WO2021046928A1 - Large pipe-diameter ni-v rotary target material containing trace elements and preparation method therefor - Google Patents

Large pipe-diameter ni-v rotary target material containing trace elements and preparation method therefor Download PDF

Info

Publication number
WO2021046928A1
WO2021046928A1 PCT/CN2019/108213 CN2019108213W WO2021046928A1 WO 2021046928 A1 WO2021046928 A1 WO 2021046928A1 CN 2019108213 W CN2019108213 W CN 2019108213W WO 2021046928 A1 WO2021046928 A1 WO 2021046928A1
Authority
WO
WIPO (PCT)
Prior art keywords
diameter
trace elements
rotating target
containing trace
temperature
Prior art date
Application number
PCT/CN2019/108213
Other languages
French (fr)
Chinese (zh)
Inventor
吴宇宁
卿海标
周其刚
Original Assignee
南京达迈科技实业有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南京达迈科技实业有限公司 filed Critical 南京达迈科技实业有限公司
Publication of WO2021046928A1 publication Critical patent/WO2021046928A1/en

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/023Alloys based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/3407Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering

Definitions

  • the invention relates to a magnetron sputtering target material and its preparation, in particular to a large-diameter Ni-V rotating target material containing trace elements and a preparation method thereof.
  • Magnetron sputtering coating technology which occupies an important position in the coating field, is also being further improved.
  • Target materials are the most critical basic consumables in the magnetron sputtering coating process. Only the most suitable target materials with high utilization rate, high quality and high quality can fully meet the demand and drive the development of science and technology.
  • the magnetron sputtering coating technology of nickel-vanadium targets has a relatively large market in the domestic solar field, but most of the nickel-vanadium targets are flat targets, and rotating targets only account for a small part.
  • the main reason is that the current domestic technology can only mass-produce some small-diameter nickel-vanadium rotating targets with a diameter of less than 100mm.
  • Large-diameter nickel-vanadium rotating targets with a diameter of more than 100mm are produced in the traditional pipe-piercing and rolling process. It requires multiple reaming and mold replacement, and the cost is quite high, and defects such as cracks, inclusions and eccentricity often occur, the scrap rate is extremely high, and the cost is too high.
  • the utilization rate of the rotating target can be as high as 70%, especially the utilization rate of the large-diameter nickel-vanadium rotating target can be as high as 80% and above, and the utilization rate of the large-diameter nickel-vanadium rotating target can be as high as 80% and above.
  • the nickel-vanadium rotating target can also be bound by brazing material to meet more market demands. Therefore, it is imperative to find a method for preparing a large-diameter nickel-vanadium rotating target with suitable composition, simple production process, high yield, high precision, and low cost.
  • One of the objectives of the present invention is to provide a large-diameter Ni-V rotating target containing trace elements, which uses the addition of trace elements C, B, Ti, and Mg to improve the performance of the rotating target;
  • the second purpose is to provide a method for preparing a large-diameter Ni-V rotating target containing trace elements, which can overcome the problems of nickel-vanadium tube cracking, inclusions, defects, eccentricity, and processing difficulties. Vanadium rotating target.
  • the large-diameter Ni-V rotating target containing trace elements of the present invention includes the following raw material components in terms of mass percentage: C 0.01-0.05%, B 0.01-0.08%, Ti 0.001-0.006%, Mg 0.01 ⁇ 0.05%, V 6 ⁇ 8%, the balance Ni and unavoidable impurities. Among them, the inevitable impurities such as Al, Fe and so on.
  • the present invention also provides a method for preparing the large-diameter Ni-V rotating target material containing trace elements.
  • the preparation steps mainly include raw material preparation, vacuum melting, hot forging, machining, hot extrusion, pickling treatment, Solution treatment, cold rolling or boring, annealing treatment, machining or binding; the specific process is:
  • Vacuum smelting prepare raw materials before smelting, graphite with purity ⁇ 99.9, boron particles with purity ⁇ 99.9, metallic titanium with purity ⁇ 99.9, metallic magnesium with purity ⁇ 99.9, metallic vanadium with purity ⁇ 99.9, electrolytic nickel with purity ⁇ 99.96; Then, the raw materials are mixed with electrolytic nickel, metallic vanadium, and graphite according to the content of the above-mentioned components, and then smelted in a vacuum at 1400-1550°C for 70-90 minutes, and then titanium, magnesium, and boron are added for refining for 10-20 minutes, and then under a protective atmosphere The ingot is obtained by casting; wherein the vacuum degree is kept at less than 4 Pa during the whole smelting process; the protective atmosphere during casting can be argon;
  • Hot forging rough machining of the ingot before hot forging.
  • the lathe can be used to remove the surface oxide scale and some defects, and the riser can be cut to obtain a round truncated cone-shaped bright ingot, which is carefully ground to remove microcracks, etc.;
  • the ingot is hot forged, the ingot is heated to 1090 ⁇ 1120°C, and after holding for 20 ⁇ 50min, forging is carried out, the forging temperature is 1090 ⁇ 1120°C, and the final forging temperature is 990 ⁇ 1050°C; the ingot is repeatedly roughed and then drawn Long, the deformation is greater than 50%; the deformation of the drawing here is greater than 50%, which is compared with the forging rod after the pier is thick.
  • Hot extrusion The alloy cylinder obtained in step (3) is heated by induction heating at a heating temperature of 990 to 1130°C; then the hole is expanded at a speed of 150 to 220 mm/s; and then a secondary induction is used Heat treatment, the heating temperature is 1000 ⁇ 1150°C, and the hot extruder is used for extrusion, and the extrusion speed is 120 ⁇ 150mm/s;
  • Pickling treatment the waste pipe is pickled to remove defects such as surface pits; the pickling treatment can adopt the common pickling process in the prior art.
  • Solution treatment The acid-washed waste pipe is solid-solution treated to obtain a single-phase austenite structure at room temperature, so that the material has the best corrosion resistance, high plasticity, good formability, and can refine the waste pipe The grain structure.
  • the surface-treated waste tube is rolled or bored with high precision to obtain a bright tube with an inner hole size tolerance of ⁇ 0.2mm.
  • Annealing treatment the bright tube is annealed, the annealing temperature is 840 ⁇ 870°C, and the heat preservation is 80 ⁇ 90min.
  • the bright tube is processed to the overall rotating target of the required size, or processed to a certain size, and then the binding rotating target of the required size is made by binding.
  • the electrolytic nickel is baked at 580-620° C. for 5-8 hours. Long-term baking can effectively remove most of the hydrogen contained in electrolytic nickel.
  • titanium, magnesium, and boron are added in the vacuum melting process by using nickel foil to enclose the titanium, magnesium, and boron; during the vacuum melting process, the micro-alloying elements metal titanium and metal magnesium are added in the above-mentioned manner.
  • Boron particles can avoid boiling and sputtering of molten steel caused by direct addition.
  • the deformation of the pier thickness in the step (2) is greater than 50%.
  • the pier roughening and drawing length are repeated, the pier rough deformation is more than 50%, and the coarse grain structure is fully broken, thereby increasing the extrusion yield.
  • the diameter of the central through hole in the step (3) is 20-40 mm, and the taper of the tapered hole is 20°-40°.
  • the central through hole and tapered hole here facilitate the reaming head to correspond to the alloy, and prevent eccentricity caused by reaming.
  • the temperature of the secondary induction heating is 10-20°C higher than the temperature of the previous induction heating. Enlarging the hole after induction heating, and then extruding after the second induction heating; and the temperature of the second induction heating is slightly higher by 10-20°C, which can prevent defects or scrapping in the extrusion process caused by the temperature drop during the extrusion preparation process .
  • the waste pipe is heated to 950-1000° C. for heat preservation, and then water quenched.
  • a solution treatment at a lower temperature and rapid cooling are adopted to obtain a waste tube with fine grains and improve the plasticity and corrosion resistance of the material.
  • annealing treatment annealing the bright tube, the annealing temperature is 840-870°C, and the heat preservation is 80-90 min.
  • the present invention optimizes the composition by adding trace elements C, B, Ti, Mg in the high vacuum smelting process, reduces the content of oxygen, sulfur, etc., and can inhibit the initiation of cracks, and improve the grain boundary bonding force of the target material. Strength, and refine the grains, thereby increasing the yield.
  • adding B element, B segregates on the grain boundary or vacancy type defects, improves the grain boundary bonding force, forms fine M 3 B 2 type borides, and reduces the formation of ⁇ phase in the TCP phase formed by the combination of impurity elements , Inhibit the generation of cracks; due to the relatively high viscosity of nickel and vanadium during the smelting process, it is difficult to feed during the solidification process.
  • element B can improve the feeding of the alloy in the later stage of solidification and reduce the generation of microscopic shrinkage; adding Ti Since the impurity element Al and Ni in the alloy form a Ni 3 Al intermetallic compound, the addition of Ti can replace the Al atom in Ni 3 Al to form a Ni 3 (Al, Ti) type strengthening phase, thereby further improving the alloy’s Strength; adding C and Mg elements, mainly for deoxidation, desulfurization, and purification of molten metal, and will volatilize at high temperatures, and does not affect the purity of molten metal. Thereby reducing the content of interstitial gases such as hydrogen, oxygen and nitrogen in the nickel-vanadium alloy, while removing harmful sulfur impurities and refining crystal grains. Thereby improving the quality of the alloy and optimizing the alloy composition.
