TiSiCe target material and preparation method thereof
Through vacuum induction smelting and powder metallurgy forming processes, TiSiCe targets were prepared, which solved the brittleness and uniformity of the ingot blank caused by high Si content in traditional methods, and achieved the improvement of the stability and performance of the target.
Patent Information
- Application Number
- CN202411939723.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-26
- Publication Date
- 2025-04-25
AI Technical Summary
When traditional TiSiCe targets have high Si content, complex alloy phases are generated during the smelting process, resulting in high brittleness of the ingot and the inability to process the finished target. At the same time, when the Si ratio increases, the uniformity of the ingot is difficult to control.
Si and Ce are melted into CeSi2 alloy ingots with a vacuum degree of less than 100Pa, and then crushed into CeSi2 alloy powder by ball milling, and then mixed with Ti powder and Si powder in a specific proportion. After molding, degassing, and thermal isostatic treatment, TiSiCe target material is finally obtained.
It effectively avoids risk factors such as oxidation and spontaneous combustion in the production process, ensures the stable quality and performance of TiSiCe targets, and realizes the preparation of targets with Si content within 30%.
Smart Images
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Abstract
Description
Technical Field
[0001] The present application relates to the technical field of powder metallurgy materials, and in particular to a TiSiCe target material and a preparation method thereof. Background Art
[0002] Since the 1960s, the deposition of superhard thin film materials on the surface of metal cutting tools through PVD technology can significantly increase cutting speed and wear resistance, extend tool life, and become the main method to improve tool performance. In recent years, driven by the development of high-end equipment manufacturing, aerospace, and automobile industries, the global manufacturing technology level and production efficiency have made great progress, and the demand for high-performance tools and molds has increased.
[0003] In practical applications, processing different types of materials requires different tool and die performance. To meet the requirements of higher-speed dry cutting, tool coatings must have higher red hardness and high-temperature oxidation resistance, but existing TiN, CrN, TiAlN, and CrAlN coatings can no longer meet these requirements. Hard coatings are gradually developing in the direction of diversification, nano-ization, and composites, and high-speed and dry cutting will become the main direction of tool coating development in the future.
[0004] It is known that TiSiN coating forms a special nanocomposite structure of amorphous Si3N4 wrapped around TiN due to the addition of Si element, which significantly improves the hardness and oxidation resistance of the coating. It can work at high cutting speeds and can even cut without coolant, and can easily process nickel-based alloys and titanium materials. At present, with the rapid development of coating technology, further introducing other metal or non-metal elements on the basis of TiSiN coating to improve the performance of the film layer has gradually become the main development direction of coatings in this field. Among them, the introduction of a certain amount of Ce element in TiSiN coating to effectively improve the high temperature resistance and wear resistance of the coating has been widely used.
[0005] Traditional TiSiCe targets can be prepared by vacuum melting process, but according to the TiSi phase diagram, when the Si content is greater than 20at%, a very complex alloy phase will be generated during the melting process, resulting in the smelted ingot being brittle and unable to be processed into finished target products. At the same time, due to the large difference in density between Ti and Si, when the Si ratio increases, the uniformity of the smelted ingot is difficult to control. Summary of the invention
[0006] In order to solve the above technical problems, the present application provides a TiSiCe target material and a preparation method thereof.
[0007] The present application provides a method for preparing a TiSiCe target material, which specifically comprises the following steps in sequence: (1) Si and Ce are melted into CeSi2 alloy ingots by vacuum induction melting method with a vacuum degree of less than 100 Pa, and then crushed into CeSi2 alloy powder by ball milling; (2) CeSi2 alloy powder, Ti powder or CeSi2 alloy powder, Si powder and Ti powder are weighed and mixed uniformly according to the ratio of Ti = 60-99at%, Si = 2-30at%, Ce = 1-10at%, to obtain TiSiCe alloy powder; wherein the Si content is ≥ Ce content × 2; (3) The TiSiCe alloy powder is subjected to compression molding, degassing treatment, hot isostatic pressing treatment, and finished product processing to obtain the TiSiCe target material.
[0008] Preferably, in step (1), the purity of Ce and Si is ≥2N5.
[0009] Preferably, in step (1), the purity of Ce and Si is ≥2N8.
[0010] Preferably, in step (2), the particle size of the CeSi2 alloy powder is -80 mesh; the particle size of the Si powder is -80 mesh; and the particle size of the Ti powder is -80 mesh.
[0011] Preferably, the particle size of the CeSi2 alloy powder is 200-325 mesh; the particle size of the Si powder is 200-325 mesh; and the particle size of the Ti powder is 200-325 mesh.
