5wt% partially reduced graphene oxide were dissolved in distilled water. Ultrasonication at a frequency of 8kHz to 10kHz was then performed for 100 to 120 minutes to prepare a TiO2-bRGO dispersion. The dispersion was then dried at 150°C to 180°C for 2 hours, then ball-milled in a vacuum ball mill for 1.5 to 2 hours and dried for 0.5 to 2 hours to produce a TiO2-bRGO powder with a particle size of 0.1μm to 3μm.

[0050] Among them, the nano powder ratio in the micro-nano TiC powder is 10wt% to 15wt%, the nano TiC particle size is 50nm to 100nm, the micron TiC particle size is 0.1μm to 0.5μm, and the powder purity is greater than 99.5%;

[0051] Among them, the particle size of Ti6Al4V titanium alloy powder is 60μm~150μm, D50 is 80~100μm, 35s / 100g≤fluidity≤40s / 100g, and its composition meets the requirements of GB / T3620.1-2016 standard.

[0052] A graphene-modified titanium alloy oil drill pipe wear-resistant belt is prepared according to a method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt. The performance indicators of the graphene-modified titanium alloy drill pipe wear-resistant belt meet the following requirements:

[0053] (1) Surface hardness is 56-62HRC;

[0054] (2) The surface of the wear-resistant belt was subjected to fluorescent penetrant non-destructive testing in accordance with JB / T 4730.5-2005 standard, and no crack defects were found;

[0055] (3) The bonding strength test was carried out in accordance with the SY / T 6948-2018 standard, and the wear-resistant belt did not peel off;

[0056] (4) In the simulated drilling (water-based drilling mud solution with a density of 2.0 g / cm3, a loading force of 10 N, and a customized friction pair The wear rate in the conglomerate ball) environment is ≤0.3μm / h, and the friction coefficient is 0.29~0.43;

[0057] (5) The corrosion rate in a high temperature, high pressure, high salt and high acidity corrosive environment (160°C, 35 MPa, a water-based drilling mud solution with a density of 2.0 g / cm3 and a carbon dioxide partial pressure of 1 MPa) is ≤0.025 mm / a.

[0058] Example 1

[0059] A method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt, comprising:

[0060] S1: The surface of the titanium alloy drill pipe joint base is degreased and ground to a roughness of 10 ≤ Ra ≤ 25 μm and an ovality of ≤ 0.5%;

[0061] S2: Under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture, the mixed powder was clad on the surface of the titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process. The bonding bottom layer cladding thickness was 0.6 mm. The ultra-high-speed laser cladding process parameters were: laser power 2400 W, spot diameter 1.5 mm, scanning linear speed 35 m / min, overlap rate 30%, and powder feeding rate 18 g / min.

[0062] S3: Under the protection of an argon-oxygen mixture and an ultra-low partial pressure oxygen mixture, an ultra-high-speed laser cladding process was used to deposit a wear-resistant surface layer onto the bonding base layer. The wear-resistant surface layer had a thickness of 1.6 mm. The ultra-high-speed laser cladding process parameters were: laser power 2700 W, spot diameter 1.9 mm, scanning speed 40 m / min, overlap ratio 40%, and powder feed rate 30 g / min. The wear-resistant surface layer was formed in two passes, with a single pass thickness of 0.8 mm. This produced a graphene-modified titanium alloy oil drill pipe double-layer composite wear-resistant belt.

[0063] The raw materials for the bonding bottom layer are a mixture of Ti6Al4V titanium alloy powder and TiO2-bRGO. The mixture is placed in a vacuum ball mill and vacuum milled for 4 hours, and then dried for 1 hour. The proportion of TiO2-bRGO is 1wt%.

[0064] The raw materials for the wear-resistant surface layer are a mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder. The mixture is placed in a vacuum ball mill and vacuum milled for 5 hours, and then dried for 1 hour. The proportion of TiO2-bRGO is 5wt%, and the proportion of micro-nano TiC powder is 7wt%.

[0065] Utilizing the principle of selective oxidation of aluminum and vanadium under ultra-low oxygen partial pressure, a graphene-reinforced titanium-based double-layer composite wear-resistant belt was fabricated on a titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture. This process achieved in-situ generation of Al2O3 and V2O5 nano-reinforced particles from Al, V, and O.