  • interstitial gases such as hydrogen, oxygen and nitrogen in the nickel-vanadium alloy
  • the large-diameter Ni-V rotating target containing trace elements in the present invention is very critical in hot forging and hot extrusion temperature during the hot working process.
  • the nickel-based alloy Ni93V7
  • the research method of thermal processing map of dynamic material model has now become the most effective method to study the workability of metal materials and control the deformed structure.
  • a thermal simulation single-pass compression experiment was performed on a nickel-based alloy (Ni93V7).
  • three sets of rates were set, namely 0.001s -1 , 0.1s -1 , and 1s -1 , and each set of rates set four temperatures: 1000 °C, 1050°C, 1100°C, 1150°C.
  • the thermal deformation behavior of the new material is systematically explored.
  • the thermal processing diagram of the nickel-based alloy is drawn. Based on the flow stress curve of the nickel-vanadium alloy, the power dissipation of the alloy based on the dynamic material model is established Figure. Because there is no instability phenomenon, the generation of the thermal processing map does not need to superimpose the power dissipation map and the rheological instability map.
  • the power dissipation map is the final thermal processing map.
  • the best hot working parameters of nickel-vanadium alloy are in the interval of 1090 ⁇ 1120°C, 1s -1.
  • the two key technical links of the present invention are the ratio design of the Ni-V rotating target material and the control of the process conditions, which are complementary to each other.
  • Ni-V rotating targets have been successfully prepared through suitable component ratios and optimized preparation methods.
  • the entire rotating target can be made or bound with the rotating target to meet more requirements. More usage needs.
  • the present invention adds a small amount of alloying elements C, B, Ti, Mg to optimize the composition, reduces the content of oxygen, sulfur, etc., and can inhibit the initiation of cracks, and improve the grain boundary bonding of the target material Strength, strength, and grain refinement can improve the feeding of the alloy in the later stage of solidification, reduce the generation of microscopic shrinkage, and increase the yield.
  • Electrolytic nickel can effectively remove part of the hydrogen contained in electrolytic nickel through long-term high-temperature baking; through repeated thickening and elongation forging process, hole expansion after induction heating, and extrusion and finish rolling after secondary induction heating Or boring and other technological processes can improve the concentricity and yield rate of the rotating target;
  • the present invention does not need to add rare earth elements, and successfully prepares a large diameter Ni-V rotating target with low cost and excellent performance through the optimization of the composition and the control of the process conditions;
  • the present invention draws the hot processing diagram of the nickel-based alloy, obtains the hot forging and hot extrusion optimization parameters of the rotating target, and greatly improves the finished product of the large-diameter Ni-V rotating target rate;
  • the preparation method of the present invention can overcome the problems of nickel-vanadium tube cracking, inclusions, defects, eccentricity, and processing difficulties, etc., a large-diameter nickel-vanadium rotating target material;
  • the present invention can achieve 70%-80% utilization rate by manufacturing an integral rotating target or a bound rotating target, which can not only meet more market demands and special demands, but also increase the utilization rate of materials and reduce costs.
  • Figure 1 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 1;
  • Example 2 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 2;
  • Example 3 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 3;
  • Example 4 is a 100 times metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 4;
  • Example 5 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 5;
  • Fig. 6 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 6;
  • Figure 7 is a low-magnification photo of the comparative example during the preparation of Ni-V rotating target
  • Figure 8 is a 100-fold metallographic picture of the target of the comparative example.
  • the reagents and materials used to prepare the large-diameter Ni-V rotating target in the following examples are all commercially available.
  • composition and content of the large-diameter Ni-V rotating target containing trace elements are as follows: C 0.02%, B 0.03%, Ti 0.005%, Mg 0.01%, V 6% and The balance Ni and unavoidable impurities.
  • the preparation method of the large diameter Ni-V rotating target includes the following steps:
  • Vacuum melting prepare raw material graphite, boron particles, metallic titanium, metallic magnesium, metallic vanadium, electrolytic nickel, among which the purity of raw materials is 99.9% graphite, 99.9% boron particles, 99.9% metallic titanium, 99.9% Metal magnesium, 99.9% metallic vanadium, 99.96% electrolytic nickel;
  • the surface oil stains and oxides of electrolytic nickel and metal vanadium are cleaned and dried and weighed. Then, the electrolytic nickel is baked at 600°C for 6 hours; then the raw materials are prepared according to the content of the above components.
  • the electrolytic nickel, metal vanadium, Graphite is put into a vacuum melting crucible and smelted with electricity. The melting temperature is 1500°C, and the melting time is 80 minutes. Then, the metal titanium, metal magnesium and boron particles wrapped in nickel foil are added successively, and then refined for 15 minutes.
  • the vacuum degree during the entire melting process Less than 4Pa; casting is performed after smelting, and argon gas 4Mpa is passed in a vacuum state before casting, and the casting is performed under protective atmosphere conditions, and the ingot is demolded after 40 minutes of casting.
  • the first machining Use a lathe to remove the oxide scale and some defects on the surface of the ingot, cut off the riser to obtain a round truncated cone-shaped bright ingot, and carefully grind to remove microcracks, etc.;
  • Hot forging heat the machined ingot to 1100°C, hold for 30 minutes, and then perform forging.
  • the forging temperature is 1100°C and the final forging temperature is 1000°C; the ingot is repeatedly thickened and thickened.
  • the amount of deformation is 60%, and then the drawing is carried out, and the drawing deformation is 60%; the drawing deformation here is compared with the forging rod after the pier is thick; the final forging is Forging rod
  • Second machining remove the oxide scale on the surface of the cylindrical forging rod, and process both ends of the forging rod to be flat, ensuring that the end face is perpendicular to the cylindrical surface, and after machining, it will be a cylinder with a diameter of 300 ⁇ 3 mm and a length greater than 500 mm. Processed a central through hole with a diameter of 30mm, and processed a tapered hole with a 20° taper at one end to obtain an alloy cylinder;
  • Hot extrusion The alloy cylinder is heated by induction heating at a heating temperature of 1000°C, and then the hole is expanded by a reaming head at a reaming speed of 200mm/s, and then subjected to secondary induction heating at a heating temperature of 1020. °C, and then use a 6500-ton hot extruder for extrusion at a speed of 120mm/s to obtain a waste pipe with an outer diameter of 170-200mm, an inner diameter of 130-160mm, and a length of 2500-4500mm;
  • Annealing treatment under the condition of annealing temperature of 850°C, annealing holding time is 80min for annealing treatment;
  • the bright tube is processed to the overall rotating target of the required size, or processed to a certain size, and then the binding rotating target of the required size is made by binding.
  • the metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out.
  • the metallographic picture under 100 times is shown in Figure 1. It can be seen that there are fine precipitates dispersed at the grain boundary, thus Play a strengthening effect, the grain distribution is uniform, and the average grain size is 47-63 ⁇ m.
  • the composition and content of the large-diameter Ni-V rotating target are as follows: C 0.03%, B 0.01%, Ti 0.003%, Mg 0.03%, V 7% and the balance Ni and Inevitable impurities.
  • the preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
  • step (1) the electrolytic nickel is baked at 580°C for 5 hours; the melting temperature is 1450°C, the melting time is 70 minutes, and the refining time is 10 minutes;
  • step (3) the ingot is heated to 1090°C and held for 20 minutes before forging.
  • the forging temperature is 1090°C and the final forging temperature is 1000°C;
  • the deformation of the pier thickness is 55%, and the deformation after drawing is 55%;
  • step (4) a central through hole with a diameter of 20mm is machined, and one end is machined into a tapered hole with a 30° taper;
  • step (5) the induction heating temperature is 1100°C, and the hole expanding speed is 180mm/s; the second induction heating temperature is 1110°C, and the extrusion speed is 130mm/s;
  • step (7) the solution treatment is heated to 980°C;
  • step (9) the annealing temperature is 840° C., and the annealing holding time is 85 min.
  • composition and content of the large-diameter Ni-V rotating target in this embodiment are as follows in terms of mass percentage: C 0.05%, B 0.08%, Ti 0.001%, Mg 0.05%, V 8%, and the balance Ni and Inevitable impurities.
  • the preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
  • step (1) the electrolytic nickel is baked at 610°C for 8 hours; the melting temperature is 1400°C, the melting time is 90 minutes, and the refining time is 20 minutes;
  • step (3) the ingot is heated to 1110°C and kept for 40 minutes before forging.
  • the forging temperature is 1110°C and the final forging temperature is 990°C; the deformation of the upset thickness is 65%;
  • step (4) a central through hole with a diameter of 30mm is machined, and a tapered hole with a 40° taper is machined at one end;
  • step (5) the induction heating temperature is 990°C, and the hole expanding speed is 150mm/s; the second induction heating temperature is 1000°C, and the extrusion speed is 140mm/s;
  • step (7) the solution treatment is heated to 970°C;
  • step (9) the annealing temperature is 860°C, and the annealing holding time is 90 min.
  • the metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out.
