Method for manufacturing titanium-silicon target material by utilizing recycled waste target

Abstract

The invention provides a method for manufacturing a titanium-silicon target material by utilizing a recycled waste target, which comprises the following steps of: firstly, preparing Ti5Si3 powder from the recycled waste target through the technological processes of primary sintering, acid pickling, crushing and powdering, powder mixing, isostatic cool pressing, secondary sintering and crushing and powdering, and then mixing the prepared Ti5Si3 powder with Ti powder, and carrying out vacuum hot degassing, hot isostatic pressing and machining to obtain a finished product titanium-silicon target material, wherein the titanium-silicon target material can be recycled for preparing a new target after being used. The prepared titanium-silicon target material only contains the Ti phase and the Ti5Si3 phase, the coating performance is excellent, meanwhile, the recycled waste target is used for preparing the Ti5Si3 powder, the technical barrier is broken through, the cost is reduced, and the titanium-silicon target material is suitable for batch production.

Description

Technical Field

[0001] This invention belongs to the field of tool coating and coating target preparation technology, and relates to a method for manufacturing titanium-silicon targets, and more particularly to a method for manufacturing titanium-silicon targets using recycled waste materials. Background Technology

[0002] Applying a high-hardness, wear-resistant coating to the surface of cutting tools can effectively resolve the contradiction between the tool's hardness, wear resistance, bending strength, and impact toughness. Tool coatings are often achieved through physical vapor deposition (PVD), which offers significant advantages such as low preparation temperature, fine structure, smooth surface, and thin coating. This process uses a target material as raw material; the atoms leave the target surface and enter the coating chamber. Inside the chamber, the atoms react with the introduced gas to generate nitrides, oxides, etc., which are ultimately deposited on the tool surface to form the coating.

[0003] TiSiN coatings possess numerous properties such as high hardness, good wear and corrosion resistance, good oxidation resistance, low coefficient of friction, and excellent thermal stability, making them a hot topic in the field of superhard coatings. The preparation of TiSiN coatings requires titanium-silicon sputtering targets. A commonly used titanium-silicon sputtering target ratio is Ti / Si x / (100-x)at%, where 50≤x<100. The most suitable titanium-silicon sputtering targets, in addition to meeting requirements for density, grain size, and uniformity, should contain only Ti and Ti5Si3 phases internally.

[0004] The preparation process of titanium-silicon sputtering targets is usually powder metallurgy. Using Ti powder and Ti5Si3 powder as raw materials to prepare titanium-silicon sputtering targets containing only the Ti and Ti5Si3 phases is the most convenient method. X Si 1-x Powder is usually obtained through a process of melting and ingot forming followed by crushing and powdering. However, due to its high melting point and instability, the Ti5Si3 phase is difficult to obtain through melting. Solid-solid reaction sintering can overcome the above technical barriers to prepare Ti5Si3 powder. Specifically, it involves promoting the full reaction and sintering of a Ti / Si 62.5 / 37.5 at% billet at high temperature to generate the Ti5Si3 phase, followed by crushing to prepare Ti5Si3 powder.

[0005] The solid-solid reaction sintering process for preparing Ti5Si3 powder typically uses Ti powder and Si as raw materials. After mixing them in a Ti / Si ratio of 62.5 / 37.5 at%, the mixture undergoes cold isostatic pressing, sintering, and crushing to obtain Ti5Si3 powder. However, the high cost of Ti powder in this process leads to an excessively high market price for Ti5Si3 powder, making it difficult for manufacturers to commercialize it on a large scale. To reduce production costs, some manufacturers use TiSi2 powder instead of Ti5Si3 powder to prepare titanium-silicon targets. The resulting targets have a complex phase composition and poor coating quality stability, making it difficult to meet the increasingly stringent requirements of coating manufacturers. Summary of the Invention

[0006] The purpose of this invention is to ensure the quality of titanium-silicon targets and reduce production costs. This invention proposes a method for preparing Ti5Si3 powder using recycled titanium-silicon waste targets, and then preparing titanium-silicon targets. This invention effectively reduces the production cost of targets and improves material utilization by establishing a target recycling mechanism, and is suitable for mass production.

[0007] The above-mentioned objective of this invention is mainly achieved through the following technical solution: a method for manufacturing titanium-silicon target materials using recycled waste targets, comprising:

[0008] The recycled titanium-silicon waste targets are sintered once and acid-washed to remove surface contaminants.

