Alloy column peg cast-inlay composite wear-resistant grinding disc and preparation process thereof
By utilizing the manufacturing process of alloy stud-inlaid composite wear-resistant grinding discs and the cross-linking structure of ceramic particles and iron-based alloys, the problems of insufficient wear resistance and low cutting efficiency of grinding discs are solved, achieving high wear resistance and high-efficiency cutting effect, and extending the service life of the mill.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HUBEI QINHONG NEW MATERIALS CO LTD
- Filing Date
- 2023-09-20
- Publication Date
- 2026-06-26
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Figure CN117564275B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of grinding disc technology, and in particular to an alloy stud-inlaid composite wear-resistant grinding disc and its manufacturing process. Background Technology
[0002] Vertical grinding mills are widely used in grinding industries such as cement, building materials, power plants, and steel mills. During the service life of the mill, the grinding disc and grinding disc liners are the main wear-resistant working parts. Over long-term service, excessive wear of these wear-resistant parts can lead to a decrease in mill output. Therefore, the service life and operating condition of the grinding disc and grinding disc liners directly affect the economic benefits of the enterprise. Currently, the main methods for manufacturing wear-resistant components such as grinding discs and grinding disc liners are integral casting of high-chromium cast iron and surface surfacing or integral surfacing. High-chromium cast iron is the most widely used, demonstrating excellent wear resistance in equipment used in the power industry, mining, metallurgy, building materials, and coal mines. However, cast high-chromium cast iron contains a large amount of primary carbides, making it brittle and prone to brittle fracture under high-stress wear conditions, leading to component failure. Surfacing wear-resistant materials involve depositing a layer of highly wear-resistant metal onto the surface of the workpiece through welding, thereby achieving surface strengthening and dimensional restoration. There are various types of wear-resistant surfacing materials, with high-chromium cast iron surfacing materials being the most commonly used in wear-resistant applications. These materials exhibit excellent wear resistance under pure abrasive wear conditions. Compared to high-chromium cast iron produced by casting, high-chromium cast iron manufactured by surfacing has a higher chromium-to-carbon ratio, more primary carbides in its microstructure, and superior wear resistance. However, the thickness and location of the surfacing layer are usually limited, and it is prone to fracture and spalling under impact loads. Furthermore, the amount of surfacing repair required is large, and the repair frequency is high. Therefore, the preparation of grinding discs with high wear resistance has become a research focus in this field.
[0003] Chinese patent CN108994744A discloses a wear-resistant diamond grinding disc and its preparation method. The wear-resistant diamond grinding disc prepared by this patent is made from the following raw materials: FeCu pre-alloy, CuSn pre-alloy, diamond micro powder, tin, rare earth elements, and iron. By adding FeCu pre-alloy and CuSn pre-alloy to the diamond grinding disc raw materials, the holding force of the diamond grinding disc is increased, the matrix alloying is promoted, and the sharpness and wear resistance of the diamond grinding disc are improved. The addition of rare earth elements promotes matrix alloying and increases the hardness and anti-deformation strength of the matrix. However, the wear-resistant grinding disc prepared by the above materials still has the following disadvantages: on the one hand, mixing the alloy with the diamond raw materials has limited effect on improving the wear resistance of the grinding disc, affecting the grinding effect and working safety; on the other hand, the addition of the alloy may reduce the cutting efficiency of the grinding disc, resulting in a slower grinding process or the need for more power. Summary of the Invention
[0004] In view of this, the present invention proposes an alloy pin-inlaid composite wear-resistant grinding disc and its preparation process to solve the technical problems of insufficient wear resistance and low cutting efficiency of grinding discs in the prior art.
[0005] The technical solution of this invention is achieved as follows: On one hand, this invention provides a manufacturing process for an alloy stud-inlaid composite wear-resistant grinding disc, comprising the following steps:
[0006] Step 1: Mix the composite ceramic powder and the iron-based alloy powder evenly, granulate and sinter to prepare metal ceramic particles. The amount of composite ceramic powder added is 65-80 wt%, and the amount of iron-based alloy powder added is 20-35%.