[0012] Preferably, the element composition of the TiSiCe target is: Ti=65-80at%, Si=17-27at%, Ce=1-8at%.
[0013] Preferably, in step (3), the parameters of the compression molding are: the pressure is 300-1000 tons; the density of the blank obtained by the compression molding is 56-70%; the blank is a round cake-shaped blank with a diameter of D = 50-200 mm and a height of L = 5-30 mm.
[0014] Preferably, the degassing treatment parameters are: temperature of 400-600°C, degassing vacuum of 2×10 -2 -1×10 -3 Pa, time is 4-10h.
[0015] Preferably, the degassing treatment parameters are: temperature of 450-550°C, degassing vacuum of 2×10 -2 -1×10 -3 Pa, time is 6-8h.
[0016] Preferably, the parameters of the hot isostatic pressing treatment are: treatment temperature of 900-1100° C., pressure of 110-140 MPa, and heat and pressure holding time of 2-6 h.
[0017] Preferably, the parameters of the hot isostatic pressing treatment are: first increase the sintering temperature to 700-800°C for pre-sintering for 1-2h; then increase the temperature to 900-1100°C at a heating rate of 2-10°C / min, apply a pressure of 100-150MPa, and keep the temperature and pressure for 2-6h.
[0018] Preferably, the parameters of the hot isostatic pressing treatment are: first, the sintering temperature is raised to 720-780°C for pre-sintering for 1-2 hours; then, the temperature is raised to 950-1050°C at a heating rate of 4-8°C / min, a pressure of 110-140MPa is applied, and the heat and pressure holding time is 3-5 hours.
[0019] In a second aspect, the present application provides a TiSiCe target material prepared using the above-mentioned TiSiCe target material preparation method.
[0020] The present application adopts a powder metallurgy forming process to prepare TiSiCe target materials, which can realize the preparation of TiSiCe target materials with Si content within 30%. At the same time, a vacuum induction melting method with a vacuum degree of less than 100Pa is used to melt Si and Ce into CeSi2 alloy ingots, and CeSi2 is used as the source material of Ce, replacing pure Ce powder and adding it to the TiSiCe target material, which can effectively avoid the oxidation and spontaneous combustion of pure Ce metal powder during the production process.
[0021] In summary, the technical solution of this application has the following effects: The present application adopts a vacuum induction melting method with a vacuum degree of less than 100Pa to melt Si and Ce into a CeSi2 alloy ingot, and uses CeSi2 as the source material of Ce, replacing pure Ce powder and adding it to the TiSiCe target material, which can effectively avoid the oxidation, spontaneous combustion and other dangerous factors of pure Ce metal powder during the production process.
[0022] The preparation method provided in the present application ensures the stability of the quality or performance of the TiSiCe target material by setting a heat preservation step and controlling the heating rate during the hot isostatic pressing process. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is a process roadmap for the preparation method of the TiSiCe target material in Example 1 of the present application.
[0024] Figure 2 This is an ultrasonic flaw detection image of the smelting product of the TiSiCe target material in Example 1 of the present application.
[0025] Figure 3 This is a diagram of the spontaneous combustion phenomenon that occurred during the TiSiCe target material preparation process in Comparative Example 1 of the present application.
[0026] Figure 4 This is an ultrasonic flaw detection image of the smelting product of the TiSiCe target material in Comparative Example 2 of the present application. DETAILED DESCRIPTION
[0027] The present application is further described in detail below in conjunction with examples, comparative examples and performance testing experiments. These examples should not be construed as limiting the scope of protection claimed in the present application. Example
[0028] Example 1 Example 1 provides a TiSiCe target material and a preparation method thereof.
[0029] The process route diagram of the target material preparation method in this embodiment is as follows: Figure 1 As shown, it includes the following steps: (1) Si and Ce are melted into CeSi2 alloy ingots by vacuum induction melting method with a vacuum degree less than 100 Pa, and then ball milled into CeSi2 alloy powder with a particle size of 200-325 mesh; the purity of Ce and Si is ≥2N8.
[0030] (2) CeSi2 alloy powder, Si powder and Ti powder were weighed according to the ratio of Ti = 70at%, Si = 25at%, Ce = 5at%, and mixed in a three-dimensional mixer for 6 hours to obtain TiSiCe alloy powder; wherein the particle size of CeSi2 alloy powder is 200-325 mesh; the particle size of Si powder is 200-325 mesh; the particle size of Ti powder is 200-325 mesh.
