Corrosion-resistant nickel-based alloy column tooth and preparation method thereof

Abstract

The invention relates to a corrosion-resistant nickel-based alloy column tooth, which comprises a hard phase, a binding phase and an additive, the hard phase is tungsten carbide (WC), the Fsss particle size of the tungsten carbide is 2.4-2.8 [mu] m, and the tungsten carbide accounts for 81%; the binding phase is carbonyl nickel powder, the Fsss particle size of the nickel powder is smaller than 1.8 microns, and the nickel powder accounts for 15.5%; the additive is chromium carbide, the Fsss particle size of the chromium carbide is smaller than or equal to 1.2 microns, and the chromium carbide accounts for 3.5%. The carbonyl nickel powder is uniformly dispersed, so that the bonding effect can be enhanced, the toughness of the material is improved, and the hardness stability is not damaged, and chromium carbide is added, so that the wetting angle of nickel and tungsten carbide can be reduced, and the interface bonding force is optimized to improve the toughness; and meanwhile, grain growth is effectively inhibited, the hardness stability is maintained, the corrosion resistance of the material is remarkably improved, the defect that an existing cobalt-based column tooth is poor in corrosion resistance is overcome, and the service life in a sulfur-containing environment is prolonged.

Description

TECHNICAL FIELD

[0001] The application relates to the field of corrosion-resistant nickel-based alloy column teeth and a preparation method thereof. BACKGROUND

[0002] In the field of extreme working conditions such as mine exploitation, geological drilling, oil and gas development, alloy column teeth as the core wear-resistant components directly determine the engineering efficiency and equipment life. Such components are subjected to multiple tests of high stress impact, severe friction and wear, and complex corrosion environment for a long time, and therefore, the materials are required to have excellent hardness and wear resistance to resist wear, good toughness to avoid fracture failure, and stable corrosion resistance in a corrosion environment containing sulfur and moisture to prolong the service cycle.

[0003] The widely used alloy column teeth in the industry are mainly of a classic system taking tungsten carbide (WC) as a hard phase and cobalt (Co) as a binder phase. The design idea of the system is to balance the hardness and toughness of the material by adjusting the particle size (usually controlled at 0.5-5 μm) of the hard phase WC and the content (generally 3%-20%) of the binder phase Co: when the Co content is high, the toughness of the material is improved, and the cracking risk under impact is reduced, but the hardness is reduced, the wear resistance is insufficient, and the column teeth are quickly failed in high wear working conditions; when the Co content is reduced, the hardness of the material is improved, and the wear resistance is enhanced, but the toughness is significantly reduced, so that the column teeth are prone to brittle fracture under impact load, and it is also difficult to meet the actual use requirements. The performance contradiction of "hardness-toughness" becomes the core bottleneck restricting the optimization and upgrading of the traditional cobalt-based alloy column teeth.

[0004] More importantly, the alloy column teeth taking cobalt as the binder phase have significant defects in corrosion resistance. In a sulfur-containing working environment (such as sulfur-containing mineral layer drilling, sulfur-containing hydrogen sulfide oil and gas well development, etc.), cobalt as an active metal is easy to react with sulfides in the environment to form corrosion products, resulting in failure of the binder phase, and then causing the shedding of the hard phase WC, which seriously shortens the service life of the column teeth.

[0005] In addition, from the economic point of view, as a strategic scarce resource, the market price of cobalt metal fluctuates sharply and is in a high position for a long time, resulting in high production cost of the cobalt-based alloy column teeth

[0006] Therefore, we propose a corrosion-resistant nickel-based alloy column tooth and a preparation method thereof, which can solve the above problems. SUMMARY

[0007] The present application aims to overcome the deficiencies of the prior art, adapt to the actual needs, and provide a corrosion-resistant nickel-based alloy column tooth and a preparation method thereof, so as to solve the problems of insufficient wear resistance or easy cracking of the current cobalt-based column tooth, and poor corrosion resistance, which affects the service life in a sulfur-containing environment.

[0008] In order to achieve the object of the present application, the technical scheme adopted by the present application is as follows: a corrosion-resistant nickel-based alloy column tooth is designed, which comprises a hard phase, a binder phase and an additive, the hard phase is tungsten carbide (WC), the Fsss particle size of the tungsten carbide is 2.4-2.8 μm, and the proportion is 81%; the binder phase is nickel carbonyl powder, the Fsss particle size of the nickel powder is <1.8 μm, and the proportion is 15.5%; the additive is chromium carbide, the Fsss particle size of the chromium carbide is ≤1.2 μm, and the proportion is 3.5%.

[0009] Preferably, the Fsss particle size of the tungsten carbide is 2.4 μm.

[0010] Preferably, the Fsss particle size of the tungsten carbide is 2.6 μm.