  • the metallographic picture at 100 times is shown in Figure 3. It can be seen that a small amount of fine precipitates are distributed at the grain boundaries, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 45-73 ⁇ m.
  • composition and content of the large-diameter Ni-V rotating target in this embodiment are as follows in terms of mass percentage: C 0.03%, B 0.05%, Ti 0.002%, Mg 0.04%, V 6% and the balance Ni and Inevitable impurities.
  • the preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
  • step (1) the electrolytic nickel is baked at 620°C for 7 hours; the smelting temperature is 1550°C, and the smelting time is 70min;
  • step (3) the ingot is heated to 1120°C and held for 50 minutes before forging.
  • the forging temperature is 1120°C and the final forging temperature is 1050°C; the deformation of the upset thickness is 55%;
  • step (4) a central through hole with a diameter of 40mm is machined, and a tapered hole with a 40° taper is machined at one end;
  • step (5) the induction heating temperature is 1050°C, and the hole expanding speed is 200mm/s; the second induction heating temperature is 1060°C, and the extrusion speed is 150mm/s;
  • step (7) the solution treatment is heated to 1000°C;
  • step (9) the annealing temperature is 870°C, and the annealing holding time is 90 minutes.
  • the metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out.
  • the metallographic picture at 100 times is shown in Figure 4. It can be seen that there are fine precipitates dispersed at the grain boundary, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 47-80 ⁇ m.
  • composition and content of the large-diameter Ni-V rotating target are as follows in terms of mass percentage: C 0.04%, B 0.06%, Ti 0.006%, Mg 0.02%, V 7%, and the balance Ni and Inevitable impurities.
  • the preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
  • step (1) the electrolytic nickel is baked at 590°C for 6 hours;
  • step (4) a central through hole with a diameter of 20mm is machined, and a tapered hole with a 40° taper is machined at one end;
  • step (5) the induction heating temperature is 1130°C, and the reaming speed is 220mm/s; the second induction heating temperature is 1150°C, and the extrusion speed is 130mm/s;
  • step (7) the solution treatment is heated to 960°C;
  • the metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out.
  • the metallographic picture at 100 times is shown in Figure 5. It can be seen that there are fine precipitates dispersed in the grain boundary, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 40-54 ⁇ m.
  • composition and content of the large-diameter Ni-V rotating target are as follows in terms of mass percentage: C 0.01%, B 0.02%, Ti 0.002%, Mg 0.01%, V 8%, and the balance Ni and Inevitable impurities.
  • the preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
  • step (1) the electrolytic nickel is baked at 590°C for 6 hours;
  • step (4) a central through hole with a diameter of 20mm is machined, and a tapered hole with a 40° taper is machined at one end;
  • step (5) the induction heating temperature is 1120°C, and the reaming speed is 160mm/s; the second induction heating temperature is 1140°C, and the extrusion speed is 125mm/s;
  • step (7) the solution treatment is heated to 1000°C.
  • the metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out.
  • the metallographic picture at 100 times is shown in Figure 6. It can be seen that a small amount of fine precipitates are distributed at the grain boundaries, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 45-69 ⁇ m.
  • This comparative example is basically the same as Example 1, except that:
  • step (3) the ingot is heated to 1150°C, and after holding for 50 minutes, forging is performed, the opening forging temperature is 1150°C, and the final forging temperature is 1000°C;
  • step (5) the induction heating temperature is 1140°C; the second induction heating temperature is 1160°C.
  • the Ni-V target material of this comparative example was severely cracked after hot extrusion, and obvious cracks can be seen; from Figure 8, it can be seen that the grains are relatively coarse.
  • the grain size is between 80-100 ⁇ m, the inclusions at the grain boundary are coarse, and the grain boundary is damaged; therefore, the appropriate hot forging temperature and hot extrusion temperature are very important.

Abstract

Disclosed are a large pipe-diameter Ni-V rotary target material containing trace elements and a preparation method therefor. The rotary target material comprises the following components in mass percentages: 0.01-0.05% of C, 0.01-0.08% of B, 0.001-0.006% of Ti, 0.01-0.05% of Mg, 6-8% of V, and the balance being Ni and inevitable impurities. The preparation steps successively use vacuum melting, hot forging, machining, hot squeezing, an acid pickling treatment, a solution treatment, cold rolling or boring, an annealing treatment, and machining or binding. On the basis of Ni-V, the present invention optimizes the ingredients by adding trace elements C, B, Ti and Mg, and decreases the content of oxygen, sulfur, etc., and the present invention can inhibit the creation of cracks, improves the grain boundary binding force and strength of the target material, and refines the crystal grains, thereby improving the yield; furthermore, the invention reduces the rejection rate by optimizing the hot processing parameters.

Description

一种含微量元素的大管径Ni-V旋转靶材及其制备方法Large-diameter Ni-V rotating target material containing trace elements and preparation method thereof 技术领域Technical field
本发明涉及磁控溅射靶材及其制备,特别是涉及一种含微量元素的大管径Ni-V旋转靶材及其制备方法。The invention relates to a magnetron sputtering target material and its preparation, in particular to a large-diameter Ni-V rotating target material containing trace elements and a preparation method thereof.
背景技术Background technique
随着科学技术的发展,镀膜技术的发展也日益完善,在镀膜领域占有重要位置的磁控溅射镀膜技术也在进一步完善,而靶材作为磁控溅射镀膜过程中最为关键的基本耗材,只有高利用率、高质量、最合适的靶材才能充分满足需求,带动科技的发展。With the development of science and technology, the development of coating technology is becoming more and more perfect. Magnetron sputtering coating technology, which occupies an important position in the coating field, is also being further improved. Target materials are the most critical basic consumables in the magnetron sputtering coating process. Only the most suitable target materials with high utilization rate, high quality and high quality can fully meet the demand and drive the development of science and technology.
目前,镍钒靶材磁控溅射镀膜技术在国内太阳能领域的使用有比较大的市场,但是镍钒靶材大部分为平面靶材,旋转靶材只占很少的一部分。主要原因是国内现有技术只能批量生产一些直径小于100mm的小管径的镍钒旋转靶材,超过100mm的大管径镍钒旋转靶材制作在传统的穿管、轧管工艺过程中,需要多次扩孔与更换模具,成本相当大,而且常出现开裂、夹杂物及偏心等缺陷,报废率极高,成本过大。相较于利用率只有30%的平面靶材而言,旋转靶材的利用率可以高达70%,尤其大管径的镍钒旋转靶材利用率可以高达80%及以上,且大管径的镍钒旋转靶材还能通过钎焊料进行绑定,从而满足更多的市场需求。因此,寻求一种成分合适、生产工艺简单、成材率高、精度高、成本较低的大管径镍钒旋转靶材的制备方法势在必行。At present, the magnetron sputtering coating technology of nickel-vanadium targets has a relatively large market in the domestic solar field, but most of the nickel-vanadium targets are flat targets, and rotating targets only account for a small part. The main reason is that the current domestic technology can only mass-produce some small-diameter nickel-vanadium rotating targets with a diameter of less than 100mm. Large-diameter nickel-vanadium rotating targets with a diameter of more than 100mm are produced in the traditional pipe-piercing and rolling process. It requires multiple reaming and mold replacement, and the cost is quite high, and defects such as cracks, inclusions and eccentricity often occur, the scrap rate is extremely high, and the cost is too high. Compared with the plane target with a utilization rate of only 30%, the utilization rate of the rotating target can be as high as 70%, especially the utilization rate of the large-diameter nickel-vanadium rotating target can be as high as 80% and above, and the utilization rate of the large-diameter nickel-vanadium rotating target can be as high as 80% and above. The nickel-vanadium rotating target can also be bound by brazing material to meet more market demands. Therefore, it is imperative to find a method for preparing a large-diameter nickel-vanadium rotating target with suitable composition, simple production process, high yield, high precision, and low cost.
发明内容Summary of the invention
发明目的:本发明的目的之一是提供一种含微量元素的大管径Ni-V旋转靶材,利用微量元素C、B、Ti、Mg的添加,提高旋转靶材的性能;本发明的目的之二是提供一种含微量元素的大管径Ni-V旋转靶材的制备方法,制备过程中能够克服镍钒管开裂、夹杂物、缺陷、偏心及加工困难等问题的大管径镍钒旋转靶材。Objective of the invention: One of the objectives of the present invention is to provide a large-diameter Ni-V rotating target containing trace elements, which uses the addition of trace elements C, B, Ti, and Mg to improve the performance of the rotating target; The second purpose is to provide a method for preparing a large-diameter Ni-V rotating target containing trace elements, which can overcome the problems of nickel-vanadium tube cracking, inclusions, defects, eccentricity, and processing difficulties. Vanadium rotating target.
技术方案:本发明的含微量元素的大管径Ni-V旋转靶材,包括按质量百分比计的如下原料组分:C 0.01~0.05%,B 0.01~0.08%,Ti 0.001~0.006%,Mg 0.01~0.05%,V 6~8%以及余量Ni和不可避免的杂质。其中不可避免的杂质如Al、Fe等。Technical solution: The large-diameter Ni-V rotating target containing trace elements of the present invention includes the following raw material components in terms of mass percentage: C 0.01-0.05%, B 0.01-0.08%, Ti 0.001-0.006%, Mg 0.01~0.05%, V 6~8%, the balance Ni and unavoidable impurities. Among them, the inevitable impurities such as Al, Fe and so on.
