Modified high-temperature-resistant, high-wear-resistant and corrosion-resistant composite functional material as well as preparation process and application thereof

Abstract

The invention discloses a modified composite functional material with high temperature resistance, high wear resistance and corrosion resistance as well as a preparation process and application thereof, the material contains modified TiC, Mo, Ni, Mn, Co, C, Cr, Y2O3 and the balance of Fe, and interface bonding is enhanced by TiC modified by a silane coupling agent. The preparation method comprises the steps of segmented two-step ball milling, vacuum freeze drying, ultrasonic-assisted pressing and gradient vacuum sintering. The HRC hardness of the product is 62.8-63.8, the density is 6.13-6.15 g / cm < 3 >, the bending strength is 1629-1658 MPa, the hardness retention rate at the high temperature of 1100 DEG C exceeds 95%, and the composite functional material has good high-temperature oxidation resistance, high-temperature wear resistance and corrosion resistance. The material is suitable for manufacturing high-temperature-resistant furnace bottom plates, high-temperature atmosphere furnace bottom plates, high-precision die steel and the like, and the service life of the material is remarkably better than that of a traditional material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alloy materials, in particular to a modified high-temperature-resistant and high-wear-resistant and corrosion-resistant composite functional material and a preparation process and application thereof, and is especially suitable for key components in metallurgy and mechanical manufacturing that need to withstand high temperature, friction and corrosion for a long time. BACKGROUND

[0002] In the industrial fields of metallurgy, casting, and mechanical processing, the service life of key components of equipment, such as high-temperature furnace roller, hot-working die punch, and hammer head of a crusher, directly determines the production efficiency and cost. Such components are in extreme working conditions for a long time: high temperature, high-frequency friction, alternating cold and hot impact, and corrosion by corrosive gas / liquid, which puts strict requirements on the comprehensive performance of the materials.

[0003] In traditional materials, hot-working die steel has certain toughness, but it is prone to temper softening at high temperature, and the hardness and wear resistance decrease sharply. For example, H13 steel products will have large-scale peeling on the surface due to oxidation corrosion after 8 months of continuous work, which leads to unstable workpiece conveying and even safety accidents. Hard alloy has high hardness, but it is brittle and expensive, and tungsten resources are scarce, so it is not suitable for mass production of large components.

[0004] The existing powder metallurgy prepared wear-resistant materials have the following defects: component design limitation: high TiC content leads to increased material brittleness, and insufficient binder phase content makes it difficult to effectively wrap hard phase, and hard phase peeling easily occurs in use; process defects: uneven wet grinding and mixing lead to sintering organization segregation; hot air distillation is used in the drying process, which easily leaves alcohol or water, causing sintering pores; insufficient high-temperature resistance: low sintering temperature leads to poor high-temperature stability of the material, and the hardness decreases by 10-15% after long-term use; poor application adaptability: the microstructure of the material is not optimized for different working conditions of components, such as local high hardness required for punches, and the existing materials have uniform properties, making it difficult to balance toughness and wear resistance.

[0005] In addition, the existing technology lacks precise control of trace elements. For example, the addition of Cr element can significantly improve the oxidation resistance of the material, but its role is often ignored in traditional formulations; the introduction of nanoparticles can strengthen the performance, but uneven dispersion can lead to agglomeration, which can actually deteriorate the mechanical properties of the material. At the same time, the sintering curve design in the preparation process is rough, and the difference in diffusion rate of different components is not considered, which leads to low interfacial bonding strength and easy delamination at high temperature.

[0006] Therefore, it is necessary to develop a modified high-temperature-resistant and high-wear-resistant and corrosion-resistant composite functional material to solve the short life problem of industrial components.

[0007] The above background information is provided only to aid in understanding the inventive concept and technical solution of this invention. It does not necessarily belong to the prior art of this patent application. In the absence of clear evidence that the above information was disclosed on the filing date of this patent application, the above background information should not be used to evaluate the novelty and inventiveness of this application. Summary of the Invention

[0008] The purpose of this invention is to propose a modified high-temperature resistant, high-wear resistant, and corrosion resistant composite functional material, its preparation process, and its application, so as to solve the technical problems existing in the prior art.

[0009] Therefore, the present invention adopts the following technical solution:

[0010] A modified high-temperature resistant, high-wear resistant, and corrosion resistant composite functional material comprises the following components by mass percentage: modified TiC: 38.0%-52.0%, Mo: 2.0%-4.0%, Ni: 3.0%-5.0%, Mn: 7.0%-10.0%, Co: 0.5%-1.5%, C: 0.5%-1.0%, Cr: 0.5%-1.5%, Y2O3: 0.1-0.3%, with the balance being Fe and unavoidable impurities.

[0011] Furthermore, the modified TiC has a particle size of 1-5 μm and has been modified with a surface silane coupling agent.