[0031] (3) The TiSiCe alloy powder is subjected to compression molding, degassing treatment, hot isostatic pressing treatment, and finished product processing to obtain a TiSiCe target material; wherein the compression molding process is specifically as follows: the TiSiCe alloy powder is subjected to compression molding at a pressure of 600 tons to obtain a blank with a relative density of 62%; the blank is a round cake-shaped blank with a diameter of D = 100 mm and a height of L = 15 mm; The degassing process is as follows: the blank is placed in the package and then heated and vacuum degassed through the reserved degassing port. The degassing temperature is 450°C and the degassing vacuum degree is 1×10 -3 Pa, time is 7h; The specific hot isostatic pressing process is as follows: put the degassed package into the hot isostatic pressing furnace, first raise the sintering temperature to 750°C for pre-sintering for 1.5 hours; then raise the temperature to 1000°C at a heating rate of 6°C / min, apply a pressure of 125MPa, and keep the temperature and pressure for 4 hours; The specific processing technology of the finished product is as follows: after removing the sheath from the hot isostatically pressed blank, it is processed into a TiSiCe target product that meets the requirements of the drawing by wire cutting, milling, grinding, turning, etc.
[0032] like Figure 2 The ultrasonic flaw detection image of the smelting product of the TiSiCe target material in this embodiment is shown. It can be seen that the target material has excellent uniformity of structure and good performance.
[0033] Example 2-11 Examples 2-11 respectively provide a TiSiCe target material and a preparation method thereof.
[0034] The difference between the above embodiment and embodiment 1 is that the hot isostatic pressing process parameter conditions are different, as shown in Table 1.
[0035] Table 1 Hot isostatic pressing process parameters in Examples 1-11 The other process parameters in the above embodiment are the same as those in embodiment 1.
[0036] Examples 12-13 Examples 12-13 respectively provide a TiSiCe target material and a preparation method thereof.
[0037] The difference between the above embodiment and embodiment 1 is that the particle size of the raw material powder is different, as shown below.
[0038] In Example 12: the particle size of CeSi2 alloy powder is 200-325 mesh; the particle size of Si powder is 400-500 mesh; the particle size of Ti powder is 400-500 mesh.
[0039] In Example 13: the particle size of CeSi2 alloy powder is 400-500 mesh; the particle size of Si powder is 400-500 mesh; the particle size of Ti powder is 400-500 mesh.
[0040] The other process parameters in the above embodiment are the same as those in embodiment 1.
[0041] Examples 14-17 Examples 14-17 respectively provide a TiSiCe target material and a preparation method thereof.
[0042] The difference between the above embodiment and embodiment 1 is that the element composition of the TiSiCe target is different, as shown below.
[0043] In Example 14: the element composition of the TiSiCe target is: Ti=70at%, Si=22at%, Ce=8at%.
[0044] In Example 15: the element composition of the TiSiCe target is: Ti=94at%, Si=4at%, Ce=2at%.
[0045] In Example 16: the elemental composition of the TiSiCe target is: Ti=74at%, Si=20at%, Ce=6at%.
[0046] In Example 17: the elemental composition of the TiSiCe target is: Ti=80at%, Si=17at%, Ce=3at%.
[0047] The other process parameters in the above embodiment are the same as those in embodiment 1.
[0048] Comparative Example Comparative Example 1 This comparative example provides a TiSiCe target material and a preparation method thereof.
[0049] The difference between this comparative example and Example 1 is that the CeSi2 alloy powder is added in a different form, specifically: the mixed powder is a uniform mixture of element powders: Ce powder, Si powder and Ti powder are weighed according to the ratio of Ti = 70at%, Si = 25at%, Ce = 5at%, and then mixed in a three-dimensional mixer at a speed of 700r / min and a mixing time of 6h to obtain TiSiCe alloy powder; wherein the particle size of Ce powder is -325 mesh, the particle size of Ti powder is -325 mesh, and the particle size of Si powder is -325 mesh.
[0050] The other process parameters in this comparative example are the same as those in Example 1.
[0051] The drawback of this comparative example is that during the mixing process, the Ce powder is highly active and is prone to spontaneous combustion; Figure 2 shown.
[0052] Comparative Example 2 This comparative example provides a TiSiCe target material and a preparation method thereof.
[0053] The difference between this comparative example and Example 1 is that the TiSiCe target material is prepared by using a traditional vacuum consumable melting process.