[0066] When the high-speed laser cladding process is used to prepare the bonding base layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.1ppm and the gas flow rate is 21L / min; when the high-speed laser cladding process is used to prepare the wear-resistant surface layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.3ppm and the gas flow rate is 21L / min.

[0067] Among them, the characteristics of TiO2-bRGO are as follows:

[0068] The partially reduced graphene oxide has 1 to 5 layers, a sheet size of 1 μm to 7 μm, a reduction degree of 60%, and is rich in functional groups such as hydroxyl groups;

[0069] The preparation method of TiO2-bRGO includes:

[0070] 20wt% α-titanic acid and 5wt% partially reduced graphene oxide were dissolved in distilled water. Ultrasonication at an 8kHz frequency was then applied for 100 minutes to prepare a TiO2-bRGO dispersion. The dispersion was then dried at 150°C for 2 hours, ball-milled in a vacuum ball mill for 1.5 hours, and dried for 0.5 hours to produce a TiO2-bRGO powder with a particle size of 0.1 to 3μm.

[0071] Among them, the nanometer powder ratio in the micro-nanometer TiC powder is 10wt%, the nanometer TiC particle size is 50nm-100nm, the micrometer TiC particle size is 0.1μm-0.5μm, and the powder purity is greater than 99.5%;

[0072] Among them, the Ti6Al4V titanium alloy powder is 60μm~150μm, D50 is 80~100μm, and fluidity is 35s / 100g. Its composition meets the requirements of GB / T3620.1-2016 standard.

[0073] The performance indicators of the graphene-modified titanium alloy drill pipe wear-resistant belt in Example 1 meet the following requirements:

[0074] (1) Surface hardness is 61HRC;

[0075] (2) The surface of the wear-resistant belt was subjected to fluorescent penetrant non-destructive testing in accordance with JB / T 4730.5-2005 standard, and no crack defects were found;

[0076] (3) The bonding strength test was carried out in accordance with the SY / T 6948-2018 standard, and the wear-resistant belt did not peel off;

[0077] (4) In the simulated drilling (density 2.0g / cm 3 The water-based drilling mud solution, the loading force is 10N, and the friction pair is customized The wear rate in the conglomerate ball environment is 0.25 μm / h and the friction coefficient is 0.35;

[0078] (5) High temperature, high pressure, high salt and high acidity (160℃ temperature, 35MPa, density 2.0g / cm 3 The corrosion rate in the corrosive environment of water-based drilling mud solution (1MPa carbon dioxide partial pressure) is 0.024mm / a.

[0079] Example 2

[0080] A method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt, comprising:

[0081] S1: The surface of the titanium alloy drill pipe joint base is degreased and ground to a roughness of 10 ≤ Ra ≤ 25 μm and an ovality of ≤ 0.5%;

[0082] S2: Under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture, the mixed powder was clad on the surface of the titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process. The bonding bottom layer cladding thickness was 0.7 mm. The ultra-high-speed laser cladding process parameters were: laser power 2500 W, spot diameter 1.8 mm, scanning linear speed 45 m / min, overlap rate 45%, and powder feeding rate 20 g / min.

[0083] S3: Under the protection of an argon-oxygen mixture and an ultra-low partial pressure oxygen mixture, an ultra-high-speed laser cladding process was used to deposit a wear-resistant surface layer onto the bonding base layer. The wear-resistant surface layer had a thickness of 1.4 mm. The ultra-high-speed laser cladding process parameters were: laser power 2700 W, spot diameter 1.6 mm, scanning speed 50 m / min, overlap ratio 55%, and powder feed rate 25 g / min. The wear-resistant surface layer was formed in two passes, with a single pass thickness of 0.7 mm. This produced a graphene-modified titanium alloy oil drill pipe double-layer composite wear-resistant belt.

[0084] The raw materials for the bonding bottom layer are a mixture of Ti6Al4V titanium alloy powder and TiO2-bRGO. The mixture is placed in a vacuum ball mill and vacuum milled for 5 hours, and then dried for 1.5 hours. The proportion of TiO2-bRGO is 1wt%.