[0007] Step 2: Press and sinter the metal-ceramic particles to prepare alloy studs;
[0008] Step 3: Fix the alloy studs with copper pins welded to the ends into the sand mold of the wear-resistant grinding disc, and use the sand casting process to cast the composite alloy studs into the composite wear-resistant grinding disc.
[0009] Based on the above technical solutions, preferably, the iron-based alloy powder is one or more of iron-nickel alloy powder, iron-molybdenum alloy powder, iron-aluminum alloy powder, and iron-titanium alloy powder. More preferably, the iron-based alloy powder comprises the following components by mass percentage: Ni: 1.8-2.1%, C: 0.3-0.5%, Mo: 1.3-1.6%, Mn: 9-12%, and Fe balance.
[0010] Based on the above technical solutions, preferably, the composite ceramic powder includes ceramic particles, an inorganic crosslinking agent, and a binder, and the mass fractions of each component in the composite ceramic powder are: 88-92 parts of ceramic particles, 4-6 parts of inorganic crosslinking agent, and 4-6 parts of binder.
[0011] In this invention, ceramic particles, inorganic crosslinking agents, binders, and iron-based alloy powder are mixed and granulated. The ceramic particles themselves act as a hard filler; when dispersed in the iron-based alloy matrix, they can hinder crack propagation and disperse stress, thereby improving the strength of the composite material. Simultaneously, the high strength of the ceramic particles themselves increases the wear resistance of the composite material. However, the dispersion and arrangement of the ceramic particles in the iron-based alloy significantly affect the performance of the resulting composite material. By adding inorganic crosslinking agents and binders, the inorganic crosslinking agents react with the binders to form a silicate ester crosslinking structure. In this structure, the silicate groups react with the hydroxyl or oxide groups on the surfaces of the ceramic and iron-based alloy particles to form chemical bonds, enhancing the interfacial bonding strength between the ceramic and iron-based alloy particles and preventing particle peeling and detachment. Furthermore, the silicate ester crosslinking structure can form a stable silicate film, protecting the interface from external environmental erosion and oxidation. The formation of the silicate ester crosslinking structure can also regulate the chemical properties and surface energy of the interface, improving the compatibility between the ceramic and iron-based alloy particles and reducing stress concentration and crack formation at the interface. Based on this, alloy studs are prepared by pressing, molding, and sintering, and then embedded in the grinding disc substrate by sand casting process. That is, the composite wear-resistant grinding disc prepared by this invention is an integrated structure in which alloy studs are embedded in the grinding disc substrate. The alloy studs form the wear-resistant layer of the grinding disc, which can improve the wear resistance of the working surface of the grinding disc. At the same time, the cross-linking effect between the inorganic cross-linking agent, ceramic particles and iron-based alloy particles can further improve the thermal stability and cutting efficiency of the wear-resistant layer compared with a simple alloy grinding disc.
[0012] Based on the above technical solutions, preferably, the ceramic particles include one of TiC and SiC; the binder includes isocyanate or silicate; and the inorganic crosslinking agent includes sodium silicate or potassium silicate.
[0013] Further preferably, the binder is isocyanate and the inorganic crosslinking agent is sodium silicate. A crosslinking structure is formed between sodium silicate and isocyanate, which improves the material's heat resistance and mechanical properties. A strong network structure is formed between sodium silicate and isocyanate through a crosslinking reaction, firmly fixing the ceramic particles and iron-based alloy particles together, helping to prevent peeling and breakage during friction and wear. Simultaneously, sodium silicate can lower the sintering temperature between ceramic particles, promoting particle bonding. Sodium silicate can also adsorb onto the surface of iron-based alloy particles, forming a protective silicate film, thereby improving the dispersibility and stability of the iron-based alloy particles and reducing particle aggregation and oxidation.
[0014] Based on the above technical solutions, preferably, the method further includes pretreatment of the ceramic particles. The pretreatment method is as follows: alumina powder, ceramic particles and anhydrous ethanol are ultrasonically dispersed for 15-20 minutes, and then filtered and dried to obtain pretreated ceramic particles.