本发明还提供了一种所述含微量元素的大管径Ni-V旋转靶材的制备方法,制备步骤主要包括原料准备、真空熔炼、热锻、机加工、热挤压、酸洗处理、固溶处理、冷轧或镗孔、退火处理、机加工或绑定;具体过程为:The present invention also provides a method for preparing the large-diameter Ni-V rotating target material containing trace elements. The preparation steps mainly include raw material preparation, vacuum melting, hot forging, machining, hot extrusion, pickling treatment, Solution treatment, cold rolling or boring, annealing treatment, machining or binding; the specific process is:
(1)真空熔炼:熔炼前准备原料,纯度≥99.9的石墨、纯度≥99.9硼粒、纯度≥99.9金属钛、纯度≥99.9的金属镁、纯度≥99.9的金属钒、纯度≥99.96的电解镍;后将原料按照上述各组分含量将电解镍、金属钒、石墨混合,后在1400~1550℃条件下真空熔炼70~90min,再加入钛、镁、硼精炼10~20min,后在保护气氛下浇铸得到铸锭;其中整个 熔炼过程中真空度保持在小于4Pa;浇铸时的保护气氛可以是氩气;(1) Vacuum smelting: prepare raw materials before smelting, graphite with purity ≥ 99.9, boron particles with purity ≥ 99.9, metallic titanium with purity ≥ 99.9, metallic magnesium with purity ≥ 99.9, metallic vanadium with purity ≥ 99.9, electrolytic nickel with purity ≥ 99.96; Then, the raw materials are mixed with electrolytic nickel, metallic vanadium, and graphite according to the content of the above-mentioned components, and then smelted in a vacuum at 1400-1550°C for 70-90 minutes, and then titanium, magnesium, and boron are added for refining for 10-20 minutes, and then under a protective atmosphere The ingot is obtained by casting; wherein the vacuum degree is kept at less than 4 Pa during the whole smelting process; the protective atmosphere during casting can be argon;
(2)热锻:热锻前对铸锭进行粗加工,可以利用车床去除表面氧化皮和一些缺陷,切除冒口,得到圆台型光亮锭,并仔细修磨,去除微裂纹等;后将铸锭进行热锻,将铸锭加热至1090~1120℃,保温20~50min后,进行锻造,开锻温度为1090~1120℃,终锻温度为990~1050℃;将铸锭反复墩粗后拔长,变形量大于50%;此处的拔长的变形量大于50%,是和墩粗后的锻棒相对比的。(2) Hot forging: rough machining of the ingot before hot forging. The lathe can be used to remove the surface oxide scale and some defects, and the riser can be cut to obtain a round truncated cone-shaped bright ingot, which is carefully ground to remove microcracks, etc.; The ingot is hot forged, the ingot is heated to 1090~1120℃, and after holding for 20~50min, forging is carried out, the forging temperature is 1090~1120℃, and the final forging temperature is 990~1050℃; the ingot is repeatedly roughed and then drawn Long, the deformation is greater than 50%; the deformation of the drawing here is greater than 50%, which is compared with the forging rod after the pier is thick.
(3)机加工:将经过热锻的圆柱型锻件表面氧化皮去除,将锻件两端加工平整,确保端面与圆柱面垂直,然后根据要求加工出中心通孔,并在锻棒的一端加工出锥形孔,得到合金圆柱。(3) Machining: remove the oxide scale on the surface of the hot forged cylindrical forgings, and process the two ends of the forgings smoothly to ensure that the end surface is perpendicular to the cylindrical surface, and then process the center through hole according to the requirements, and process one end of the forging rod Taper holes to obtain alloy cylinders.
(4)热挤压:通过感应加热对步骤(3)得到的合金圆柱进行加热,加热温度为990~1130℃;后进行扩孔,扩孔速度为150~220mm/s;再采用二次感应加热处理,加热温度为1000~1150℃,采用热挤压机进行挤压,挤压速度为120~150mm/s;(4) Hot extrusion: The alloy cylinder obtained in step (3) is heated by induction heating at a heating temperature of 990 to 1130°C; then the hole is expanded at a speed of 150 to 220 mm/s; and then a secondary induction is used Heat treatment, the heating temperature is 1000~1150℃, and the hot extruder is used for extrusion, and the extrusion speed is 120~150mm/s;
(5)对荒管依次进行酸洗处理、固溶处理、冷轧或镗孔、退火处理、机加工或绑定。(5) Pickling treatment, solution treatment, cold rolling or boring, annealing treatment, machining or binding are carried out on the waste pipe in sequence.
酸洗处理:将荒管进行酸洗,去除表面凹坑等缺陷;酸洗处理可采用现有技术中的常用酸洗工艺。Pickling treatment: the waste pipe is pickled to remove defects such as surface pits; the pickling treatment can adopt the common pickling process in the prior art.
固溶处理:将酸洗过的荒管进行固溶处理,室温下得到单相奥氏体组织,使材料具有最好的耐蚀性,并且塑性高、成形性好,并且能够细化荒管的晶粒组织。Solution treatment: The acid-washed waste pipe is solid-solution treated to obtain a single-phase austenite structure at room temperature, so that the material has the best corrosion resistance, high plasticity, good formability, and can refine the waste pipe The grain structure.
冷轧或镗孔:将表面处理过的荒管进行高精度的轧制或者进行镗孔,得到内孔尺寸公差为±0.2mm光亮管。Cold rolling or boring: the surface-treated waste tube is rolled or bored with high precision to obtain a bright tube with an inner hole size tolerance of ±0.2mm.
退火处理:对光亮管进行退火处理,退火温度为840~870℃,保温80~90min。Annealing treatment: the bright tube is annealed, the annealing temperature is 840~870℃, and the heat preservation is 80~90min.
机加工或绑定:最后将光亮管加工到所需尺寸的整体旋转靶材,或加工到一定的尺寸,再通过绑定的方式制作所需尺寸的绑定旋转靶材。Machining or binding: Finally, the bright tube is processed to the overall rotating target of the required size, or processed to a certain size, and then the binding rotating target of the required size is made by binding.
优选地,上述制备过程中的步骤(1)中电解镍在580~620℃条件下烘烤5~8小时。长时间的烘烤,可以有效去除电解镍中含有的大部分氢气。Preferably, in step (1) of the above-mentioned preparation process, the electrolytic nickel is baked at 580-620° C. for 5-8 hours. Long-term baking can effectively remove most of the hydrogen contained in electrolytic nickel.
优选地,所述步骤(1)中真空熔炼过程中添加钛、镁、硼采用镍箔包住钛、镁、硼的方式加入;真空熔炼过程中采用上述方式加入微量合金元素金属钛、金属镁、硼粒,可以避免直接加入引起钢液沸腾及溅射。Preferably, in the step (1), titanium, magnesium, and boron are added in the vacuum melting process by using nickel foil to enclose the titanium, magnesium, and boron; during the vacuum melting process, the micro-alloying elements metal titanium and metal magnesium are added in the above-mentioned manner. , Boron particles can avoid boiling and sputtering of molten steel caused by direct addition.
优选地,所述步骤(2)中墩粗的变形量为大于50%。在锻造过程中,反复墩粗和拔长,其墩粗变形量为大于50%,充分破碎粗大晶粒组织,从而提高挤压成材率。Preferably, the deformation of the pier thickness in the step (2) is greater than 50%. In the forging process, the pier roughening and drawing length are repeated, the pier rough deformation is more than 50%, and the coarse grain structure is fully broken, thereby increasing the extrusion yield.
优选地,所述步骤(3)中心通孔的直径为20~40mm,所述锥形孔的锥度为20°~40°。此处的中心通孔、锥形孔方便扩孔头与合金对应,防止扩歪造成偏心。Preferably, the diameter of the central through hole in the step (3) is 20-40 mm, and the taper of the tapered hole is 20°-40°. The central through hole and tapered hole here facilitate the reaming head to correspond to the alloy, and prevent eccentricity caused by reaming.
优选地,所述步骤(4)中,二次感应加热的温度比前一次感应加热的温度高10~20℃。通过感应加热后再扩孔,二次感应加热后再挤压;并且二次感应加热温度略高10~20℃, 可以防止挤压准备过程中温度下降而造成的挤压过程中产生缺陷或报废。Preferably, in the step (4), the temperature of the secondary induction heating is 10-20°C higher than the temperature of the previous induction heating. Enlarging the hole after induction heating, and then extruding after the second induction heating; and the temperature of the second induction heating is slightly higher by 10-20°C, which can prevent defects or scrapping in the extrusion process caused by the temperature drop during the extrusion preparation process .
优选地,所述步骤(5)固溶处理将荒管加热到950~1000℃保温,然后水淬。采用较低温度的固溶处理,快速冷却,从而得到细小晶粒的荒管,提高材料的塑性和耐蚀性。Preferably, in the step (5) solution treatment, the waste pipe is heated to 950-1000° C. for heat preservation, and then water quenched. A solution treatment at a lower temperature and rapid cooling are adopted to obtain a waste tube with fine grains and improve the plasticity and corrosion resistance of the material.