[0012] Furthermore, the specific steps for preparing the modified TiC are as follows:

[0013] a. Place TiC powder with a particle size of 1-5 μm in a 4-6% (w / w) dilute hydrochloric acid solution and stir in a constant temperature water bath at 55-65℃ for 1.5-2.5 h to remove the surface oxide layer and impurities; then wash with water until pH = 6.5-7.5, and dry in a vacuum drying oven at 75-85℃ for 3.5-4.5 h to obtain clean and dry TiC powder;

[0014] b. The surface silane coupling agent is prepared by mixing γ-aminopropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1-3:45-55:5-8. The pH of the solution is adjusted to 3.5-4.5 with glacial acetic acid, and stirred at 25-30℃ for 20-40 min to fully hydrolyze the silane and form a stable hydrolysate.

[0015] c. Add the pretreated TiC powder to the above hydrolysate, with a mass ratio of TiC to hydrolysate of 1:10. Stir at 45-55℃ for 1-2 hours until the condensation reaction is complete, allow to stand and precipitate, and filter to discard the supernatant.

[0016] d. Wash the modified TiC powder with anhydrous ethanol 2-4 times; dry it in a vacuum drying oven at 90-110℃ for 5-7 hours to obtain modified TiC powder.

[0017] This invention also provides a method for preparing a modified high-temperature resistant, high-wear resistant, and corrosion resistant composite functional material, comprising the following steps:

[0018] S1. Batching calculation: Calculate the weight according to the grouping ratio, and weigh the metal raw materials after calculating the evaporation replenishment value; among them, Cr is added in the form of Cr-Fe-C master alloy, Mo is added in the form of Mo-Fe master alloy, and Mn is added in the form of Mn-Fe-C master alloy.

[0019] S2. Two-step ball milling and mixing: First stage: Mo, Ni, Mn, Co, Cr, C, and Fe are introduced into the corresponding elements based on the intermediate alloy form described in step S1, and ball milled in a high-energy ball mill at 400-500 rpm for 4-6 hours to form a pre-alloyed powder; Second stage: Modified TiC and Y2O3 are added to the pre-alloyed powder, and ball milled in a low-energy ball mill at 150-200 rpm for 12-15 hours, with 350-450 ml / kg of anhydrous ethanol added;

[0020] S3. Vacuum freeze drying: Dry the wet milled mixture at -25 to -20°C and a vacuum of 1-5 Pa for 8-12 hours;

[0021] S4. Rubber-blended granulation: Add 105-115 ml / kg of sodium butadiene rubber-polyvinyl alcohol composite molding agent, and prepare material granules through a granulator;

[0022] S5. Ultrasonic-assisted pressing: Pressing is assisted by 50-80kHz ultrasonic vibration at a pressure of 800-1000MPa;

[0023] S6. Gradient vacuum sintering:

[0024] Degumming stage: room temperature to 600-650℃, microwave power density 5-10W / cm³ 3 Heating rate: 8-12℃ / min;

[0025] Solid-state sintering stage: 600-650℃ to 1100-1200℃, microwave power density 10-15W / cm² 3 The heating rate is 13-18℃ / min;

[0026] Liquid phase sintering stage: 1100-1200℃ to 1420-1480℃, microwave power density 12-15W / cm³ 3 The heating rate is 20℃ / min; after reaching the highest temperature, 120-180MPa high-purity argon gas is introduced and the pressure and temperature are maintained for 60±5min.

[0027] Furthermore, in step S2, the first stage of high-energy ball milling uses WC-Co cemented carbide grinding balls, and the second stage of low-energy ball milling uses ZrO2 grinding balls.

[0028] Furthermore, in step S2, the ball-to-material ratio in the first stage is 4-5:1, and the ball-to-material ratio in the second stage is 2-3:1.

[0029] Further, the composite molding agent in step S4 is a mixture of sodium butadiene rubber and polyvinyl alcohol in a mass ratio of 6-8:2-4.

[0030] Furthermore, the particle size obtained in step S4 is 65-75 mesh.

[0031] Furthermore, the microwave frequency in step S6 is 2-2.45 GHz.

[0032] Furthermore, the argon gas purity in step S6 is ≥99.999%.

[0033] Compared with the prior art, the technical advantages of this invention are specifically reflected in the following aspects:

[0034] 1. Significantly Improved Interfacial Bonding Strength and Wear Resistance: This invention modifies TiC with a surface silane coupling agent, introducing organic functional groups onto the TiC surface. These organic functional groups form strong chemical bonds with the metal matrix, significantly improving the interfacial bonding strength. Compared to unmodified TiC, the modified TiC exhibits better dispersion in the metal matrix and is less prone to detachment, thereby enhancing the material's wear resistance. Experimental data shows that the materials prepared in Examples 1-3 achieve an HRC hardness of 62.8-63.8, far exceeding the 40-52 HRC of traditional hot work die steel H13, fully verifying the significant improvement in wear resistance resulting from the modification treatment and component design.

[0035] 2. Excellent High-Temperature Stability and Oxidation Resistance: This invention effectively refines grains and improves the high-temperature strength and oxidation resistance of the material by adding Y2O3 rare earth oxide and optimizing the alloy element ratio. Y2O3 can inhibit grain growth, enhance grain boundary stability, and form a dense oxide film to prevent oxygen from diffusing into the material. After a high-temperature resistance test at 1100℃ for 45 minutes, the materials in Examples 1-3 still maintained a hardness of 59.8-60.7 HRC, with a hardness retention rate of over 95%, far superior to the approximately 60% high-temperature hardness retention rate of traditional H13 steel. This fully demonstrates its excellent high-temperature stability and oxidation resistance, enabling it to work stably for a long time in extreme high-temperature environments.