[0085] The raw materials for the wear-resistant surface layer are a mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder. The mixture is placed in a vacuum ball mill and vacuum milled for 6 hours, and then dried for 1.5 hours. The proportion of TiO2-bRGO is 5wt%, and the proportion of micro-nano TiC powder is 7wt%.

[0086] Utilizing the principle of selective oxidation of aluminum and vanadium under ultra-low oxygen partial pressure, a graphene-reinforced titanium-based double-layer composite wear-resistant belt was fabricated on a titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture. This process achieved in-situ generation of Al2O3 and V2O5 nano-reinforced particles from Al, V, and O.

[0087] When the high-speed laser cladding process is used to prepare the bonding base layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.2ppm and the gas flow rate is 25L / min; when the high-speed laser cladding process is used to prepare the wear-resistant surface layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.5ppm and the gas flow rate is 25L / min.

[0088] Among them, the characteristics of TiO2-bRGO are as follows:

[0089] The partially reduced graphene oxide has 1 to 5 layers, a sheet size of 1 μm to 7 μm, a reduction degree of 70%, and is rich in functional groups such as hydroxyl groups;

[0090] The preparation method of TiO2-bRGO includes:

[0091] 20wt% α-titanic acid and 5wt% partially reduced graphene oxide were dissolved in distilled water. Ultrasonic treatment at a frequency of 10 kHz was then performed for 120 minutes to prepare a TiO2-bRGO dispersion. The dispersion was then dried at 150°C for 2 hours, ball-milled in a vacuum ball mill for 2 hours, and dried for 1 hour to produce a TiO2-bRGO powder with a particle size of 0.1 to 3μm.

[0092] Among them, the nano powder ratio in the micro-nano TiC powder is 15wt%, the nano TiC particle size is 50nm-100nm, the micron TiC particle size is 0.1μm-0.5μm, and the powder purity is >99.5%;

[0093] Among them, the Ti6Al4V titanium alloy powder is 60μm~150μm, D50 is 80~100μm, and fluidity is 40s / 100g. Its composition meets the requirements of GB / T3620.1-2016 standard.

[0094] The performance indicators of the graphene-modified titanium alloy drill pipe wear-resistant belt in Example 2 meet the following requirements:

[0095] (1) Surface hardness is 62HRC;

[0096] (2) The surface of the wear-resistant belt was subjected to fluorescent penetrant non-destructive testing in accordance with JB / T 4730.5-2005 standard, and no crack defects were found;

[0097] (3) The bonding strength test was carried out in accordance with the SY / T 6948-2018 standard, and the wear-resistant belt did not peel off;

[0098] (4) In the simulated drilling (density 2.0g / cm 3 The water-based drilling mud solution, the loading force is 10N, and the friction pair is customized The wear rate in the conglomerate ball environment is 0.21 μm / h and the friction coefficient is 0.29;

[0099] (5) High temperature, high pressure, high salt and high acidity (160℃ temperature, 35MPa, density 2.0g / cm 3 The corrosion rate in the corrosive environment of water-based drilling mud solution (1MPa carbon dioxide partial pressure) is 0.021mm / a.

[0100] Example 3

[0101] A method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt, characterized in that the method comprises the following steps:

[0102] S1: The surface of the titanium alloy drill pipe joint base is degreased and ground to a roughness of 10 ≤ Ra ≤ 25 μm and an ovality of ≤ 0.5%;

[0103] S2: Under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture, the mixed powder was clad on the surface of the titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process. The bonding bottom layer cladding thickness was 0.65 mm. The ultra-high-speed laser cladding process parameters were: laser power 2450 W, spot diameter 1.6 mm, scanning linear speed 40 m / min, overlap rate 40%, and powder feeding rate 19 g / min.

[0104] S3: Under the protection of an argon-oxygen mixture and an ultra-low partial pressure oxygen mixture, an ultra-high-speed laser cladding process was used to deposit a wear-resistant surface layer onto the bonding base layer. The wear-resistant surface layer had a cladding thickness of 1.5 mm. The ultra-high-speed laser cladding process parameters were: laser power 2650 W, spot diameter 1.7 mm, scanning speed 45 m / min, overlap ratio 50%, and powder feed rate 27 g / min. The wear-resistant surface layer was formed in two passes, with a single pass thickness of 0.75 mm. This produced a graphene-modified titanium alloy oil drill pipe double-layer composite wear-resistant belt.