优选地,退火处理:对光亮管进行退火处理,退火温度为840~870℃,保温80~90min。Preferably, annealing treatment: annealing the bright tube, the annealing temperature is 840-870°C, and the heat preservation is 80-90 min.
发明原理:本发明通过在高真空熔炼过程中添加微量的元素C、B、Ti、Mg进行成分优化,降低氧、硫等含量,且能抑制裂纹的萌生,提高靶材的晶界结合力、强度,并细化晶粒,从而提高成材率。其中,添加B元素,B偏聚在晶界或空位型缺陷上,提高晶界结合力,形成细小的M 3B 2型硼化物,减少由杂质元素结合形成的TCP相中μ相的的形成,抑制裂纹的产生;由于镍钒在熔炼过程中黏性比较大,在凝固过程中补缩难,B元素的加入能够改善合金在凝固后期的补缩,减少显微缩孔的产生;添加Ti元素,由于合金中的杂质元素Al与Ni形成Ni 3Al型金属间化合物,Ti的加入可替代Ni 3Al中的Al原子,形成Ni 3(Al、Ti)型强化相,从而进一步提高合金的强度;添加C、Mg元素,主要是脱氧、去硫,净化金属液,而且高温下会挥发,不影响金属液的纯度。从而降低镍钒合金中的氢、氧、氮等间隙气体含量,同时去除有害杂质硫与细化晶粒。从而提高合金的质量,优化合金成分。 Principle of the invention: The present invention optimizes the composition by adding trace elements C, B, Ti, Mg in the high vacuum smelting process, reduces the content of oxygen, sulfur, etc., and can inhibit the initiation of cracks, and improve the grain boundary bonding force of the target material. Strength, and refine the grains, thereby increasing the yield. Among them, adding B element, B segregates on the grain boundary or vacancy type defects, improves the grain boundary bonding force, forms fine M 3 B 2 type borides, and reduces the formation of μ phase in the TCP phase formed by the combination of impurity elements , Inhibit the generation of cracks; due to the relatively high viscosity of nickel and vanadium during the smelting process, it is difficult to feed during the solidification process. The addition of element B can improve the feeding of the alloy in the later stage of solidification and reduce the generation of microscopic shrinkage; adding Ti Since the impurity element Al and Ni in the alloy form a Ni 3 Al intermetallic compound, the addition of Ti can replace the Al atom in Ni 3 Al to form a Ni 3 (Al, Ti) type strengthening phase, thereby further improving the alloy’s Strength; adding C and Mg elements, mainly for deoxidation, desulfurization, and purification of molten metal, and will volatilize at high temperatures, and does not affect the purity of molten metal. Thereby reducing the content of interstitial gases such as hydrogen, oxygen and nitrogen in the nickel-vanadium alloy, while removing harmful sulfur impurities and refining crystal grains. Thereby improving the quality of the alloy and optimizing the alloy composition.
其中本发明中的含微量元素的大管径Ni-V旋转靶材在热加工工艺过程中,热锻和热挤压温度十分关键,基于镍基合金的热加工原理,对镍基合金(Ni93V7)进行试验和理论模拟,利用热加工图不仅可以得到材料的形变组织演变规律,而且可以区别出,材料变形的安全区域(稳定区域)和不安全区域(失稳区域),以至于达到控制组织演变、避免不安全区域(失稳区域)以及优化热加工参数的目的。动态材料模型的热加工图研究方法,现在已成为最有效的方法去研究金属材料可加工性以及控制形变组织。Among them, the large-diameter Ni-V rotating target containing trace elements in the present invention is very critical in hot forging and hot extrusion temperature during the hot working process. Based on the hot working principle of the nickel-based alloy, the nickel-based alloy (Ni93V7 ) Carry out experiments and theoretical simulations, and use the thermal processing map to not only get the evolution law of the deformed structure of the material, but also to distinguish the safe area (stable area) and unsafe area (instability area) of the material deformation, so as to achieve the control structure The purpose of evolving, avoiding unsafe areas (instability areas) and optimizing thermal processing parameters. The research method of thermal processing map of dynamic material model has now become the most effective method to study the workability of metal materials and control the deformed structure.
对镍基合金(Ni93V7)进行热模拟单道次压缩实验,实验过程中设置了三组速率,分别为0.001s -1、0.1s -1、1s -1,每组速率设置四个温度:1000℃、1050℃、1100℃、1150℃。然后根据得出的流变应力曲线结果结合加工图技术对新材料的热变形行为进行系统的探索。并通过动态材料模型理论和基于DMM的流变失稳判定,绘制得到镍基合金的热加工图,以镍钒合金的流变应力曲线为基础,建立了基于动态材料模型的合金的功率耗散图。因为没有失稳现象的发生,所以热加工图的产生不需要再通过叠加功率耗散图和流变失稳图,功率耗散图即是最终的热加工图。 A thermal simulation single-pass compression experiment was performed on a nickel-based alloy (Ni93V7). During the experiment, three sets of rates were set, namely 0.001s -1 , 0.1s -1 , and 1s -1 , and each set of rates set four temperatures: 1000 ℃, 1050℃, 1100℃, 1150℃. Then, based on the flow stress curve results obtained, combined with the processing drawing technology, the thermal deformation behavior of the new material is systematically explored. And through the dynamic material model theory and DMM-based rheological instability determination, the thermal processing diagram of the nickel-based alloy is drawn. Based on the flow stress curve of the nickel-vanadium alloy, the power dissipation of the alloy based on the dynamic material model is established Figure. Because there is no instability phenomenon, the generation of the thermal processing map does not need to superimpose the power dissipation map and the rheological instability map. The power dissipation map is the final thermal processing map.
依据热加工图的分析,得出具体结论如下:Based on the analysis of the thermal processing diagram, the specific conclusions are as follows:
(1)镍钒合金在三组应变速率,分别为0.001s -1、0.1s -1、1s -1,和每组速率设置四个温度:1000℃、1050℃、1100℃、1150℃的实验条件下,没有出现失稳状态,也就没有了失稳区域和流变失稳图。 (1) Experiments with nickel-vanadium alloy in three sets of strain rates, 0.001s -1 , 0.1s -1 , 1s -1 , and four temperatures for each set of rates: 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ Under the conditions, there is no unstable state, and there is no unstable area and rheological instability diagram.
(2)基于应变量为0.2下的功率耗散图,功率耗散η值是持续增加的,所以镍钒合金 仅出现一个峰值区域,功率耗散峰值区基本稳定在高温高应变速率下。(2) Based on the power dissipation diagram with a strain of 0.2, the value of power dissipation η continues to increase, so there is only one peak area in the nickel-vanadium alloy, and the peak power dissipation area is basically stable at high temperature and high strain rate.
(3)由热加工图得出,镍钒合金的最佳热加工参数在1090~1120℃、1s -1的区间内。 (3) According to the hot working diagram, the best hot working parameters of nickel-vanadium alloy are in the interval of 1090~1120℃, 1s -1.
本发明的两个关键技术环节分别为Ni-V旋转靶材原材料的配比设计及工艺条件的控制,两者相辅相成。尤其是热锻和热挤压工艺参数,通过合适的成分配比、结合优化的制备方法,成功制备得到了Ni-V旋转靶材,可以制作整体旋转靶材或者绑定旋转靶材,满足更多的使用需求。The two key technical links of the present invention are the ratio design of the Ni-V rotating target material and the control of the process conditions, which are complementary to each other. Especially for hot forging and hot extrusion process parameters, Ni-V rotating targets have been successfully prepared through suitable component ratios and optimized preparation methods. The entire rotating target can be made or bound with the rotating target to meet more requirements. More usage needs.
有益效果:与现有技术相比,Beneficial effect: Compared with the prior art,
(1)本发明在Ni-V的基础上,添加微量的合金元素C、B、Ti、Mg进行成分优化,降低氧、硫等含量,且能抑制裂纹的萌生,提高靶材的晶界结合力、强度,并细化晶粒,能够改善合金在凝固后期的补缩,减少显微缩孔的产生,从而提高成材率。(1) On the basis of Ni-V, the present invention adds a small amount of alloying elements C, B, Ti, Mg to optimize the composition, reduces the content of oxygen, sulfur, etc., and can inhibit the initiation of cracks, and improve the grain boundary bonding of the target material Strength, strength, and grain refinement can improve the feeding of the alloy in the later stage of solidification, reduce the generation of microscopic shrinkage, and increase the yield.