[0036] 3. Outstanding corrosion resistance: In this invention, Cr works synergistically with other alloying elements. The Cr carbides not only enhance high-temperature oxidation resistance but also construct a dense and stable Cr2O3 oxide film on the material surface. This oxide film effectively blocks Cl- and H-. + When corrosive media penetrate the matrix, the corrosion rate of Examples 1-3 in 3.5% NaCl solution is only 0.028-0.035 mm / year, which is much lower than that of traditional materials. This gives the material the ability to adapt to complex corrosive conditions such as chlorine and humidity, and expands its application scenarios.

[0037] 4. Comprehensive Performance Improvement Resulting from Innovative Preparation Processes: This invention employs a segmented two-step ball milling and mixing process, combined with microwave-assisted gradient sintering and ultrasonic-assisted pressing techniques, to achieve material homogeneity and densification. The segmented two-step ball milling and mixing process ensures sufficient alloying of the metal powder while avoiding excessive crushing of the modified TiC particles; microwave-assisted sintering offers advantages such as rapid heating, uniform temperature distribution, and low energy consumption, effectively inhibiting grain growth and improving material density; ultrasonic-assisted pressing technology reduces frictional resistance between powder particles, improving the density and uniformity of the green body. The combined application of these innovative processes significantly enhances the overall performance of the material. Experimental data show that the material density is consistently between 6.13-6.15 g / cm³. 3 It has high density and bending strength of 1629-1658MPa, far exceeding the traditional H13 steel of about 1200MPa. It solves the problem of traditional high-hardness materials being "hard and brittle". Moreover, the performance of products with different composition ranges and different quality is roughly the same, which reflects the stability and reliability of the process. Detailed Implementation

[0038] The foregoing has broadly described the features and technical advantages of the invention to facilitate a better understanding of its detailed description. Other features and advantages of the invention will be described below. Those skilled in the art will understand that the disclosed concepts and specific embodiments can be readily used as a basis for modifying or designing other structures to accomplish the same objectives of the invention. Those skilled in the art will also recognize that such equivalent constructions do not depart from the spirit and scope of the invention. However, it should be clearly understood that each feature provided is for description and illustration only and is not intended to limit the definition of the invention.

[0039] It should be understood that the terminology used herein is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, regarding numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included within the invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range. The terms "comprising," "including," "having," "containing," etc., as used herein are open-ended, meaning they include but are not limited to.

[0040] In an embodiment of the present invention, a modified high-temperature resistant, high-wear-resistant, and corrosion-resistant composite functional material comprises the following components by mass percentage: modified TiC: 38.0%-52.0%, Mo: 2.0%-4.0%, Ni: 3.0%-5.0%, Mn: 7.0%-10.0%, Co: 0.5%-1.5%, C: 0.5%-1.0%, Cr: 0.5%-1.5%, Y2O3: 0.1-0.3%, with the balance being Fe and unavoidable impurities.

[0041] The modified TiC has a particle size of 1-5 μm and has undergone surface modification with a silane coupling agent. The specific steps for preparing the modified TiC are as follows:

[0042] a. Place TiC powder with a particle size of 1-5 μm in a 5% (w / w) dilute hydrochloric acid solution and stir in a 60°C constant temperature water bath for 2 h to remove the surface oxide layer and impurities; then wash with water until pH = 6.5-7.5, and dry in a vacuum drying oven at 80°C for 4 h to obtain clean and dry TiC powder;

[0043] b. The surface silane coupling agent is prepared by mixing γ-aminopropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1-3:45-55:5-8. The pH of the solution is adjusted to 3.5-4.5 with glacial acetic acid, and the mixture is stirred at 30°C for 30 min to allow the silane to be fully hydrolyzed and form a stable hydrolysate.

[0044] c. Add the pretreated TiC powder to the above hydrolysate, with a mass ratio of TiC to hydrolysate of 1:10. Stir at 50°C for 1.5 h until the condensation reaction is complete, allow to stand and precipitate, filter and discard the supernatant.

[0045] d. Wash the modified TiC powder twice with anhydrous ethanol; dry it in a vacuum drying oven at 100℃ for 6 hours to obtain modified TiC powder.

[0046] The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material includes the following steps:

[0047] S1. Batching calculation: Calculate the weight according to the grouping ratio, and weigh the metal raw materials after calculating the evaporation replenishment value; among them, Cr is added in the form of Cr-Fe-C master alloy, Mo is added in the form of Mo-Fe master alloy, and Mn is added in the form of Mn-Fe-C master alloy.

[0048] S2. Two-step ball milling and mixing: First stage: Mo, Ni, Mn, Co, Cr, C, and Fe are introduced into the corresponding elements based on the intermediate alloy form described in step S1. The mixture is ball-milled in a high-energy ball mill at 400-500 rpm for 4-6 hours using WC-Co hard alloy grinding balls with a ball-to-material ratio of 4-5:1 to form a pre-alloyed powder. Second stage: Modified TiC and Y2O3 are added to the pre-alloyed powder. The mixture is ball-milled in a low-energy ball mill at 150-200 rpm for 12-15 hours using ZrO2 grinding balls with a ball-to-material ratio of 2-3:1. 350-450 ml / kg of anhydrous ethanol is also added.