[0009] The acid-washed titanium-silicon waste target is crushed, powdered, and sieved. The sieved powder is then mixed with Si powder.

[0010] The obtained mixed powder is subjected to cold isostatic pressing to obtain a cold isostatic pressed compact;

[0011] The cold isostatic pressing billet is sintered twice, and the sintered billet is crushed, powdered, and sieved to obtain Ti5Si3 powder.

[0012] Ti5Si3 powder was mixed with Ti powder;

[0013] The mixed powder is loaded into a sleeve and vacuum thermally degassed. The degassed sleeve is then hot isostatically pressed.

[0014] Titanium-silicon sputtering targets are obtained by hot isostatic pressing of billets.

[0015] Preferably, the first sintering is vacuum sintering, with a temperature of 900–1300℃, a time of 6–10 h, and a vacuum degree ≤2×10⁻⁶. -3 Pa.

[0016] Preferably, the pickling solution is (1%–4%) HF + (25%–30%) HNO3, and the process is at room temperature for 15–30 minutes.

[0017] Preferably, the acid-washed titanium-silicon waste target is crushed and powdered by air jet milling, with Ar gas as the medium and a flow rate of 300-600 m / s; the powder is sieved, and the particle size of the powder used for mixing is D90≤75μm.

[0018] Preferably, the powder mixing process for mixing waste target sieved powder with Si powder and Ti5Si3 powder with Ti powder is Ar gas as the protective medium, with a ball-to-material ratio of 1:2 to 3:1 and a time of 4 to 10 hours.

[0019] Preferably, the Si powder laser particle size D90 ≤ 60 μm.

[0020] Preferably, the cold isostatic pressing process is carried out at a pressure of 120-300 MPa for 10-25 min; the secondary sintering is vacuum sintering, with a temperature of 1100-1500℃ for 8-15 h and a vacuum degree ≤2×10⁻⁶. -3 Pa.

[0021] Preferably, the secondary sintering billet is crushed and powdered by air jet milling, with Ar gas as the medium and a flow rate of 400-600 m / s; the powder is sieved, and the particle size of the powder used for mixing is D10≥25μm and D90≤150μm.

[0022] Preferably, the Ti powder has a laser particle size of D10 ≥ 20 μm and D90 ≤ 150 μm.

[0023] Preferably, the vacuum thermal degassing process is carried out at a temperature of 300–650°C for 4–8 hours, with a vacuum degree ≤2×10⁻⁶. -3 Pa; the hot isostatic pressing process is carried out at a temperature of 800-1000℃, a pressure of 100-150MPa, and a time of 2-5h.

[0024] The present invention also provides a titanium-silicon target material, which is prepared by the above-described method of manufacturing titanium-silicon target material using recycled waste targets.

[0025] Compared with the prior art, the present invention has at least the following beneficial effects:

[0026] In this invention, waste titanium-silicon sputtering targets are innovatively used as raw materials, establishing a recycling mechanism to achieve the preparation of Ti5Si3 powder and titanium-silicon sputtering targets. This not only breaks through technical barriers but also improves material utilization and reduces production costs. The invention involves a first sintering process on the recycled waste targets to improve their brittleness before crushing and powdering. Impurities are then removed through acid washing to ensure the purity of the target material. Ti5Si3 powder is successfully prepared through a second sintering process, and high-quality titanium-silicon sputtering targets are then prepared using hot isostatic pressing. This meets industry demands and enables mass production, showing broad application prospects. Attached Figure Description

[0027] Figure 1 This is a process flow diagram for the preparation of the titanium-silicon target material of the present invention;

[0028] Figure 2 The XRD pattern of the powder obtained by secondary sintering and crushing in this invention;

[0029] Figure 3 This is a typical microstructure diagram of the titanium-silicon target material of this invention. Detailed Implementation

[0030] To facilitate understanding of this invention, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments:

[0031] To reduce production costs, overcome the shortcomings of existing technologies, and enrich the manufacturing methods of titanium-silicon sputtering targets, this invention provides a method for manufacturing titanium-silicon sputtering targets using recycled waste targets. This method effectively improves material utilization, reduces manufacturing costs, and is suitable for mass production. The method for preparing titanium-silicon sputtering targets using recycled waste targets is as follows: Figure 1 As shown, it includes the following steps:

[0032] I. Waste Target Recycling and Pretreatment

[0033] This invention utilizes the composition of recycled titanium-silicon waste targets: Ti / Si x / (100-x)at%, where 50 ≤ x < 100. For example, it can be one or more of Ti / Si 95 / 5at%, Ti / Si 90 / 10at%, Ti / Si 85 / 15at%, Ti / Si 80 / 20at%, Ti / Si 75 / 25at%, and Ti / Si 70 / 30at%. Because the titanium-silicon waste targets are not brittle enough to be directly crushed and powdered, a primary sintering process is required to promote the diffusion reaction between Ti-Si atoms and improve the brittleness of the waste targets. The primary sintering process involves a temperature of 900–1300℃, a time of 6–10 h, and a vacuum degree ≤ 2 × 10⁻⁶. -3 Pa. Due to surface contamination during the coating and sintering process, waste titanium-silicon targets need to be acid-washed to remove surface contaminants before they can be used for crushing and powdering. The acid washing solution is (1%–4%) HF + (25%–30%) HNO3, and the process is carried out at room temperature for 15–30 minutes.

[0034] II. Preparation of Ti5Si3 Powder

[0035] This invention prepares Ti5Si3 powder from recycled titanium-silicon waste targets. The pretreated waste targets are crushed and pulverized using an air-jet mill with Ar gas as the medium at a flow rate of 300–600 m / s. To facilitate sufficient diffusion of Ti-Si atoms during subsequent secondary sintering, the powder is sieved after crushing, selecting powder with a laser particle size D90 ≤ 75 μm for subsequent mixing. The crushed powder is mixed with Si powder with a laser particle size D90 ≤ 60 μm at a ratio of Ti / Si 62.5 / 37.5 at%, using a three-dimensional mechanical mixing process with Ar gas as the protective medium, a ball-to-powder ratio of 1:2–3:1, and a mixing time of 4–10 h. The mixed powder is then placed in a rubber sleeve and cold isostatically pressed at a pressure of 120–300 MPa for 10–25 min. The cold isostatically pressed compact is then subjected to a secondary sintering process. The secondary sintering process is carried out at a temperature of 1100–1500℃ for 8–15 hours, with a vacuum degree ≤2×10⁻⁶. -3Pa. The secondary sintered billet is crushed and pulverized by air jet milling with Ar gas as the medium at a flow rate of 400–600 m / s. Ti5Si3 powder is finally obtained by sieving. The Ti5Si3 powder used to prepare titanium-silicon targets has a laser particle size D10 ≥ 25 μm and D90 ≤ 135 μm. The powder XRD pattern is shown in the attached figure. Figure 2 As shown.

[0036] III. Preparation of Titanium-Silicon Sputtering Targets

[0037] This invention prepares titanium-silicon target materials using Ti5Si3 powder and Ti powder prepared from waste targets. The titanium-silicon target material composition is Ti / Six / (100-x)at%, where 50≤x<100, for example, Ti / Si 95 / 5at%, Ti / Si 90 / 10at%, Ti / Si 85 / 15at%, Ti / Si 80 / 20at%, Ti / Si 75 / 25at%, Ti / Si 70 / 30at%, etc. The laser particle size of the Ti powder is D10≥20μm, D90≤150μm. The Ti5Si3 powder and Ti powder are mixed using Ar gas as the protective medium, with a ball-to-powder ratio of 1:2 to 3:1, for 4 to 10 hours. The mixed powder is then placed in a casing for vacuum thermal degassing at a temperature of 300 to 650℃ for 4 to 8 hours, with a vacuum degree ≤2×10⁻⁶. -3 Pa. The degassed casing is then subjected to hot isostatic pressing (HIP). The HIP process is performed at a temperature of 800–1000℃, a pressure of 100–150 MPa, and a time of 2–5 hours. The final machined product is a titanium-silicon target. The typical microstructure of the target is shown in the attached figure. Figure 3 As shown.