(2)电解镍通过长时间高温烘烤,能有效去除电解镍中含有的部分氢气;通过反复墩粗和拔长的锻造工艺、感应加热后扩孔及二次感应加热后挤压、精轧或镗孔等工艺过程,能够提高旋转靶材的同心率和成材率;(2) Electrolytic nickel can effectively remove part of the hydrogen contained in electrolytic nickel through long-term high-temperature baking; through repeated thickening and elongation forging process, hole expansion after induction heating, and extrusion and finish rolling after secondary induction heating Or boring and other technological processes can improve the concentricity and yield rate of the rotating target;
(3)本发明无需加入稀土元素,通过成分的优化和工艺条件的控制,成功制备得到成本低、性能优的大管径Ni-V旋转靶材;(3) The present invention does not need to add rare earth elements, and successfully prepares a large diameter Ni-V rotating target with low cost and excellent performance through the optimization of the composition and the control of the process conditions;
(4)本发明通过试验和理论模拟相结合,绘制镍基合金的热加工图,得到旋转靶材的热锻和热挤压优化参数,大大提高了大管径Ni-V旋转靶材的成品率;(4) Through the combination of experiment and theoretical simulation, the present invention draws the hot processing diagram of the nickel-based alloy, obtains the hot forging and hot extrusion optimization parameters of the rotating target, and greatly improves the finished product of the large-diameter Ni-V rotating target rate;
(5)本发明的制备方法能够克服镍钒管开裂、夹杂物、缺陷、偏心及加工困难等问题的大管径镍钒旋转靶材;(5) The preparation method of the present invention can overcome the problems of nickel-vanadium tube cracking, inclusions, defects, eccentricity, and processing difficulties, etc., a large-diameter nickel-vanadium rotating target material;
(6)本发明通过制作整体旋转靶或绑定旋转靶,其利用率可达到70%~80%,既能满足更多的市场需求和特殊需求,又能提高材料的利用率,降低成本。(6) The present invention can achieve 70%-80% utilization rate by manufacturing an integral rotating target or a bound rotating target, which can not only meet more market demands and special demands, but also increase the utilization rate of materials and reduce costs.
附图说明Description of the drawings
图1是实施例1制备的大管径Ni-V旋转靶材的100倍金相照片;Figure 1 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 1;
图2是实施例2制备的大管径Ni-V旋转靶材的100倍金相照片;2 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 2;
图3是实施例3制备的大管径Ni-V旋转靶材的100倍金相照片;3 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 3;
图4是实施例4制备的大管径Ni-V旋转靶材的100倍金相照片;4 is a 100 times metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 4;
图5是实施例5制备的大管径Ni-V旋转靶材的100倍金相照片;5 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 5;
图6是实施例6制备的大管径Ni-V旋转靶材的100倍金相照片;Fig. 6 is a 100-fold metallographic photograph of the large-diameter Ni-V rotating target prepared in Example 6;
图7是对比例制备Ni-V旋转靶材过程中的低倍照片;Figure 7 is a low-magnification photo of the comparative example during the preparation of Ni-V rotating target;
图8是对比例靶材的100倍金相图片。Figure 8 is a 100-fold metallographic picture of the target of the comparative example.
具体实施方式detailed description
下面结合实施例对本发明进行详细说明。The present invention will be described in detail below in conjunction with embodiments.
以下实施例中用于制备大管径Ni-V旋转靶材的试剂和材料均为市售。The reagents and materials used to prepare the large-diameter Ni-V rotating target in the following examples are all commercially available.
实施例1:Example 1:
本实施例中含微量元素的大管径Ni-V旋转靶材的组分及含量,按质量百分比计分别为:C 0.02%,B 0.03%,Ti 0.005%,Mg 0.01%,V 6%以及余量Ni和不可避免的杂质。In this embodiment, the composition and content of the large-diameter Ni-V rotating target containing trace elements are as follows: C 0.02%, B 0.03%, Ti 0.005%, Mg 0.01%, V 6% and The balance Ni and unavoidable impurities.
该大管径Ni-V旋转靶材的制备方法包括如下步骤:The preparation method of the large diameter Ni-V rotating target includes the following steps:
(1)真空熔炼:准备原料石墨、硼粒、金属钛、金属镁、金属钒、电解镍,其中原料的纯度为99.9%的石墨、99.9%的硼粒、99.9%的金属钛、99.9%的金属镁、99.9%的金属钒、99.96%的电解镍;(1) Vacuum melting: prepare raw material graphite, boron particles, metallic titanium, metallic magnesium, metallic vanadium, electrolytic nickel, among which the purity of raw materials is 99.9% graphite, 99.9% boron particles, 99.9% metallic titanium, 99.9% Metal magnesium, 99.9% metallic vanadium, 99.96% electrolytic nickel;
将电解镍、金属钒的表面油污及氧化物处理干净并干燥称重,再将电解镍600℃,保温6小时烘烤;然后将原料按照上述各组分含量,首先将电解镍、金属钒、石墨放入真空熔炼坩埚中,通电熔炼,熔炼温度为1500℃,熔炼时间为80min,再先后加入用镍箔包好的金属钛、金属镁和硼粒,再精炼15min,整个熔炼过程中真空度小于4Pa;熔炼后进行浇铸,浇铸前在真空状态中先通氩气4Mpa,在保护气氛的条件下进行浇注,浇注40min后脱模得到铸锭。The surface oil stains and oxides of electrolytic nickel and metal vanadium are cleaned and dried and weighed. Then, the electrolytic nickel is baked at 600°C for 6 hours; then the raw materials are prepared according to the content of the above components. First, the electrolytic nickel, metal vanadium, Graphite is put into a vacuum melting crucible and smelted with electricity. The melting temperature is 1500℃, and the melting time is 80 minutes. Then, the metal titanium, metal magnesium and boron particles wrapped in nickel foil are added successively, and then refined for 15 minutes. The vacuum degree during the entire melting process Less than 4Pa; casting is performed after smelting, and argon gas 4Mpa is passed in a vacuum state before casting, and the casting is performed under protective atmosphere conditions, and the ingot is demolded after 40 minutes of casting.
(2)第一次机加工:利用车床去除铸锭表面氧化皮和一些缺陷,切除冒口,得到圆台型光亮锭,并仔细修磨,去除微裂纹等;(2) The first machining: Use a lathe to remove the oxide scale and some defects on the surface of the ingot, cut off the riser to obtain a round truncated cone-shaped bright ingot, and carefully grind to remove microcracks, etc.;
(3)热锻:将经机加工处理后的铸锭加热至1100℃,保温30min后,进行锻造,开锻温度为1100℃,终锻温度为1000℃;将铸锭反复墩粗,墩粗的变形量为60%,后进行拔长,拔长变形量为60%;此处的拔长的变形量是和墩粗后的锻棒相对比的;最终锻造至
Figure PCTCN2019108213-appb-000001
的锻棒;
(3) Hot forging: heat the machined ingot to 1100°C, hold for 30 minutes, and then perform forging. The forging temperature is 1100°C and the final forging temperature is 1000°C; the ingot is repeatedly thickened and thickened. The amount of deformation is 60%, and then the drawing is carried out, and the drawing deformation is 60%; the drawing deformation here is compared with the forging rod after the pier is thick; the final forging is
Figure PCTCN2019108213-appb-000001
Forging rod
(4)第二次机加工:将圆柱型锻棒的表面氧化皮去除,将锻棒两端加工平整,确保端面与圆柱面垂直,加工后为直径300±3mm,长度大于500mm的圆柱,然后加工出直径为30mm的中心通孔,并在其中一端加工出成20°锥度的锥形孔,得到合金圆柱;(4) Second machining: remove the oxide scale on the surface of the cylindrical forging rod, and process both ends of the forging rod to be flat, ensuring that the end face is perpendicular to the cylindrical surface, and after machining, it will be a cylinder with a diameter of 300 ± 3 mm and a length greater than 500 mm. Processed a central through hole with a diameter of 30mm, and processed a tapered hole with a 20° taper at one end to obtain an alloy cylinder;
(5)热挤压:通过感应加热对合金圆柱进行加热,加热温度为1000℃,再利用扩孔头进行扩孔,扩孔速度为200mm/s,再经过二次感应加热,加热温度为1020℃,再利用6500吨热挤压机进行挤压,挤压速度为120mm/s,得到外径为170~200mm,内径为130~160mm,长度为2500~4500mm的荒管;(5) Hot extrusion: The alloy cylinder is heated by induction heating at a heating temperature of 1000°C, and then the hole is expanded by a reaming head at a reaming speed of 200mm/s, and then subjected to secondary induction heating at a heating temperature of 1020. ℃, and then use a 6500-ton hot extruder for extrusion at a speed of 120mm/s to obtain a waste pipe with an outer diameter of 170-200mm, an inner diameter of 130-160mm, and a length of 2500-4500mm;
(6)酸洗处理:将荒管进行酸洗,去除表面凹坑等缺陷;(6) Pickling treatment: pickling the waste pipe to remove defects such as surface pits;
(7)固溶处理:将荒管加热到950℃保温,保温1小时,然后水淬;(7)Solution treatment: heat the waste pipe to 950℃ for heat preservation, heat preservation for 1 hour, and then water quench;
(8)冷轧或镗孔:将表面处理过的荒管进行高精度的轧制或者进行镗孔,得到内孔尺寸公差为±0.2mm光亮管;(8) Cold rolling or boring: high-precision rolling or boring of the surface-treated waste tube to obtain a bright tube with an inner hole size tolerance of ±0.2mm;
(9)退火处理:在退火温度850℃的条件下,退火保温时间为80min进行退火处理;(9) Annealing treatment: under the condition of annealing temperature of 850℃, annealing holding time is 80min for annealing treatment;
(10)机加工或绑定:将光亮管加工到所需尺寸的整体旋转靶材,或加工到一定的尺寸,再通过绑定的方式制作所需尺寸的绑定旋转靶材。(10) Machining or binding: the bright tube is processed to the overall rotating target of the required size, or processed to a certain size, and then the binding rotating target of the required size is made by binding.