[0049] S3. Vacuum freeze drying: Dry the wet milled mixture at -25 to -20°C and a vacuum of 1-5 Pa for 8-12 hours;

[0050] S4. Rubber-blended granulation: Add 105-115 ml / kg of sodium butadiene rubber-polyvinyl alcohol composite molding agent, which is a mixture of sodium butadiene rubber and polyvinyl alcohol in a mass ratio of 6-8:2-4; prepare material granules through a granulator to obtain granules with a mesh size of 65-75 mesh.

[0051] S5. Ultrasonic-assisted pressing: Pressing is assisted by 50-80kHz ultrasonic vibration at a pressure of 800-1000MPa;

[0052] S6. Gradient vacuum sintering:

[0053] Degumming stage: room temperature to 600-650℃, microwave power density 5-10W / cm³ 3 Heating rate: 8-12℃ / min;

[0054] Solid-state sintering stage: 600-650℃ to 1100-1200℃, microwave power density 10-15W / cm² 3 The heating rate is 13-18℃ / min;

[0055] Liquid phase sintering stage: 1100-1200℃ to 1420-1480℃, microwave power density 12-15W / cm³ 3 The heating rate is 20℃ / min; after reaching the highest temperature, 120-180MPa high-purity argon gas is introduced and the pressure and temperature are maintained for 60±5min. The microwave frequency is 2-2.45GHz and the argon purity is ≥99.999%.

[0056] Technical principle of the invention:

[0057] 1. Technical principles of each component of the raw material:

[0058] Modified TiC, as the core hard phase, provides the material with high hardness and wear resistance, and its high melting point of 3140℃ exhibits excellent high-temperature stability. Amino groups are introduced into the TiC surface through silane coupling agent modification, forming chemical bonds with the metal matrix to enhance interfacial bonding strength. Controlling the lower limit of TiC dosage ensures sufficient hard phase content to maintain wear resistance, while the upper limit prevents a significant increase in material brittleness leading to fracture failure.

[0059] Mo and Ni work together to lower the sintering temperature, promote liquid phase sintering, and increase the density of the material. Mo forms carbides, refines the grains, and improves high-temperature strength, while Ni expands the austenite region, enhancing the toughness and corrosion resistance of the matrix. The amount of both needs to be controlled to avoid excessive amounts that could lead to a decline in material performance.

[0060] Mn stabilizes the austenitic structure and improves work hardening ability, while Cr forms carbides to enhance high-temperature oxidation resistance. At the same time, Cr forms a dense and stable Cr2O3 oxide film on the material surface, which prevents corrosive media from penetrating the matrix and significantly improves corrosion resistance. However, if the amount of Cr is too high, it will form coarse and brittle carbides, which will reduce toughness and destroy the continuity of the oxide film, thus weakening corrosion resistance.

[0061] Co can integrate well with the metal matrix. During sintering, it can reduce the sintering activation energy of the system, promote the bonding between components, and improve the density of the material. At the same time, Co can dissolve in the matrix, and through the solid solution strengthening effect, it can enhance the strength and hardness of the material. Under high temperature conditions, it can also hinder dislocation movement and inhibit grain growth. Combined with other elements, it can further improve the high-temperature mechanical properties of the material. In addition, Co has a positive effect on improving the toughness of the material, absorbing impact energy, mitigating the tendency of crack propagation, helping to balance the high hardness and toughness of the material, avoiding brittle fracture, and making the material more stable when subjected to complex stresses.

[0062] Y2O3 inhibits grain growth by pinning grain boundaries, adsorbs impurities to purify the interface, and promotes the formation of a dense protective film to enhance oxidation resistance. However, if the amount exceeds 0.3%, it will agglomerate, forming defects and reducing the strength of the material.

[0063] Carbon regulates the formation of carbides, optimizing the balance between hardness and toughness. Too little carbon leads to insufficient carbide content and decreased hardness, while too much carbon forms coarse carbides, reducing the material's toughness.

[0064] 2. Technical principles of the process steps:

[0065] The two-stage ball milling process involves two stages. The first stage uses high-energy ball milling to fully alloy the metal elements and form a uniform pre-alloyed powder. If the rotation speed is too low or the time is too short, the alloying will be insufficient and the components will segregate. If the speed is too high, impurities will be introduced. The second stage uses low-energy ball milling to avoid breaking the modified TiC particles and ensure their uniform dispersion. Using high-energy ball milling will damage the modified TiC surface layer and reduce the interfacial bonding force.

[0066] Vacuum freeze drying avoids particle agglomeration and oxidation caused by traditional drying. Ice crystal sublimation forms a porous structure, which improves the densification rate of subsequent sintering. If the temperature is too high, the ice crystals melt and cause particle agglomeration. If the vacuum degree is insufficient, moisture residue will cause pores to be generated during sintering.