[0038] Example 1

[0039] This example provides a method for preparing a titanium-silicon target with a composition of Ti / Si 80 / 20 at%, the method comprising the following:

[0040] The recycled titanium-silicon targets used in this example have two compositions: Ti / Si 75 / 25at% and Ti / Si 90 / 10at%. The targets were heated at 1050℃ for 8 hours with a vacuum degree ≤2×10⁻⁶. -3Sintering was performed once under Pa conditions, followed by acid washing at room temperature for 15 min in a (3%) HF + (25%) HNO3 solution. Waste targets of two different compositions were crushed under an Ar gas flow rate of 450 m / s, and then sieved to obtain Ti / Si powder with a laser particle size of D90 = 46 μm and a composition of 75 / 25 at% and D90 = 57 μm, respectively, with a composition of 90 / 10 at% and D90 = 57 μm. These two powders and Si powder with a laser particle size of D90 = 49 μm were then three-dimensionally mixed with each other at a composition of 62.5 / 37.5 at% using Ar gas as the mixing medium, a ball-to-material ratio of 1:2, and a mixing time of 6 h. The mixed powder was then placed in a rubber sleeve and subjected to cold isostatic pressing at a pressure of 220 MPa for 10 min. The cold isostatically pressed blank was then subjected to a temperature of 1400℃ for 12 h with a vacuum degree ≤ 2 × 10⁻⁶. -3 Secondary sintering was performed under Pa conditions. The secondary sintered billet was crushed under an Ar gas flow rate of 410 m / s and sieved to obtain Ti5Si3 powder with laser particle sizes D10 = 36 μm and D90 = 125 μm. The Ti5Si3 powder and Ti powder with laser particle sizes D10 = 23 μm and D90 = 144 μm were three-dimensionally mixed at a Ti / Si ratio of 80 / 20 at%, using Ar gas as the mixing medium, a ball-to-powder ratio of 1:1, and a mixing time of 4 h. The mixed powder was then placed in a casing for vacuum thermal degassing at a temperature of 450 °C for 5 h, with a vacuum degree ≤ 2 × 10⁻⁶. -3 Pa. The cladding was hot isostatically pressed at a temperature of 870℃, a pressure of 135MPa, and a time of 3h, and finally machined to obtain a titanium-silicon sputtering target with a composition of Ti / Si 80 / 20at%.

[0041] Example 2

[0042] This example provides a method for preparing a titanium-silicon target with a composition of Ti / Si 85 / 15 at%, the method comprising the following:

[0043] The recycled titanium-silicon target used in this example has a composition of Ti / Si 80 / 20 at%. The target was heated at 1100℃ for 6 hours with a vacuum degree ≤2×10⁻⁶. -3The target was sintered once under Pa conditions, and then acid-washed for 15 min at room temperature in a (3%) HF + (30%) HNO3 solution. The waste target was crushed under an Ar gas flow rate of 350 m / s, and then sieved to obtain a Ti / Si powder with a laser particle size of D90 = 61 and a composition of 75 / 25 at%. The above powder and Si powder with a laser particle size of D90 = 42 μm were mixed in three dimensions with a Ti / Si composition of 62.5 / 27.5 at%, using Ar gas as the mixing medium, a ball-to-material ratio of 1:2, and a mixing time of 6 h. The mixed powder was then placed in a rubber sleeve and subjected to cold isostatic pressing at a pressure of 250 MPa for 15 min. The cold isostatic pressed blank was then subjected to a temperature of 1350℃ for 14 h and a vacuum degree of ≤2×10 -3 Secondary sintering was performed under Ar gas flow conditions. The sintered billet was crushed under Ar gas flow at a velocity of 510 m / s and sieved to obtain Ti5Si3 powder with laser particle sizes D10 = 28 μm and D90 = 131 μm. The Ti5Si3 powder and Ti powder with laser particle sizes D10 = 26 μm and D90 = 131 μm were three-dimensionally mixed at a Ti / Si ratio of 85 / 15 at%, using Ar gas as the mixing medium, a ball-to-powder ratio of 1:2, and a mixing time of 6 h. The mixed powder was then placed in a package for vacuum thermal degassing at a temperature of 400 °C for 3 h, with a vacuum degree ≤ 2 × 10⁻⁶. -3 Pa. The cladding was hot isostatically pressed at 930℃, 150MPa, and 2.5h, and finally machined to obtain a titanium-silicon sputtering target with a composition of Ti / Si 85 / 15at%.