对本实施例制备得到的大管径Ni-V旋转靶材进行金相分析,100倍下的金相图片如图1所示,可以看出,有细小的析出物弥散分布在晶界处,从而起到强化的效果,晶粒分布均匀,且晶粒大小平均在47~63μm。The metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out. The metallographic picture under 100 times is shown in Figure 1. It can be seen that there are fine precipitates dispersed at the grain boundary, thus Play a strengthening effect, the grain distribution is uniform, and the average grain size is 47-63μm.
实施例2:Example 2:
本实施例中大管径Ni-V旋转靶材的组分及含量,按质量百分比计分别为:C 0.03%,B 0.01%,Ti 0.003%,Mg 0.03%,V 7%以及余量Ni和不可避免的杂质。In this embodiment, the composition and content of the large-diameter Ni-V rotating target are as follows: C 0.03%, B 0.01%, Ti 0.003%, Mg 0.03%, V 7% and the balance Ni and Inevitable impurities.
本实施例的大管径Ni-V旋转靶材的制备方法与实施例1基本相同,不同之处在于:The preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
步骤(1)中,电解镍在580℃,保温5小时进行烘烤;熔炼温度为1450℃,熔炼时间为70min,精炼时间为10min;In step (1), the electrolytic nickel is baked at 580°C for 5 hours; the melting temperature is 1450°C, the melting time is 70 minutes, and the refining time is 10 minutes;
步骤(3)中,铸锭加热至1090℃,保温20min后,进行锻造,开锻温度为1090℃,终锻温度为1000℃;墩粗的变形量为55%,后拔长的变形量为55%;In step (3), the ingot is heated to 1090°C and held for 20 minutes before forging. The forging temperature is 1090°C and the final forging temperature is 1000°C; the deformation of the pier thickness is 55%, and the deformation after drawing is 55%;
步骤(4)中,机加工出直径为20mm的中心通孔,并在其中一端加工出成30°锥度的锥形孔;In step (4), a central through hole with a diameter of 20mm is machined, and one end is machined into a tapered hole with a 30° taper;
步骤(5)中,感应加热温度为1100℃,扩孔速度为180mm/s;第二次感应加热温度为1110℃,挤压速度为130mm/s;In step (5), the induction heating temperature is 1100°C, and the hole expanding speed is 180mm/s; the second induction heating temperature is 1110°C, and the extrusion speed is 130mm/s;
步骤(7)中,固溶处理加热到980℃;In step (7), the solution treatment is heated to 980°C;
步骤(9)中,退火温度840℃,退火保温时间为85min。In step (9), the annealing temperature is 840° C., and the annealing holding time is 85 min.
对本实施例制备得到的大管径Ni-V旋转靶材进行金相分析,100倍下的金相图片如图2所示,可以看出,有细小的析出物弥散分布在晶界处,从而起到强化的效果,晶粒分布比较均匀,且晶粒大小平均在47~80μmThe metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out. The metallographic picture under 100 times is shown in Figure 2. It can be seen that there are fine precipitates dispersed in the grain boundary, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 47~80μm
实施例3:Example 3:
本实施例中大管径Ni-V旋转靶材的组分及含量,按质量百分比计分别为:C 0.05%,B 0.08%,Ti 0.001%,Mg 0.05%,V 8%以及余量Ni和不可避免的杂质。The composition and content of the large-diameter Ni-V rotating target in this embodiment are as follows in terms of mass percentage: C 0.05%, B 0.08%, Ti 0.001%, Mg 0.05%, V 8%, and the balance Ni and Inevitable impurities.
本实施例的大管径Ni-V旋转靶材的制备方法与实施例1基本相同,不同之处在于:The preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
步骤(1)中,电解镍在610℃,保温8小时进行烘烤;熔炼温度为1400℃,熔炼时间为90min,精炼时间为20min;In step (1), the electrolytic nickel is baked at 610°C for 8 hours; the melting temperature is 1400°C, the melting time is 90 minutes, and the refining time is 20 minutes;
步骤(3)中,铸锭加热至1110℃,保温40min后,进行锻造,开锻温度为1110℃,终锻温度为990℃;墩粗的变形量为65%;In step (3), the ingot is heated to 1110°C and kept for 40 minutes before forging. The forging temperature is 1110°C and the final forging temperature is 990°C; the deformation of the upset thickness is 65%;
步骤(4)中,机加工出直径为30mm的中心通孔,并在其中一端加工出成40°锥度的锥形孔;In step (4), a central through hole with a diameter of 30mm is machined, and a tapered hole with a 40° taper is machined at one end;
步骤(5)中,感应加热温度为990℃,扩孔速度为150mm/s;第二次感应加热温度为1000℃,挤压速度为140mm/s;In step (5), the induction heating temperature is 990°C, and the hole expanding speed is 150mm/s; the second induction heating temperature is 1000°C, and the extrusion speed is 140mm/s;
步骤(7)中,固溶处理加热到970℃;In step (7), the solution treatment is heated to 970°C;
步骤(9)中,退火温度860℃,退火保温时间为90min。In step (9), the annealing temperature is 860°C, and the annealing holding time is 90 min.
对本实施例制备得到的大管径Ni-V旋转靶材进行金相分析,100倍下的金相图片如图3所示,可以看出,有少量的细小析出物分布在晶界处,从而起到强化的效果,晶粒分布比较均匀,且晶粒大小平均在45~73μm。The metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out. The metallographic picture at 100 times is shown in Figure 3. It can be seen that a small amount of fine precipitates are distributed at the grain boundaries, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 45-73μm.
实施例4:Example 4:
本实施例中大管径Ni-V旋转靶材的组分及含量,按质量百分比计分别为:C 0.03%,B 0.05%,Ti 0.002%,Mg 0.04%,V 6%以及余量Ni和不可避免的杂质。The composition and content of the large-diameter Ni-V rotating target in this embodiment are as follows in terms of mass percentage: C 0.03%, B 0.05%, Ti 0.002%, Mg 0.04%, V 6% and the balance Ni and Inevitable impurities.
本实施例的大管径Ni-V旋转靶材的制备方法与实施例1基本相同,不同之处在于:The preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
步骤(1)中,电解镍在620℃,保温7小时进行烘烤;熔炼温度为1550℃,熔炼时间为70min;In step (1), the electrolytic nickel is baked at 620°C for 7 hours; the smelting temperature is 1550°C, and the smelting time is 70min;
步骤(3)中,铸锭加热至1120℃,保温50min后,进行锻造,开锻温度为1120℃,终锻温度为1050℃;墩粗的变形量为55%;In step (3), the ingot is heated to 1120°C and held for 50 minutes before forging. The forging temperature is 1120°C and the final forging temperature is 1050°C; the deformation of the upset thickness is 55%;
步骤(4)中,机加工出直径为40mm的中心通孔,并在其中一端加工出成40°锥度的锥形孔;In step (4), a central through hole with a diameter of 40mm is machined, and a tapered hole with a 40° taper is machined at one end;
步骤(5)中,感应加热温度为1050℃,扩孔速度为200mm/s;第二次感应加热温度为1060℃,挤压速度为150mm/s;In step (5), the induction heating temperature is 1050°C, and the hole expanding speed is 200mm/s; the second induction heating temperature is 1060°C, and the extrusion speed is 150mm/s;
步骤(7)中,固溶处理加热到1000℃;In step (7), the solution treatment is heated to 1000°C;
步骤(9)中,退火温度870℃,退火保温时间为90min。In step (9), the annealing temperature is 870°C, and the annealing holding time is 90 minutes.
对本实施例制备得到的大管径Ni-V旋转靶材进行金相分析,100倍下的金相图片如图4所示,可以看出,有细小的析出物弥散分布在晶界处,从而起到强化的效果,晶粒分布比较均匀,且晶粒大小平均在47~80μm。The metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out. The metallographic picture at 100 times is shown in Figure 4. It can be seen that there are fine precipitates dispersed at the grain boundary, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 47-80μm.
实施例5:Example 5:
本实施例中大管径Ni-V旋转靶材的组分及含量,按质量百分比计分别为:C 0.04%,B 0.06%,Ti 0.006%,Mg 0.02%,V 7%以及余量Ni和不可避免的杂质。In this embodiment, the composition and content of the large-diameter Ni-V rotating target are as follows in terms of mass percentage: C 0.04%, B 0.06%, Ti 0.006%, Mg 0.02%, V 7%, and the balance Ni and Inevitable impurities.
本实施例的大管径Ni-V旋转靶材的制备方法与实施例1基本相同,不同之处在于:The preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
步骤(1)中,电解镍在590℃,保温6小时进行烘烤;In step (1), the electrolytic nickel is baked at 590°C for 6 hours;
步骤(4)中,机加工出直径为20mm的中心通孔,并在其中一端加工出成40°锥度的锥形孔;In step (4), a central through hole with a diameter of 20mm is machined, and a tapered hole with a 40° taper is machined at one end;
步骤(5)中,感应加热温度为1130℃,扩孔速度为220mm/s;第二次感应加热温度为1150℃,挤压速度为130mm/s;In step (5), the induction heating temperature is 1130°C, and the reaming speed is 220mm/s; the second induction heating temperature is 1150°C, and the extrusion speed is 130mm/s;
步骤(7)中,固溶处理加热到960℃;In step (7), the solution treatment is heated to 960°C;
对本实施例制备得到的大管径Ni-V旋转靶材进行金相分析,100倍下的金相图片如图5所示,可以看出,有细小的析出物弥散分布在晶界处,从而起到强化的效果,晶粒分布 比较均匀,且晶粒大小平均在40~54μm。The metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out. The metallographic picture at 100 times is shown in Figure 5. It can be seen that there are fine precipitates dispersed in the grain boundary, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 40-54μm.