[0015] In this invention, alumina powder and ceramic particles are ultrasonically dispersed, allowing the alumina powder to uniformly modify the surface of the ceramic particles. The alumina-modified ceramic particle surface has high surface energy and active sites, which further promotes the formation of a cross-linking network between the ceramic particles and the inorganic cross-linking agent. Simultaneously, it can undergo physical adsorption and chemical bonding with the surface of iron-based alloy particles, increasing the contact area between the ceramic particles and the iron-based alloy particles and improving their bonding strength. Ceramic particles possess high hardness and wear resistance, effectively resisting friction and wear. By mixing alumina-modified ceramic particles with iron-based alloy particles, the wear resistance of ceramic particles can be introduced into the composite material. The combination of ceramic particles and iron-based alloy particles can form a composite interface, providing better wear resistance.
[0016] Based on the above technical solutions, preferably, the amount of alumina powder added is 1% to 30% of the mass of the ceramic particles. A lower amount of alumina powder may result in an insignificant surface modification effect on the ceramic particles, failing to fully exert its reinforcing effect; while a higher amount of alumina powder may limit the performance of the composite material, such as reducing the processability of the material and increasing costs.
[0017] Based on the above technical solutions, preferably, the granulation and sintering temperature in step one is 1200-1300℃, and the granulation and sintering time is 60-80min.
[0018] Based on the above technical solutions, preferably, step two specifically includes the following steps: adding metal ceramic particles into a preset mold, and obtaining the alloy stud by pressing, low-temperature curing and sintering at 200-250MPa and 150-200℃.
[0019] Based on the above technical solutions, preferably, step three specifically includes the following steps: fixing alloy studs at intervals to the wear-resistant grinding disc sand mold, placing the wear-resistant grinding disc sand mold into the casting sand mold cavity, pouring molten iron into the casting sand mold cavity, and after the molten iron solidifies, obtaining the alloy stud-inlaid composite wear-resistant grinding disc.
[0020] Based on the above technical solutions, preferably, the alloy stud is a regular hexagonal prism, and a transverse groove is formed on the surface of one end of the alloy stud that is fixed to the grinding disc substrate. The depth of the transverse groove is 5-10 mm, and the length is 10-20 mm. Furthermore, multiple transverse grooves can be provided. By providing transverse grooves, the connection between the grinding disc substrate and the alloy stud will be tighter and the structure will be more robust after casting.
[0021] On the other hand, the present invention provides an alloy stud-inlaid cast composite wear-resistant grinding disc, which is prepared by the preparation process described above.
[0022] The alloy stud-inlaid cast composite wear-resistant grinding disc of the present invention and its preparation process have the following advantages over the prior art:
[0023] (1) By introducing TiC or SiC ceramic particles into the iron-based alloy, the ceramic particles have a similar coefficient of thermal expansion to the iron-based alloy and good compatibility. When dispersed in the iron-based alloy matrix, they can hinder the propagation of cracks and disperse stress, thereby improving the strength of the composite material. At the same time, the ceramic particles themselves have high strength, which can increase the wear resistance of the composite material. The above composite material is made into alloy studs and embedded in the working surface of the grinding disc to form a wear-resistant layer, which can improve the wear resistance and hardness of the grinding disc.
[0024] (2) Pretreatment of ceramic particles promotes the uniform modification of alumina powder on the surface of ceramic particles. The surface of alumina-modified ceramic particles has high surface energy and active sites. Inorganic crosslinking agents and binders are added. Through the combined action of inorganic crosslinking agents and binders, the inorganic crosslinking agents react chemically with the functional groups on the surface of ceramic particles and iron-based alloy particles to form a strong crosslinking network. This promotes the formation of a dense structure between ceramic particles and iron-based alloy particles, enhances the interfacial bonding force between ceramic particles and iron-based alloy particles, and thus improves the wear resistance, hardness and impact resistance of the prepared grinding disc, thereby improving the cutting efficiency of the grinding disc. Attached Figure Description
[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0026] Figure 1 This is a perspective view of the alloy stud prepared according to the present invention;
[0027] Figure 2 This is a perspective view of the alloy stud-inlaid composite wear-resistant grinding disc prepared according to the present invention.