[0011] Preferably, the Fsss particle size of the tungsten carbide is 2.8 μm.

[0012] Preferably, the Fsss particle size of the nickel carbonyl powder is 1.7 μm.

[0013] Preferably, the Fsss particle size of the nickel carbonyl powder is 1.5 μm.

[0014] Preferably, the Fsss particle size of the chromium carbide is 1.2 μm.

[0015] Preferably, the Fsss particle size of the chromium carbide is 1.0 μm.

[0016] Preferably, the chromium carbide can reduce the wetting angle between the nickel powder and the tungsten carbide, while improving the corrosion resistance of the alloy column tooth and inhibiting grain growth.

[0017] The preparation method of the above-mentioned corrosion-resistant nickel-based alloy column tooth comprises the following steps:

[0018] S1, according to the component ratio, the task book of the mixed material is issued, and the raw materials are obtained according to the task book;

[0019] S2, 2.2% of paraffin wax is used as a forming agent, and the mixed material is prepared according to the spray granulation process;

[0020] S3, when the mixed material is ball milled, the oil acid is added according to the ratio of mixed material: oil acid = 1 kg: 0.75-1.5 g, the ball milling process is ball material ratio 4:1, solid liquid ratio 270 ml / kg, and the ball milling time is 60-68 h;

[0021] S4, spray granulation is carried out after ball milling, and parameters are as follows: outlet temperature 110 DEG C, inlet temperature 200 DEG C, slurry pressure 1.12 Mpa, condensate water temperature 8-12 DEG C, and spray piece aperture phi 1.2;

[0022] S5, the blank is pressed in a one-mold two-out mode by using a 63T press;

[0023] S6, pressure sintering is carried out by using a SIP pressure sintering furnace, sintering temperature is 1430-1450 DEG C, and pressure is 4 Mpa.

[0024] Compared with the prior art, the beneficial effects of the present application are as follows:

[0025] 1. The tungsten carbide with Fsss of 2.4-2.8 mu m is selected, the hardness and toughness are balanced, the problems of insufficient hardness or poor toughness are avoided, the carbonyl nickel powder with Fsss < 1.8 mu m is used, the dispersion is uniform, the bonding effect is enhanced, the material toughness is improved, and the hardness stability is not damaged, the chromium carbide with Fsss <= 1.2 mu m is added, the wetting angle of nickel and tungsten carbide is reduced, the interface bonding force is optimized to improve the toughness, the grain growth is effectively inhibited, the hardness stability is maintained, the material corrosion resistance is significantly improved, the defects of poor corrosion resistance of the existing cobalt-based column teeth are solved, and the service life in the sulfur-containing environment is prolonged. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 It is a flowchart of the present application; DETAILED DESCRIPTION

[0027] The present application is further illustrated below in combination with the drawings and examples:

[0028] A kind of corrosion-resistant nickel-based alloy column tooth, referring to Figure 1 , including hard phase, binder and additive, the hard phase is tungsten carbide (WC), the Fsss particle size of tungsten carbide is 2.4-2.8 mu m, and the proportion is 81%;The binder is carbonyl nickel powder, the Fsss particle size of nickel powder is <1.8 mu m, and the proportion is 15.5%;The additive is chromium carbide, the Fsss particle size of chromium carbide is <=1.2 mu m, and the proportion is 3.5%.

[0029] Specifically, referring to Figure 1 , the Fsss particle size of the tungsten carbide is 2.4 mu m.

[0030] More specifically, referring to Figure 1 , the Fsss particle size of the tungsten carbide is 2.6 mu m.

[0031] Further, referring to Figure 1 , the Fsss particle size of the tungsten carbide is 2.8 mu m.

[0032] It is worth mentioning that, referring toFigure 1 The Fsss particle size of the carbonyl nickel powder is 1.7 pm.

[0033] It is worth noting that, referring to Figure 1 The Fsss particle size of the carbonyl nickel powder is 1.5 pm.

[0034] It is worth noting that, referring to Figure 1 The Fsss particle size of the chromium carbide is 1.2 pm.

[0035] It is worth noting that, referring to Figure 1 The Fsss particle size of the chromium carbide is 1.0 pm.

[0036] It is worth noting that, referring to Figure 1 The chromium carbide can reduce the wetting angle between the nickel powder and the tungsten carbide, improve the corrosion resistance of the alloy column tooth, and inhibit the grain growth.