[0067] Ultrasonic-assisted pressing utilizes the acoustic cavitation effect to break up agglomerates between particles and improve powder flowability. The acoustic flow effect promotes particle rearrangement and reduces pressing stress. If the frequency is too low, the cavitation effect is not significant, while if it is too high, the energy loss is large. If the pressure is insufficient, the green body density is low and it is easy for pores to appear after sintering.

[0068] In the microwave-assisted gradient sintering debinding stage, the forming agent is slowly decomposed to prevent cracking of the green body. Traditional heating methods, with their slow temperature rise, easily lead to carbonization and residue of the forming agent. In the solid-phase sintering stage, atomic diffusion is activated to form a preliminary sintering neck, while microwave selective heating promotes the sintering process. In the liquid-phase sintering stage, a liquid phase fills the pores, and high-pressure argon gas inhibits the evaporation of metal elements to prevent material oxidation. Furthermore, the argon atmosphere can inhibit the oxidation of elements such as Cr and Ni, ensuring the integrity of the surface oxide film and indirectly improving corrosion resistance. If the temperature is too low, the amount of liquid phase is insufficient, and densification is inadequate, which will reduce corrosion resistance due to pore residue. If the temperature is too high, the grains will coarsen, destroying the uniformity of the structure and weakening corrosion resistance. Insufficient pressure cannot effectively eliminate closed pores, providing channels for corrosive media and reducing material density and corrosion resistance.

[0069] 3. The necessity and importance of parameter control:

[0070] The amount of raw materials used is closely related to the performance. Increasing the TiC content increases hardness but decreases flexural strength. A Co content in the range of 0.5-1.5% can synergistically improve strength and toughness through solid solution strengthening; excessive Co content reduces density due to Co phase agglomeration, while insufficient content weakens high-temperature stability. Increasing the Cr content reduces the oxidation weight gain rate and optimizes the density and continuity of the Cr2O3 oxide film, improving corrosion resistance; however, excessive Cr can reduce toughness and damage the oxide film due to the influence of brittle phases, requiring precise control. Process parameters significantly affect the material microstructure and properties. Increasing the ball mill speed improves the uniformity of element distribution in the pre-alloyed powder and reduces hardness fluctuations; increasing the sintering temperature increases material density but increases grain size and decreases toughness; increasing microwave power shortens sintering time, but excessive power can lead to localized overheating and crack formation. The composition and process must be matched. High TiC content must be combined with high-pressure sintering to ensure densification. Adding Y2O3 can reduce the sintering temperature and refine the grains. Parameters can be optimized through orthogonal experiments to achieve the best comprehensive performance of the material. Especially in terms of corrosion resistance, precise control of composition and process can ensure the integrity of the oxide film and the density of the structure, avoid the formation of corrosion channels, and make the material adaptable to complex corrosion conditions.

[0071] Example 1

[0072] A modified high-temperature resistant, high-wear resistant, and corrosion resistant composite functional material comprises the following components by mass percentage: modified TiC: 45.6%, Mo: 2.4%, Ni: 3.8%, Mn: 8.5%, Co: 1.5%, C: 1.0%, Cr: 1.2%, Y2O3: 0.2%, with the balance being Fe and unavoidable impurities.

[0073] The modified TiC has a particle size of 1-5 μm and has undergone surface modification with a silane coupling agent. The specific steps for preparing the modified TiC are as follows:

[0074] a. Place TiC powder with a particle size of 1-5 μm in a 5% (w / w) dilute hydrochloric acid solution and stir in a 60°C constant temperature water bath for 2 h to remove the surface oxide layer and impurities; then wash with water until pH=7, and dry in a vacuum drying oven at 80°C for 4 h to obtain clean and dry TiC powder;

[0075] b. The surface silane coupling agent is prepared by mixing γ-aminopropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1:50:5. The pH of the solution is adjusted to 4 with glacial acetic acid, and the mixture is stirred at 30°C for 30 min to allow the silane to be fully hydrolyzed and form a stable hydrolysate.

[0076] c. Add the pretreated TiC powder to the above hydrolysate, with a mass ratio of TiC to hydrolysate of 1:10. Stir at 50°C for 1.5 h until the condensation reaction is complete, allow to stand and precipitate, filter and discard the supernatant.

[0077] d. Wash the modified TiC powder twice with anhydrous ethanol; dry it in a vacuum drying oven at 100℃ for 6 hours to obtain modified TiC powder.

[0078] The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material includes the following steps:

[0079] S1. Batching calculation: Calculate the weight according to the grouping ratio, and weigh the metal raw materials after calculating the evaporation replenishment value; among them, Cr is added in the form of Cr-Fe-C master alloy, Mo is added in the form of Mo-Fe master alloy, and Mn is added in the form of Mn-Fe-C master alloy.