[0028] Figure Labels
[0029] 1. Alloy studs; 101. Horizontal grooves; 2. Wear-resistant grinding disc sand mold. Detailed Implementation
[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0031] Some of the raw materials used in this invention are from the following sources:
[0032] Alumina powder, nano-sized, granular, content ≥99.9%, particle size 100nm, Shanghai Xingtian New Material Technology Co., Ltd.
[0033] TiC ceramic particles, nano-sized, granular, with a particle size of 30-50nm, from Hubei Huwei Jingcheng Materials Technology Co., Ltd.
[0034] Example 1
[0035] This embodiment provides a manufacturing process for an alloy stud-inlaid composite wear-resistant grinding disc, specifically including the following steps:
[0036] (1) By mass fraction, 10 parts of alumina powder, 90 parts of TiC ceramic particles and 500 parts of anhydrous ethanol are ultrasonically dispersed at 24-27℃ for 15-20 min, and then filtered and dried to obtain pretreated ceramic particles.
[0037] (2) 90 parts of pretreated TiC ceramic particles, 5 parts of sodium silicate and 5 parts of isocyanate were mixed to obtain composite ceramic powder. 75% of the composite ceramic powder and 25% of the iron-based alloy powder were mixed evenly. The iron-based alloy powder included the following components by mass percentage: Ni: 2.0%, C: 0.4%, Mo: 1.4%, Mn: 11%, Fe balance. The metal ceramic particles were prepared by granulation and sintering at 1250℃ for 70 min.
[0038] (3) Add the metal ceramic particles into a pre-set mold, and obtain alloy stud 1 by pressing, low-temperature curing and sintering at 225MPa and 180℃. Alloy stud 1 is as follows: Figure 1 As shown, a transverse groove 101 is formed on one end surface of the grinding disc base that is fixed thereto;
[0039] (4) Fix the alloy pins 1 at intervals to the wear-resistant grinding disc sand mold, place the wear-resistant grinding disc sand mold into the casting sand mold cavity, pour molten iron into the casting sand mold cavity, and after the molten iron solidifies, the alloy pin inlaid composite wear-resistant grinding disc is obtained.
[0040] Example 2
[0041] This embodiment provides a manufacturing process for an alloy stud-inlaid composite wear-resistant grinding disc, specifically including the following steps:
[0042] (1) By mass fraction, 5 parts of alumina powder, 92 parts of ceramic particles and 500 parts of anhydrous ethanol are ultrasonically dispersed at 24-27℃ for 15-20 min, and then filtered and dried to obtain pretreated ceramic particles.
[0043] (2) 92 parts of pretreated ceramic particles, 4 parts of sodium silicate and 4 parts of isocyanate were mixed to obtain composite ceramic powder. 65% of the composite ceramic powder and 35% of the iron-based alloy powder were mixed evenly. The iron-based alloy powder included the following components by mass percentage: Ni: 1.8%, C: 0.3%, Mo: 1.3%, Mn: 9%, Fe balance. The metal ceramic particles were prepared by granulation and sintering at 1200℃ for 60 min.
[0044] (3) Add the metal ceramic particles into a pre-set mold, and obtain alloy stud 1 by pressing, low-temperature curing and sintering at 200MPa and 150℃. Alloy stud 1 is as follows: Figure 1 As shown, a transverse groove 101 is formed on one end surface of the grinding disc base that is fixed thereto;
[0045] (4) Fix the alloy studs at intervals to the wear-resistant grinding disc sand mold, place the wear-resistant grinding disc sand mold into the casting sand mold cavity, pour molten iron into the casting sand mold cavity, and after the molten iron solidifies, the alloy stud inlaid composite wear-resistant grinding disc is obtained.
[0046] Example 3
[0047] This embodiment provides a manufacturing process for an alloy stud-inlaid composite wear-resistant grinding disc, specifically including the following steps:
[0048] (1) By mass fraction, 15 parts of alumina powder, 88 parts of ceramic particles and 500 parts of anhydrous ethanol are ultrasonically dispersed at 24-27℃ for 15-20 min, and then filtered and dried to obtain pretreated ceramic particles.