[0105] The raw materials for the bonding bottom layer are a mixture of Ti6Al4V titanium alloy powder and TiO2-bRGO. The mixture is placed in a vacuum ball mill and vacuum milled for 4.5 hours, and then dried for 1.2 hours. The proportion of TiO2-bRGO is 2wt%.

[0106] The raw materials for the wear-resistant surface layer are a mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder. The mixture is placed in a vacuum ball mill and vacuum milled for 5.5 hours, and then dried for 1.2 hours. The proportion of TiO2-bRGO is 4wt%, and the proportion of micro-nano TiC powder is 5wt%.

[0107] Utilizing the principle of selective oxidation of aluminum and vanadium under ultra-low oxygen partial pressure, a graphene-reinforced titanium-based double-layer composite wear-resistant belt was fabricated on a titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process under the protection of a mixture of argon and oxygen and an ultra-low partial pressure oxygen mixture. This process achieved in-situ generation of Al2O3 and V2O5 nano-reinforced particles from Al, V, and O.

[0108] When the high-speed laser cladding process is used to prepare the bonding base layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.15ppm and the gas flow rate is 23L / min; when the high-speed laser cladding process is used to prepare the wear-resistant surface layer, it is protected in a mixed atmosphere of argon and oxygen, where the oxygen content is 0.4ppm and the gas flow rate is 23L / min.

[0109] Among them, the characteristics of TiO2-bRGO are as follows:

[0110] The partially reduced graphene oxide has 1 to 5 layers, a sheet size of 1 μm to 7 μm, a reduction degree of 65%, and is rich in functional groups such as hydroxyl groups.

[0111] The preparation method of TiO2-bRGO includes:

[0112] 20wt% α-titanic acid and 5wt% partially reduced graphene oxide were dissolved in distilled water. Ultrasonication at a frequency of 9 kHz was then performed for 110 minutes to prepare a TiO2-bRGO dispersion. The dispersion was then dried at 150°C to 180°C for 2 hours, ball-milled in a vacuum ball mill for 1.8 hours, and dried for 1 hour to produce a TiO2-bRGO powder with a particle size of 0.1μm to 3μm.

[0113] Among them, the nano powder ratio in the micro-nano TiC powder is 10wt% to 15wt%, the nano TiC particle size is 50nm to 100nm, the micron TiC particle size is 0.1μm to 0.5μm, and the powder purity is greater than 99.5%;

[0114] Among them, the Ti6Al4V titanium alloy powder is 60μm~150μm, D50 is 80~100μm, and fluidity is 38s / 100g. Its composition meets the requirements of GB / T3620.1-2016 standard.

[0115] The performance indicators of the graphene-modified titanium alloy drill pipe wear-resistant belt in Example 3 meet the following requirements:

[0116] (1) Surface hardness is 56HRC;

[0117] (2) The surface of the wear-resistant belt was subjected to fluorescent penetrant non-destructive testing in accordance with JB / T 4730.5-2005 standard, and no crack defects were found;

[0118] (3) The bonding strength test was carried out in accordance with the SY / T 6948-2018 standard, and the wear-resistant belt did not peel off;

[0119] (4) In the simulated drilling (density 2.0g / cm 3 The water-based drilling mud solution, the loading force is 10N, and the friction pair is customized The wear rate in the conglomerate ball environment is 0.3 μm / h and the friction coefficient is 0.43;

[0120] (5) High temperature, high pressure, high salt and high acidity (160℃ temperature, 35MPa, density 2.0g / cm 3 The corrosion rate in the corrosive environment of water-based drilling mud solution (1MPa carbon dioxide partial pressure) is ≤0.019mm / a.