[0080] S2. Two-step ball milling and mixing: First stage: Mo, Ni, Mn, Co, Cr, C, and Fe are introduced into the corresponding elements based on the intermediate alloy form described in step S1, and ball milled at 450 rpm for 5 hours in a high-energy ball mill using WC-Co hard alloy grinding balls with a ball-to-material ratio of 5:1 to form pre-alloyed powder; Second stage: Modified TiC and Y2O3 are added to the pre-alloyed powder, and ball milled at 180 rpm for 13 hours in a low-energy ball mill using ZrO2 grinding balls with a ball-to-material ratio of 3:1, and 400 ml / kg of anhydrous ethanol is added;

[0081] S3. Vacuum freeze drying: Dry the wet-milled mixture at -20℃ and a vacuum of 1-5Pa for 12 hours;

[0082] S4. Rubber-blended granulation: Add 110 ml / kg of sodium butadiene rubber-polyvinyl alcohol composite molding agent, which is a mixture of sodium butadiene rubber and polyvinyl alcohol at a mass ratio of 8:2; prepare material granules through a granulator to obtain granules with a mesh size of 70 mesh.

[0083] S5. Ultrasonic-assisted pressing: 70kHz ultrasonic vibration is used to assist pressing at a pressure of 1000MPa;

[0084] S6. Gradient vacuum sintering:

[0085] Degumming stage: room temperature to 600℃, microwave power density 8W / cm² 3 Heating rate: 10℃ / min;

[0086] Solid-state sintering stage: 600℃ to 1200℃, microwave power density 10W / cm³ 3 Heating rate: 15℃ / min;

[0087] Liquid phase sintering stage: 1200℃ to 1450℃, microwave power density 12W / cm³ 3The heating rate is 20℃ / min; after reaching the highest temperature, 150MPa high-purity argon gas is introduced and the pressure and temperature are maintained for 60min. The microwave frequency is 2.45GHz and the argon purity is ≥99.999%.

[0088] Example 2

[0089] A modified high-temperature resistant, high-wear resistant, and corrosion resistant composite functional material comprises the following components by mass percentage: modified TiC: 46.1%, Mo: 2.9%, Ni: 3.6%, Mn: 9.5%, Co: 0.8%, C: 0.9%, Cr: 0.9%, Y2O3: 0.25%, with the balance being Fe and unavoidable impurities.

[0090] The preparation process of modified TiC is the same as in Example 1.

[0091] The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material includes the following steps:

[0092] S1. Batching calculation: Calculate the weight according to the grouping ratio, and weigh the metal raw materials after calculating the evaporation replenishment value; among them, Cr is added in the form of Cr-Fe-C master alloy, Mo is added in the form of Mo-Fe master alloy, and Mn is added in the form of Mn-Fe-C master alloy.

[0093] S2. Two-step ball milling and mixing: First stage: Mo, Ni, Mn, Co, Cr, C, and Fe are introduced into the corresponding elements based on the intermediate alloy form described in step S1, and ball milled at 400 rpm for 6 hours in a high-energy ball mill using WC-Co hard alloy grinding balls with a ball-to-material ratio of 5:1 to form pre-alloyed powder; Second stage: Modified TiC and Y2O3 are added to the pre-alloyed powder, and ball milled at 200 rpm for 12 hours in a low-energy ball mill using ZrO2 grinding balls with a ball-to-material ratio of 3:1, and 420 ml / kg of anhydrous ethanol is added;

[0094] S3. Vacuum freeze drying: The wet-milled mixture is dried at -22℃ and a vacuum of 1-5Pa for 11 hours;

[0095] S4. Rubber-blended granulation: Add 115 ml / kg of sodium butadiene rubber-polyvinyl alcohol composite molding agent, which is a mixture of sodium butadiene rubber and polyvinyl alcohol at a mass ratio of 7:3; prepare material granules through a granulator to obtain granules with a mesh size of 75 mesh.

[0096] S5. Ultrasonic-assisted pressing: Pressing is assisted by 65kHz ultrasonic vibration at a pressure of 850MPa.

[0097] S6. Gradient vacuum sintering:

[0098] Degumming stage: room temperature to 620℃, microwave power density 9W / cm³ 3 Heating rate: 10℃ / min;

[0099] Solid-state sintering stage: 620℃ to 1150℃, microwave power density 12W / ccm 3 Heating rate: 15℃ / min;

[0100] Liquid phase sintering stage: 1150℃ to 1480℃, microwave power density 15W / cm³ 3 The heating rate is 20℃ / min; after reaching the highest temperature, 180MPa high-purity argon gas is introduced and the pressure and temperature are maintained for 62min. The microwave frequency is 2.45GHz and the argon purity is ≥99.999%.

[0101] Example 3

[0102] A modified high-temperature resistant, high-wear resistant, and corrosion resistant composite functional material comprises the following components by mass percentage: modified TiC: 39.5%, Mo: 2.2%, Ni: 3.0%, Mn: 9.4%, Co: 0.5%, C: 0.9%, Cr: 0.6%, Y2O3: 0.15%, with the balance being Fe and unavoidable impurities.

[0103] The preparation process of modified TiC is the same as in Example 1.

[0104] The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material includes the following steps:

[0105] S1. Batching calculation: Calculate the weight according to the grouping ratio, and weigh the metal raw materials after calculating the evaporation replenishment value; among them, Cr is added in the form of Cr-Fe-C master alloy, Mo is added in the form of Mo-Fe master alloy, and Mn is added in the form of Mn-Fe-C master alloy.