[0049] (2) 88 parts of pretreated ceramic particles, 6 parts of sodium silicate and 6 parts of isocyanate were mixed to obtain composite ceramic powder. 80% of the composite ceramic powder and 20% of the iron-based alloy powder were mixed evenly. The iron-based alloy powder included the following components by mass percentage: Ni: 2.1%, C: 0.5%, Mo: 1.6%, Mn: 12%, Fe balance. The metal ceramic particles were prepared by granulation and sintering at 1300℃ for 80 min.
[0050] (3) Add the metal ceramic particles into a pre-set mold, and obtain the alloy stud by pressing, low-temperature curing and sintering at 250MPa and 200℃. Alloy stud 1 is as follows. Figure 1 As shown, a transverse groove 101 is formed on one end surface of the grinding disc base that is fixed thereto;
[0051] (4) Fix the alloy studs at intervals to the wear-resistant grinding disc sand mold, place the wear-resistant grinding disc sand mold into the casting sand mold cavity, pour molten iron into the casting sand mold cavity, and after the molten iron solidifies, the alloy stud inlaid composite wear-resistant grinding disc is obtained.
[0052] Example 4
[0053] This embodiment provides a preparation process for an alloy stud-inlaid composite wear-resistant grinding disc. The operation steps are the same as in Embodiment 1, except that the ceramic particles are not pretreated.
[0054] Example 5
[0055] This embodiment provides a preparation process for an alloy stud-inlaid composite wear-resistant grinding disc. The operation steps are the same as in embodiment 1, except that the amount of alumina added in step (1) is 5 parts.
[0056] Example 6
[0057] This embodiment provides a preparation process for an alloy stud-inlaid composite wear-resistant grinding disc. The operation steps are the same as in embodiment 1, except that the amount of alumina added in step (1) is 15 parts.
[0058] Example 7
[0059] This embodiment provides a process for preparing an alloy stud-inlaid composite wear-resistant grinding disc. The operation steps are the same as in embodiment 1, except that sodium silicate and isocyanate are not added in step (2).
[0060] Example 8
[0061] This embodiment provides a preparation process for an alloy stud-inlaid composite wear-resistant grinding disc. The operation steps are the same as in embodiment 1, except that isocyanate is not added in step (2).
[0062] Example 9
[0063] This embodiment provides a preparation process for an alloy stud-inlaid composite wear-resistant grinding disc. The operation steps are the same as in embodiment 1, except that: in step (2), 90 parts of ceramic particles, 4 parts of sodium silicate, and 6 parts of isocyanate are added.
[0064] Example 10
[0065] This embodiment provides a preparation process for an alloy stud-inlaid composite wear-resistant grinding disc. The operation steps are the same as in embodiment 1, except that: in step (2), 88 parts of ceramic particles, 6 parts of sodium silicate and 6 parts of isocyanate are added.
[0066] Comparative Example 1
[0067] This comparative example provides a wear-resistant diamond grinding disc and its preparation method. The wear-resistant diamond grinding disc is made from the following raw materials by weight percentage: 35% FeCu pre-alloy, 20% CuSn pre-alloy, 20% diamond micro powder, 1% tin, 0.3% rare earth elements, and the balance being iron; wherein, the Cu content of the FeCu pre-alloy is 25%; the Sn content of the CuSn pre-alloy is 12%; the particle size of the diamond micro powder is 0.5 μm; and the rare earth element is cerium.
[0068] The preparation method includes the following steps:
[0069] S1. Weigh each raw material according to its weight percentage;
[0070] S2. FeCu pre-alloy, CuSn pre-alloy, diamond micro powder, tin, rare earth elements and iron are mixed evenly in a three-dimensional mixer and made into granules to obtain a premix.
[0071] S3. According to the required diamond grinding disc geometry, the premix is cold-pressed into shape using the corresponding mold. After cold pressing, under vacuum conditions, at a temperature of 680℃ and a pressure of 8MPa, it is hot-pressed and sintered for 18 minutes to obtain a diamond grinding disc semi-finished product.
[0072] S4. Use a grinding machine to remove burrs and oxide scale from the semi-finished diamond grinding disc, and then clean it.