[0054] The defects of this comparative example are: According to the TiSi phase diagram, when the Si content is greater than 20at%, a very complex alloy phase will be generated during the smelting process, resulting in the smelted ingot being brittle and unable to be processed into a target material. At the same time, due to the large difference in density between Ti and Si, when the Si ratio increases, the uniformity of the smelted ingot is difficult to control. Figure 3 It can be seen from the ultrasonic flaw detection results of the smelting product that the target material has poor uniformity of organization and has defects such as shrinkage cavities and looseness.
[0055] Performance testing (1) Relative density: The measured density is measured by the Archimedes displacement method. The relative density is equal to the measured density divided by the theoretical density.
[0056] Test results: as shown in Table 2.
[0057] Table 2 Performance test results of TiSiCe target materials in Examples 1-17 and Comparative Examples 1-2 Combined with the test results in Table 2, Ti powder, Si powder and CeSi2 will further alloy during the sintering process, resulting in the actual density exceeding the theoretical density calculated according to the powder ratio. At the same time, the density measurement results show that the sintering temperature will affect the final density of the target material, but when the sintering temperature reaches above 1000℃, the sintering temperature and time have little effect on the density.
[0058] By comparing the test results of Examples 1-11, it can be seen that in Example 2, no pre-sintering was performed, and the alloying degree of the prepared target material was relatively low, which resulted in poor film-forming performance of the target material in subsequent applications. Therefore, the present application performed a pre-sintering step during the hot isostatic pressing process, and reasonably controlled the specific process parameters of pre-sintering and post-sintering to obtain a target material with a higher density.
[0059] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.
Claims
1. A method for preparing a TiSiCe target, characterized in that: Specifically, the following steps are performed in sequence: (1) Si and Ce are melted into CeSi2 alloy ingots by vacuum induction melting method with a vacuum degree of less than 100 Pa, and then crushed into CeSi2 alloy powder by ball milling; (2) CeSi2 alloy powder, Ti powder or CeSi2 alloy powder, Si powder and Ti powder are weighed and mixed evenly in a ratio of Ti = 60-99at%, Si = 2-30at%, Ce = 1-10at%, to obtain TiSiCe alloy powder; wherein Si content ≥ Ce content × 2; (3) The TiSiCe alloy powder is subjected to compression molding, degassing treatment, hot isostatic pressing treatment, and finished product processing to obtain the TiSiCe target material.
2. The method for preparing a TiSiCe target according to claim 1, characterized in that: In the step (1), the purity of Ce and Si is ≥2N5.
3. The method for preparing a TiSiCe target according to claim 1, characterized in that: In the step (2), the particle size of the CeSi2 alloy powder is -80 mesh; the particle size of the Si powder is -80 mesh; and the particle size of the Ti powder is -80 mesh.
4. The method for preparing a TiSiCe target according to claim 3, characterized in that: The particle size of the CeSi2 alloy powder is 200-325 mesh; the particle size of the Si powder is 200-325 mesh; the particle size of the Ti powder is 200-325 mesh.
5. The method for preparing a TiSiCe target according to claim 1, characterized in that: In the step (3), the parameters of the compression molding are as follows: the pressure is 300-1500 tons; the density of the blank obtained by the compression molding is 56-70%; the blank is a round cake-shaped blank with a diameter of D=50-200 mm and a height of L=5-30 mm.
6. The method for preparing a TiSiCe target according to claim 1, characterized in that: The degassing treatment parameters are as follows: temperature of 400-600°C, degassing vacuum of 2×10 -2 -1×10 -3 Pa, time is 4-10h.
7. The method for preparing a TiSiCe target according to claim 1, characterized in that: The parameters of the hot isostatic pressing treatment are: treatment temperature of 900-1100° C., pressure of 110-140 MPa, and heat and pressure holding time of 2-6 hours.
8. The method for preparing a TiSiCe target according to claim 1, characterized in that: The parameters of the hot isostatic pressing treatment are: first, the sintering temperature is raised to 700-800°C for pre-sintering for 1-2 hours; then, the temperature is raised to 900-1100°C at a heating rate of 2-10°C / min, a pressure of 100-150MPa is applied, and the heat and pressure holding time is 2-6 hours.
9. The method for preparing a TiSiCe target according to claim 8, characterized in that: The parameters of the hot isostatic pressing treatment are: first, the sintering temperature is raised to 720-780°C for pre-sintering for 1-2 hours; then, the temperature is raised to 950-1050°C at a heating rate of 4-8°C / min, a pressure of 110-140MPa is applied, and the heat and pressure holding time is 3-5 hours.
10. A TiSiCe target material, characterized in that: The target is prepared by the method for preparing the TiSiCe target according to any one of claims 1 to 9.