[0121] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the field should understand that the specific implementation methods of the present invention can still be modified or replaced by equivalents. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention should be covered by the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt, characterized in that: include: S1: Degreasing the surface of the titanium alloy drill pipe joint base and performing grinding; S2: When a high-speed laser cladding process is used to prepare a bonding base layer, a mixed atmosphere of argon and oxygen is used for protection, the oxygen content is 0.1-0.2 ppm, and the gas flow rate is 21-25 L / min; the bonding base layer is clad on the surface of the titanium alloy drill pipe joint substrate using an ultra-high-speed laser cladding process, and the raw materials used for the bonding base layer are a mixture of Ti6Al4V titanium alloy powder and TiO2-bRGO; the preparation method of the TiO2-bRGO includes: first, dissolving 20wt% α-titanic acid and 5wt% partially reduced graphene oxide in distilled water; The TiO2-bRGO dispersion was prepared by ultrasonicating the dispersion at an ultrasonic frequency of 8 kHz to 10 kHz for 100 to 120 minutes. The dispersion was dried at 150 to 180°C for 2 hours, ball-milled in a vacuum ball mill for 1.5 to 2 hours, and dried for 0.5 to 2 hours to prepare a TiO2-bRGO powder material with a particle size of 0.1 μm to 3 μm. S3: When using the high-speed laser cladding process to prepare the wear-resistant surface layer, a mixed atmosphere of argon and oxygen is used for protection, the oxygen content is 0.3-0.5ppm, and the gas flow rate is 21-25L / min; the wear-resistant surface layer is clad on the bonding base layer using an ultra-high-speed laser cladding process, and the raw materials used for the wear-resistant surface layer are a mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder; a graphene-modified titanium alloy oil drill pipe double-layer composite structure wear-resistant belt is prepared.

2. The method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt according to claim 1, characterized in that: In S1, grinding is performed to a roughness of 10 μm ≤ Ra ≤ 25 μm and an ovality ≤ 0.5%; The thickness of the bonding bottom layer in S2 is 0.6 mm to 0.7 mm; The ultra-high-speed laser cladding process parameters in S2 are: laser power 2400-2500W, spot diameter 1.5-1.8mm, scanning linear speed 35-45m / min, overlap rate 30-45%, and powder feeding rate 18-20g / min; The wear-resistant surface cladding thickness in S3 is 1.4 mm to 1.6 mm; The ultra-high-speed laser cladding process parameters in S3 are: laser power 2600-2700W, spot diameter 1.6-1.9mm, scanning linear speed 40-50m / min, overlap rate 40-55%, powder feeding rate 25-30g / min; the wear-resistant surface layer is formed in two passes, and the thickness of a single pass is 0.7mm-0.8mm.

3. The method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt according to claim 1, characterized in that: The proportion of TiO2-bRGO in the mixture of Ti6Al4V titanium alloy powder and TiO2-bRGO in the bonding bottom layer raw materials is 1wt% to 3wt%.

4. The method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt according to claim 1, characterized in that: In the mixture of Ti6Al4V titanium alloy powder, TiO2-bRGO and micro-nano TiC powder in the wear-resistant surface raw materials, the proportion of TiO2-bRGO is 3wt% to 5wt%, and the proportion of micro-nano TiC powder is 4wt% to 7wt%.

5. The method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt according to claim 1, characterized in that: The TiO2-bRGO is TiO2-modified partially reduced graphene oxide, the partially reduced graphene oxide has 1 to 5 layers, a sheet size of 1 μm to 7 μm, and a reduction degree of 60% to 70%.

6. The method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt according to claim 4, characterized in that: The micro-nano TiC powder has a nano powder ratio of 10 wt% to 15 wt%, a nano TiC particle size of 50 nm to 100 nm, a micro TiC particle size of 0.1 μm to 0.5 μm, and a powder purity of >99.5%. The Ti6Al4V titanium alloy powder has a particle size of 60 μm to 150 μm, a D50 of 80 to 100 μm, and a fluidity of 35 s / 100 g or less and 40 s / 100 g or less.

7. A graphene-modified titanium alloy oil drill pipe wear-resistant belt, characterized in that: The wear-resistant belt is prepared according to the method for preparing a graphene-modified titanium alloy oil drill pipe wear-resistant belt according to any one of claims 1-6.

8. The graphene-modified titanium alloy oil drill pipe wear-resistant belt according to claim 7, characterized in that: The surface hardness of the wear-resistant belt is 56-62HRC; the wear rate is ≤0.3μm / h and the friction coefficient is 0.29-0.43 in a simulated drilling environment; the corrosion rate is ≤0.025mm / a in a high-temperature, high-pressure, high-salt, and high-acid corrosion environment.

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