[0106] S2. Two-step ball milling and mixing: First stage: Mo, Ni, Mn, Co, Cr, C, and Fe are introduced into the corresponding elements based on the intermediate alloy form described in step S1, and ball milled at 500 rpm for 4 hours in a high-energy ball mill using WC-Co hard alloy grinding balls with a ball-to-material ratio of 5:1 to form pre-alloyed powder; Second stage: Modified TiC and Y2O3 are added to the pre-alloyed powder, and ball milled at 150 rpm for 15 hours in a low-energy ball mill using ZrO2 grinding balls with a ball-to-material ratio of 3:1, and 390 ml / kg of anhydrous ethanol is added;

[0107] S3. Vacuum freeze drying: The wet-milled mixture is dried at -25℃ and a vacuum of 1-5 Pa for 9 hours;

[0108] S4. Rubber-blended granulation: Add 108 ml / kg of sodium butadiene rubber-polyvinyl alcohol composite molding agent, which is a mixture of sodium butadiene rubber and polyvinyl alcohol in a mass ratio of 6:4; prepare material granules through a granulator to obtain granules with a mesh size of 68 mesh.

[0109] S5. Ultrasonic-assisted pressing: Pressing is assisted by 80kHz ultrasonic vibration at a pressure of 900MPa;

[0110] S6. Gradient vacuum sintering:

[0111] Degumming stage: room temperature to 630℃, microwave power density 8W / cm³ 3 Heating rate: 10℃ / min;

[0112] Solid-state sintering stage: 630℃ to 1200℃, microwave power density 10W / cm³ 3 Heating rate: 15℃ / min;

[0113] Liquid phase sintering stage: 1200℃ to 1460℃, microwave power density 13W / cm² 3 The heating rate is 20℃ / min; after reaching the highest temperature, 120MPa high-purity argon gas is introduced and the pressure and temperature are maintained for 60min. The microwave frequency is 2.45GHz and the argon purity is ≥99.999%.

[0114] The HRC hardness, density, and flexural strength of the materials prepared in Examples 1-3 were tested. High-temperature resistance was tested by embedding a high-temperature furnace bottom roller in an iron box protected by carbon black, placing it in a box-type resistance furnace, heating it to 1100℃, holding it at that temperature for 45 minutes, and then cooling it to room temperature in the furnace for approximately 13 hours. The samples were then removed, polished, and the hardness was tested again. The samples were machined into 50mm×10mm×5mm cuboids, polished to Ra0.8μm, weighed, and then immersed in a 3.5% NaCl solution at (25±2)℃ for 30 days, with the solution changed weekly. After the 30-day period, the samples were removed, surface corrosion products were removed, weighed, and the corrosion rate (mm / year) was calculated. The results of each experiment are shown in Table 1.

[0115] Table 1: Results of each experiment

[0116]

[0117] As shown in the table above, the hardness of products prepared according to the method of this invention, with different component ranges and different qualities, ranges from HRC 62.8 to 63.8, the flexural strength ranges from 1629 to 1658 MPa, and the density ranges from 6.13 to 6.15 g / cm³. 3 The products are roughly equivalent in performance, indicating that the component ratios and process parameters are appropriate.

[0118] Experimental data demonstrate the significant advantages of this invention. Through the synergistic effect of the composition and process, in Examples 1-3, although the HRC hardness, density, and flexural strength showed gradient changes with adjustments to key components such as modified TiC, Mo, and Ni, as well as process parameters such as ball milling speed and pressing pressure, they remained at a relatively high level overall. For example, Example 1 achieved a hardness of 63.8 and a density of 6.15 g / cm³. 3 The flexural strength of 1658MPa demonstrates that this invention, through precise control of raw materials and processes, can stably impart the basic properties of high hardness, high density, and high strength to the material, which is difficult to achieve with traditional materials.

[0119] After high-temperature testing at 1100℃, the material of this invention exhibits minimal hardness loss, with a retention rate exceeding 95%, far superior to the approximately 60% high-temperature hardness retention rate of traditional H13 steel. The modified TiC exhibits strong interfacial bonding with the matrix, preventing hard phase detachment, while Cr, Y2O3, and other components form a dense oxide film to inhibit high-temperature oxidation, resulting in excellent high-temperature stability. The hardness change trend after high-temperature testing remains consistent with the initial value, indicating that the composition-process design achieves excellent synergistic performance at both room temperature and high temperatures. This is the core advantage of this invention under extreme high-temperature conditions.

[0120] In the corrosion test with 3.5% NaCl solution, the corrosion rates of Examples 1-3 ranged from 0.028 to 0.035 mm / year, which is much lower than that of traditional materials. This is due to the dense oxide film formed by Cr, which effectively blocks the intrusion of corrosive media, and Ni, which stabilizes the austenitic matrix and reduces the sensitivity to grain boundary corrosion. The two work synergistically to give the material outstanding corrosion resistance, making it suitable for complex corrosive conditions such as those containing chlorine and humidity.

[0121] Hardness, density, and flexural strength are positively correlated, with density laying the foundation for comprehensive performance. Synergistic optimization of "composition and process" enables simultaneous improvement of multi-dimensional performance. Compared with traditional materials, the high-temperature furnace bottom rollers and other components made by this invention are expected to have a significantly longer service life under extreme conditions of high temperature and wear, effectively replacing existing technologies and expanding high-end application scenarios. This fully verifies the technical value of this invention in achieving breakthroughs in high temperature resistance and high wear resistance through precise control, providing a better solution for the field of high-temperature wear resistance.