[0037] The preparation method of the corrosion-resistant nickel-based alloy column tooth described above comprises the following steps:

[0038] S1, according to the component ratio, the task book of the mixed material production is issued, and the raw materials are obtained according to the task book;

[0039] S2, 2.2% of paraffin wax is used as a forming agent, and the mixed material is prepared according to the spray granulation process;

[0040] S3, when the mixed material is ball milled, the oil acid is added according to the ratio of mixed material: oil acid = 1 kg: 0.75~1.5 g, the ball milling process is ball material ratio 4:1, solid liquid ratio 270 ml / kg, and the ball milling time is 60~68h;

[0041] S4, after the ball milling is completed, the spray granulation is carried out, the parameters are outlet temperature 110℃, inlet temperature 200℃, slurry pressure 1.12Mpa, condensate water temperature 8~12℃, and spray piece aperture φ1.2;

[0042] S5, a 63T press is used to press the blank in a one-mold two-out mode;

[0043] S6, the SIP pressure sintering furnace is used for pressure sintering, the sintering temperature is 1430~1450℃, and the pressure is 4Mpa.

[0044] Example one

[0045] Material composition:

[0046] The tungsten carbide (WC) accounts for 81%; the carbonyl nickel powder accounts for 15.5%; and the chromium carbide accounts for 3.5%.

[0047] Material Fsss particle size:

[0048] The Fsss particle size of tungsten carbide is 2.8 μm; the Fsss particle size of carbonyl nickel powder is 1.7 μm; and the Fsss particle size of chromium carbide is 1.2 μm.

[0049] Preparation method:

[0050] S1. Issue the production task order for the mixture according to the component ratio, and collect the raw materials according to the task order;

[0051] S2. Using 2.2% paraffin as a molding agent, prepare the mixture according to the spray granulation process;

[0052] S3. When ball milling the mixture, add oleic acid at a ratio of 1 kg of mixture to 0.75~1.5 g of oleic acid. The ball milling process is as follows: ball-to-material ratio 4:1, solid-liquid ratio 270 ml / kg, and ball milling time 60 h.

[0053] S4. After ball milling, spray granulation is performed with the following parameters: outlet temperature 110℃, inlet temperature 200℃, slurry pressure 1.12Mpa, condensate temperature 8~12℃, and spray nozzle diameter φ1.2.

[0054] S5. A 63T press is used to press the billet in a two-outlet method with one die.

[0055] S6. Sintering is carried out in a SIP pressure sintering furnace at a sintering temperature of 1430~1450℃ and a pressure of 4Mpa.

[0056] Example 2

[0057] Material composition:

[0058] Tungsten carbide (WC) accounts for 81%; nickel carbonyl powder accounts for 15.5%; and chromium carbide accounts for 3.5%.

[0059] Material Fsss particle size:

[0060] The Fsss particle size of tungsten carbide is 2.6 μm; the Fsss particle size of carbonyl nickel powder is 1.5 μm; and the Fsss particle size of chromium carbide is 1.0 μm.

[0061] Preparation method:

[0062] S1. Issue the production task order for the mixture according to the component ratio, and collect the raw materials according to the task order;

[0063] S2. Using 2.2% paraffin as a molding agent, prepare the mixture according to the spray granulation process;

[0064] S3. When ball milling the mixture, add oleic acid at a ratio of 1 kg of mixture to 0.75~1.5 g of oleic acid. The ball milling process is as follows: ball-to-material ratio 4:1, solid-liquid ratio 270 ml / kg, and ball milling time 65 h.

[0065] S4. After ball milling, spray granulation is performed with the following parameters: outlet temperature 110℃, inlet temperature 200℃, slurry pressure 1.12Mpa, condensate temperature 8~12℃, and spray nozzle diameter φ1.2.

[0066] S5. A 63T press is used to press the billet in a two-outlet method with one die.

[0067] S6. Sintering is carried out in a SIP pressure sintering furnace at a sintering temperature of 1430~1450℃ and a pressure of 4Mpa.

[0068] Example 3

[0069] Material composition:

[0070] Tungsten carbide (WC) accounts for 81%; nickel carbonyl powder accounts for 15.5%; and chromium carbide accounts for 3.5%.

[0071] Material Fsss particle size:

[0072] The Fsss particle size of tungsten carbide is 2.4 μm; the Fsss particle size of carbonyl nickel powder is 1.5 μm; and the Fsss particle size of chromium carbide is 1.0 μm.

[0073] Preparation method:

[0074] S1. Issue the production task order for the mixture according to the component ratio, and collect the raw materials according to the task order;

[0075] S2. Using 2.2% paraffin as a molding agent, prepare the mixture according to the spray granulation process;

[0076] S3. When ball milling the mixture, add oleic acid at a ratio of 1 kg of mixture to 0.75~1.5 g of oleic acid. The ball milling process is as follows: ball-to-material ratio 4:1, solid-liquid ratio 270 ml / kg, and ball milling time 68 h.

[0077] S4. After ball milling, spray granulation is performed with the following parameters: outlet temperature 110℃, inlet temperature 200℃, slurry pressure 1.12Mpa, condensate temperature 8~12℃, and spray nozzle diameter φ1.2.