[0044] Example 3

[0045] This example provides a method for preparing a titanium-silicon target with a composition of Ti / Si 90 / 10 at%, the method comprising the following:

[0046] The recycled titanium-silicon target used in this example has a composition of Ti / Si 95 / 5at%. The target was heated at 1300℃ for 3 hours under a vacuum degree ≤2×10⁻⁶. -3 The target was sintered once under Pa conditions, and then acid-washed for 10 min at room temperature in a (4%) HF + (25%) HNO3 solution. The waste target was crushed under an Ar gas flow rate of 455 m / s, and then sieved to obtain a Ti / Si 90 / 10 at% powder with a laser particle size of D90 = 47 μm. The above powder and Si powder with a laser particle size of D90 = 53 μm were mixed in three dimensions with a Ti / Si 62.5 / 27.5 at% composition. The mixing medium was Ar gas, the ball-to-material ratio was 1:2, and the mixing time was 5 h. The mixed powder was then placed in a rubber sleeve and subjected to cold isostatic pressing at a pressure of 180 MPa for 25 min. The cold isostatic pressing blank was then subjected to a temperature of 1500℃ for 15 min and a vacuum degree ≤2×10 -3Secondary sintering was performed under Pa conditions. The sintered billet was crushed under an Ar gas flow rate of 480 m / s and sieved to obtain Ti5Si3 powder with laser particle sizes D10 = 21 μm and D90 = 134 μm. The Ti5Si3 powder and Ti powder with laser particle sizes D10 = 29 μm and D90 = 132 μm were three-dimensionally mixed at a Ti / Si ratio of 90 / 10 at%, using Ar gas as the mixing medium, a ball-to-powder ratio of 1:1, and a mixing time of 6 h. The mixed powder was then placed in a package for vacuum thermal degassing at a temperature of 440℃ for 3.5 h, with a vacuum degree ≤ 2 × 10⁻⁶. -3 Pa. The cladding was hot isostatically pressed at 890℃, 150MPa, and 3h, and finally machined to obtain a titanium-silicon sputtering target with a composition of Ti / Si 90 / 10at%.

[0047] The above description is only the best specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the protection scope of the present invention.

[0048] The contents not described in detail in this specification are common knowledge to those skilled in the art.

Claims

1. A method for manufacturing titanium-silicon target materials using recycled waste targets, characterized in that... include: The recycled titanium-silicon waste targets are sintered once and acid-washed to remove surface contaminants. The acid-washed titanium-silicon waste target is crushed, powdered, and sieved. The sieved powder is then mixed with Si powder. The obtained mixed powder is subjected to cold isostatic pressing to obtain a cold isostatic pressed compact; The cold isostatic pressing billet is sintered twice, and the sintered billet is crushed, powdered, and sieved to obtain Ti5Si3 powder. Ti5Si3 powder was mixed with Ti powder; The mixed powder is loaded into a sleeve and vacuum thermally degassed. The degassed sleeve is then hot isostatically pressed. Titanium-silicon sputtering targets are obtained by hot isostatic pressing of billets.

2. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The first sintering process is vacuum sintering, with a temperature of 900–1300℃, a time of 6–10 hours, and a vacuum degree of ≤2×10⁻⁶. -3 Pa.

3. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The pickling solution is (1%–4%) HF + (25%–30%) HNO3, and the process is at room temperature for 15–30 minutes.

4. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The acid-washed titanium-silicon waste target was crushed and ground into powder by air jet milling with Ar gas as the medium and a flow rate of 300-600 m / s. The powder was then sieved, and the particle size of the powder used for mixing was D90≤75μm.

5. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The powder mixing process for mixing waste target sieved powder with Si powder and Ti5Si3 powder with Ti powder is carried out with Ar gas as the protective medium, the ball-to-material ratio is 1:2 to 3:1, and the time is 4 to 10 hours.

6. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The Si powder laser particle size D90 ≤ 60 μm.

7. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The cold isostatic pressing process involves a pressure of 120-300 MPa and a time of 10-25 min; the secondary sintering is vacuum sintering, with a temperature of 1100-1500℃, a time of 8-15 h, and a vacuum degree ≤2×10⁻⁶. -3 Pa.

8. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The secondary sintering billet is crushed and powdered by air jet milling, with Ar gas as the medium and a flow rate of 400-600 m / s; the powder is sieved, and the particle size of the powder used for mixing is D10≥25μm and D90≤150μm.

9. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The Ti powder has a laser particle size of D10 ≥ 20 μm and D90 ≤ 150 μm.

10. The method for manufacturing titanium-silicon target materials using recycled waste targets according to claim 1, characterized in that, The vacuum thermal degassing process involves a temperature of 300–650℃, a time of 4–8 hours, and a vacuum degree ≤2×10⁻⁶. -3 Pa; the hot isostatic pressing process is carried out at a temperature of 800-1000℃, a pressure of 100-150MPa, and a time of 2-5h.

11. A titanium-silicon target material, characterized in that... It is prepared by the method described in any one of claims 1-10.

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