[0122] The above description, in conjunction with specific / preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various substitutions or modifications can be made to these described embodiments without departing from the inventive concept, and all such substitutions or modifications should be considered within the scope of protection of the present invention.

[0123] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0124] Although the invention and its advantages have been described in detail, it should be understood that various changes, substitutions, and modifications can be made without departing from the spirit and scope of the invention. Furthermore, the scope of the invention is not limited to the specific embodiments of the processes, machines, manufactures, compositions of matter, methods, and steps described in the specification. From the disclosure of this invention, those skilled in the art will readily utilize existing or future processes, machines, manufactures, compositions of matter, methods, or steps that substantially perform the same function or achieve the same results as the corresponding embodiments described herein. Therefore, the appended claims are intended to encompass such processes, machines, manufactures, compositions of matter, methods, or steps.

Claims

1. A modified high-temperature resistant, high-wear-resistant, and corrosion-resistant composite functional material, characterized in that, By mass percentage, the material comprises the following components: modified TiC: 38.0%-52.0%, Mo: 2.0%-4.0%, Ni: 3.0%-5.0%, Mn: 7.0%-10.0%, Co: 0.5%-1.5%, C: 0.5%-1.0%, Cr: 0.5%-1.5%, Y2O3: 0.1%-0.3%, with the balance being Fe and unavoidable impurities.

2. The modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material as described in claim 1, characterized in that, The modified TiC has a particle size of 1-5 μm and has been modified with a surface silane coupling agent.

3. The modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material as described in claim 1, characterized in that, The modified TiC is treated with a surface silane coupling agent, which is a mixture of γ-aminopropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1-3:45-55:5-8.

4. A method for preparing a modified high-temperature resistant, high-wear resistant, and corrosion-resistant composite functional material as described in any one of claims 1-3, comprising the following steps: S1. Batching calculation: Calculate the weight according to the grouping ratio, and weigh the metal raw materials after calculating the evaporation replenishment value; among them, Cr is added in the form of Cr-Fe-C master alloy, Mo is added in the form of Mo-Fe master alloy, and Mn is added in the form of Mn-Fe-C master alloy. S2. Two-step ball milling and mixing: First stage: Mo, Ni, Mn, Co, Cr, C, and Fe are introduced into the corresponding elements based on the intermediate alloy form described in step S1, and ball milled in a high-energy ball mill at 400-500 rpm for 4-6 hours to form a pre-alloyed powder; Second stage: Modified TiC and Y2O3 are added to the pre-alloyed powder, and ball milled in a low-energy ball mill at 150-200 rpm for 12-15 hours, with 350-450 ml / kg of anhydrous ethanol added; S3. Vacuum freeze drying: Dry the wet milled mixture at -25 to -20°C and a vacuum of 1-5 Pa for 8-12 hours; S4. Rubber-blended granulation: Add 105-115 ml / kg of sodium butadiene rubber-polyvinyl alcohol composite molding agent, and prepare material granules through a granulator; S5. Ultrasonic-assisted pressing: Pressing is assisted by 50-80kHz ultrasonic vibration at a pressure of 800-1000MPa; S6. Gradient vacuum sintering: Degumming stage: room temperature to 600-650℃, microwave power density 5-10W / cm³ 3 Heating rate: 8-12℃ / min; Solid-state sintering stage: 600-650℃ to 1100-1200℃, microwave power density 10-15W / cm² 3 The heating rate is 13-18℃ / min; Liquid phase sintering stage: 1100-1200℃ to 1420-1480℃, microwave power density 12-15W / cm³ 3 The heating rate is 20℃ / min; after reaching the highest temperature, 120-180MPa high-purity argon gas is introduced and the pressure and temperature are maintained for 60±5min.

5. The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material as described in claim 4, characterized in that, Step S2: The first stage of high-energy ball milling uses WC-Co cemented carbide grinding balls, and the second stage of low-energy ball milling uses ZrO2 grinding balls.

6. The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material as described in claim 4, characterized in that, Step S2: The ball-to-material ratio in the first stage is 4-5:1, and the ball-to-material ratio in the second stage is 2-3:

1.

7. The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material as described in claim 4, characterized in that, The composite molding agent described in step S4 is a mixture of sodium butadiene rubber and polyvinyl alcohol in a mass ratio of 6-8:2-4.

8. The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material as described in claim 4, characterized in that, The particle size obtained in step S4 is 65-75 mesh.

9. The preparation method of the modified high-temperature resistant and high-wear-resistant, corrosion-resistant composite functional material as described in claim 4, characterized in that, The microwave frequency in step S6 is 2-2.45 GHz, and the argon gas purity is ≥99.999%.

10. The application of a modified high-temperature resistant, high-wear resistant, and corrosion resistant composite functional material produced by the method according to any one of claims 4-9 in the manufacture of high-temperature furnace bottom plates, high-temperature atmosphere furnace bottom plates, punches, hammer inserts, and high-precision mold steel.

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