[0073] According to GB / T 18301-2012 "Test Method for Abrasion Resistance of Refractory Materials at Room Temperature", the abrasion resistance of the composite abrasion-resistant grinding discs prepared in Examples 1-10 and the grinding disc prepared in Comparative Example 1 were tested. The composite abrasion-resistant grinding discs prepared in Examples 1-10 and the grinding disc prepared in Comparative Example 1 were cut into 100×100×3mm samples, and pressure impact tests were performed using SiC abrasive for 480s. The samples were then weighed. The hardness and impact strength of the composite abrasion-resistant grinding discs prepared in Examples 1-10 and the grinding disc prepared in Comparative Example 1 were measured, and the results are shown in Table 1.
[0074] Table 1
[0075]
[0076]
[0077] As shown in Table 1, compared with Comparative Example 1, the alloy stud-inlaid composite wear-resistant grinding disc prepared by the technical solution of the present invention can significantly improve the wear resistance, hardness, and impact resistance of the grinding disc. Compared with Examples 4-6, Example 1 shows that pretreatment of ceramic particles and mixing of alumina-modified ceramic particles with iron-based alloy particles can promote the formation of the interface of the composite material of ceramic particles and iron-based alloy particles, thereby improving the performance of the grinding disc. The amount of alumina modification will affect the modification effect of ceramic particles, and thus affect the performance of the grinding disc. Compared with Examples 7-10, Example 1 shows that the addition of inorganic crosslinking agent and binder can work together to form a crosslinking network to firmly bond ceramic particles and iron-based alloy particles, thereby improving the wear resistance, hardness, and impact resistance of the grinding disc. The amount of inorganic crosslinking agent and binder added may affect the performance of the grinding disc by affecting the formation of the crosslinking network.
[0078] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A manufacturing process for an alloy stud-inlaid composite wear-resistant grinding disc, characterized in that: Includes the following steps: Step 1: Mix the composite ceramic powder and the iron-based alloy powder evenly, granulate and sinter to prepare metal-ceramic particles. The amount of composite ceramic powder added is 65~80 wt%, and the amount of iron-based alloy powder added is 20~35 wt%. Step 2: Add the metal ceramic particles into a preset mold, press and shape them at 200~250MPa and 150~200℃, cure them at low temperature, and then sinter them to obtain the alloy stud. Step 3: Fix the alloy studs with copper nails welded to the ends at intervals into the wear-resistant grinding disc sand mold, place the wear-resistant grinding disc sand mold into the casting sand mold cavity, pour molten iron into the casting sand mold cavity, and after the molten iron solidifies, the alloy stud inlaid composite wear-resistant grinding disc is obtained. The composite ceramic powder comprises pretreated ceramic particles, an inorganic crosslinking agent, and a binder. The mass fractions of each component in the composite ceramic powder are: 88-92 parts of the pretreated ceramic particles, 4-6 parts of the inorganic crosslinking agent, and 4-6 parts of the binder. The pretreatment method is as follows: alumina powder, ceramic particles, and anhydrous ethanol are ultrasonically dispersed for 15-20 minutes, followed by filtration and drying to obtain pretreated ceramic particles. The ceramic particles include one of TiC and SiC. The binder is isocyanate. The inorganic crosslinking agent includes sodium silicate or potassium silicate.
2. The manufacturing process of the alloy stud-inlaid composite wear-resistant grinding disc as described in claim 1, characterized in that: The amount of alumina powder added is 1% to 30% of the mass of the ceramic particles.
3. The manufacturing process of the alloy stud-inlaid composite wear-resistant grinding disc as described in claim 1, characterized in that: In step one, the granulation and sintering temperature is 1200~1300℃, and the granulation and sintering time is 60~80min.
4. The manufacturing process of the alloy stud-inlaid composite wear-resistant grinding disc as described in claim 1, characterized in that: The alloy stud is a regular hexagonal prism, and a transverse groove is formed on one end surface of the alloy stud that is fixed to the grinding disc base.
5. A composite wear-resistant grinding disc with alloy studs and inlays, characterized in that: The alloy stud-inlaid composite wear-resistant grinding disc is prepared using the preparation process described in any one of claims 1 to 4.