[0078] S5. A 63T press is used to press the billet in a two-outlet method with one die.

[0079] S6. Sintering is carried out in a SIP pressure sintering furnace at a sintering temperature of 1430~1450℃ and a pressure of 4Mpa.

[0080] The corrosion-resistant nickel-based alloy spur teeth and their preparation methods obtained in Examples 1 to 3 of the present invention were tested, and the results are shown in the table below:

[0081] Table 1:

[0082]

[0083] Table 2:

[0084]

[0085] Table 3:

[0086]

[0087] As shown in the table above, the embodiments of the present invention can select tungsten carbide with an Fsss of 2.4 μm to balance hardness and toughness, avoiding the problems of insufficient hardness due to excessive coarseness or poor toughness due to excessive fineness. Using carbonyl nickel powder with an Fsss of 1.5 μm ensures uniform dispersion, enhances the bonding effect, improves material toughness, and does not compromise hardness stability. Adding chromium carbide with an Fsss of 1.0 μm reduces the wetting angle between nickel and tungsten carbide, optimizes interfacial bonding to improve toughness, effectively inhibits grain growth, maintains hardness stability, and significantly improves the material's corrosion resistance, solving the defect of poor corrosion resistance in existing cobalt-based columnar teeth and extending service life in sulfur-containing environments.

[0088] In addition, all components designed in this invention are general standard parts or components known to those skilled in the art. Their structures and principles can be learned by those skilled in the art through technical manuals or conventional experimental methods. They can be fully implemented by those skilled in the art, so there is no need to elaborate. The content protected by this invention does not involve improvements to the internal structure and methods.

[0089] The embodiments disclosed in this invention are preferred embodiments, but are not limited thereto. Those skilled in the art can easily understand the spirit of this invention based on the above embodiments and make different extensions and variations, but as long as they do not depart from the spirit of this invention, they are all within the protection scope of this invention.

Claims

1. A corrosion-resistant nickel-based alloy spur tooth, characterized in that: The mixture comprises a hard phase, a binder phase, and additives. The hard phase is tungsten carbide (WC), with an Fsss particle size of 2.4~2.8μm, accounting for 81%. The binder phase is nickel carbonyl powder, with an Fsss particle size of <1.8μm, accounting for 15.5%. The additives are chromium carbide, with an Fsss particle size of ≤1.2μm, accounting for 3.5%.

2. The corrosion-resistant nickel-based alloy spur tooth according to claim 1, characterized in that: The tungsten carbide has an Fsss particle size of 2.4 μm.

3. The corrosion-resistant nickel-based alloy spur tooth according to claim 1, characterized in that: The tungsten carbide has an Fsss particle size of 2.6 μm.

4. The corrosion-resistant nickel-based alloy spur tooth according to claim 1, characterized in that: The tungsten carbide has an Fsss particle size of 2.8 μm.

5. The corrosion-resistant nickel-based alloy cylindrical tooth according to claim 1, characterized in that: The Fsss particle size of the carbonyl nickel powder is 1.7 μm.

6. The corrosion-resistant nickel-based alloy cylindrical tooth according to claim 1, characterized in that: The Fsss particle size of the carbonyl nickel powder is 1.5 μm.

7. The corrosion-resistant nickel-based alloy cylindrical tooth according to claim 1, characterized in that: The chromium carbide has an Fsss particle size of 1.2 μm.

8. The corrosion-resistant nickel-based alloy spur tooth according to claim 1, characterized in that: The chromium carbide has an Fsss particle size of 1.0 μm.

9. The corrosion-resistant nickel-based alloy cylindrical tooth according to claim 1, characterized in that: The chromium carbide can reduce the wetting angle between nickel powder and tungsten carbide, while improving the corrosion resistance of the alloy column teeth and inhibiting grain growth.

10. A method for preparing corrosion-resistant nickel-based alloy cylindrical teeth according to any one of claims 1-9: characterized in that, Includes the following steps: S1. Issue a production task order for the mixture according to the component ratio described in claim 1, and collect raw materials according to the task order; S2. Using 2.2% paraffin as a molding agent, prepare the mixture according to the spray granulation process; S3. When ball milling the mixture, add oleic acid at a ratio of 1 kg of mixture to 0.75~1.5 g of oleic acid. The ball milling process is as follows: ball-to-material ratio 4:1, solid-liquid ratio 270 ml / kg, and ball milling time 60~68 h. S4. After ball milling, spray granulation is performed with the following parameters: outlet temperature 110℃, inlet temperature 200℃, slurry pressure 1.12Mpa, condensate temperature 8~12℃, and spray nozzle diameter φ1.

2. S5. A 63T press is used to press the billet in a two-outlet method with one die. S6. Sintering is carried out in a SIP pressure sintering furnace at a sintering temperature of 1430~1450℃ and a pressure of 4Mpa.

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