实施例6:Example 6:
本实施例中大管径Ni-V旋转靶材的组分及含量,按质量百分比计分别为:C 0.01%,B 0.02%,Ti 0.002%,Mg 0.01%,V 8%以及余量Ni和不可避免的杂质。In this embodiment, the composition and content of the large-diameter Ni-V rotating target are as follows in terms of mass percentage: C 0.01%, B 0.02%, Ti 0.002%, Mg 0.01%, V 8%, and the balance Ni and Inevitable impurities.
本实施例的大管径Ni-V旋转靶材的制备方法与实施例1基本相同,不同之处在于:The preparation method of the large-diameter Ni-V rotating target of this embodiment is basically the same as that of embodiment 1, except that:
步骤(1)中,电解镍在590℃,保温6小时进行烘烤;In step (1), the electrolytic nickel is baked at 590°C for 6 hours;
步骤(4)中,机加工出直径为20mm的中心通孔,并在其中一端加工出成40°锥度的锥形孔;In step (4), a central through hole with a diameter of 20mm is machined, and a tapered hole with a 40° taper is machined at one end;
步骤(5)中,感应加热温度为1120℃,扩孔速度为160mm/s;第二次感应加热温度为1140℃,挤压速度为125mm/s;In step (5), the induction heating temperature is 1120°C, and the reaming speed is 160mm/s; the second induction heating temperature is 1140°C, and the extrusion speed is 125mm/s;
步骤(7)中,固溶处理加热到1000℃。In step (7), the solution treatment is heated to 1000°C.
对本实施例制备得到的大管径Ni-V旋转靶材进行金相分析,100倍下的金相图片如图6所示,可以看出,有少量的细小析出物分布在晶界处,从而起到强化的效果,晶粒分布比较均匀,且晶粒大小平均在45~69μm。The metallographic analysis of the large-diameter Ni-V rotating target prepared in this example is carried out. The metallographic picture at 100 times is shown in Figure 6. It can be seen that a small amount of fine precipitates are distributed at the grain boundaries, thus Play a strengthening effect, the grain distribution is relatively uniform, and the average grain size is 45-69μm.
对比例:Comparative ratio:
本对比例与实施例1基本相同,不同之处在于:This comparative example is basically the same as Example 1, except that:
步骤(3)中,铸锭加热至1150℃,保温50min后,进行锻造,开锻温度为1150℃,终锻温度为1000℃;In step (3), the ingot is heated to 1150°C, and after holding for 50 minutes, forging is performed, the opening forging temperature is 1150°C, and the final forging temperature is 1000°C;
步骤(5)中,感应加热温度为1140℃;第二次感应加热温度为1160℃。In step (5), the induction heating temperature is 1140°C; the second induction heating temperature is 1160°C.
如图7所示,本对比例的Ni-V靶材经热挤压后严重开裂,可以看到明显的裂纹;从图8所示,可以看出晶粒上可以看出晶粒比较粗大,晶粒大小在80~100μm之间,晶界处夹杂析出物粗大,晶界处受到破坏;因此,合适的热锻温度、热挤压温度至关重要。As shown in Figure 7, the Ni-V target material of this comparative example was severely cracked after hot extrusion, and obvious cracks can be seen; from Figure 8, it can be seen that the grains are relatively coarse. The grain size is between 80-100μm, the inclusions at the grain boundary are coarse, and the grain boundary is damaged; therefore, the appropriate hot forging temperature and hot extrusion temperature are very important.

Claims (9)

  1. 一种含微量元素的大管径Ni-V旋转靶材,其特征在于包括按质量百分比计的如下组分:C 0.01~0.05%,B 0.01~0.08%,Ti 0.001~0.006%,Mg 0.01~0.05%,V 6~8%以及余量Ni和不可避免的杂质。A large-diameter Ni-V rotating target material containing trace elements, which is characterized by including the following components in terms of mass percentage: C 0.01~0.05%, B 0.01~0.08%, Ti 0.001~0.006%, Mg 0.01~ 0.05%, V 6-8% and the balance Ni and unavoidable impurities.
  2. 一种制备权利要求1所述含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于包括如下步骤:A method for preparing the large-diameter Ni-V rotary target containing trace elements according to claim 1, characterized in that it comprises the following steps:
    (1)真空熔炼:按各组分含量将电解镍、金属钒、石墨混合,后在1400~1550℃条件下真空熔炼70~90min,再加入钛、镁、硼精炼10~20min,后在保护气氛下浇铸得到铸锭;(1) Vacuum smelting: mix electrolytic nickel, metallic vanadium, and graphite according to the content of each component, then vacuum smelt at 1400~1550℃ for 70~90min, then add titanium, magnesium, boron for refining for 10~20min, and then protect Casting in an atmosphere to obtain an ingot;
    (2)热锻:将铸锭经机加工处理后加热至1090~1120℃,保温20~50min后,进行锻造,开锻温度为1090~1120℃,终锻温度为990~1050℃;将铸锭反复墩粗后拔长,变形量大于50%;(2) Hot forging: heat the ingot to 1090~1120℃ after machining, keep it for 20~50min, then carry out forging, the forging temperature is 1090~1120℃, and the final forging temperature is 990~1050℃; The ingot is elongated after repeated thickening, and the deformation is greater than 50%;
    (3)机加工:将步骤(2)得到的锻棒进行外表面机加处理,根据要求加工出中心通孔,锻棒的一端加工出锥形孔,得到合金圆柱;(3) Machining: the forging rod obtained in step (2) is subjected to external surface machining treatment, a central through hole is machined according to requirements, and one end of the forging rod is machined with a tapered hole to obtain an alloy cylinder;
    (4)热挤压:通过感应加热对步骤(3)得到的合金圆柱进行加热,加热温度为990~1130℃;后进行扩孔,扩孔速度为150~220mm/s;再采用二次感应加热处理,加热温度为1000~1150℃,采用热挤压机进行挤压,挤压速度为120~150mm/s,得到荒管;(4) Hot extrusion: The alloy cylinder obtained in step (3) is heated by induction heating at a heating temperature of 990 to 1130°C; then the hole is expanded at a speed of 150 to 220 mm/s; and then a secondary induction is used Heat treatment, the heating temperature is 1000-1150℃, and the hot extruder is used for extrusion, and the extrusion speed is 120-150mm/s to obtain a waste tube;
    (5)对荒管依次进行酸洗处理、固溶处理、冷轧或镗孔、退火处理、机加工或绑定。(5) Pickling treatment, solution treatment, cold rolling or boring, annealing treatment, machining or binding are carried out on the waste pipe in sequence.
  3. 根据权利要求2所述的含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于:所述步骤(1)中电解镍在580~620℃条件下烘烤5~8小时。The method for preparing a large-diameter Ni-V rotating target containing trace elements according to claim 2, wherein the electrolytic nickel in the step (1) is baked at 580-620°C for 5-8 hours .
  4. 根据权利要求2所述的含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于:所述步骤(1)中真空熔炼过程中添加钛、镁、硼采用镍箔包住钛、镁、硼的方式加入。The method for preparing a large-diameter Ni-V rotating target containing trace elements according to claim 2, wherein the addition of titanium, magnesium, and boron in the vacuum melting process in the step (1) is wrapped by nickel foil Titanium, magnesium, boron are added.
  5. 根据权利要求2所述的含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于:所述步骤(2)中墩粗的变形量大于50%。The method for preparing a large-diameter Ni-V rotating target containing trace elements according to claim 2, wherein the deformation of the thickness of the pier in the step (2) is greater than 50%.
  6. 根据权利要求2所述的含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于:所述步骤(3)中心通孔的直径为20~40mm,所述锥形孔的锥度为20°~40°。The method for preparing a large-diameter Ni-V rotating target containing trace elements according to claim 2, wherein the diameter of the central through hole in the step (3) is 20-40 mm, and the diameter of the tapered hole The taper is 20°~40°.
  7. 根据权利要求2所述的含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于:所述步骤(4)中,二次感应加热的温度比前一次感应加热的温度高10~20℃。The method for preparing a large-diameter Ni-V rotating target containing trace elements according to claim 2, characterized in that: in the step (4), the temperature of the secondary induction heating is higher than the temperature of the previous induction heating 10~20℃.
  8. 根据权利要求2所述的含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于:所述步骤(5)固溶处理将荒管加热到950~1000℃保温,然后水淬。The method for preparing a large-diameter Ni-V rotating target containing trace elements according to claim 2, characterized in that: in step (5) solution treatment, the waste pipe is heated to 950-1000°C for heat preservation, and then water Quenched.
  9. 根据权利要求2所述的含微量元素的大管径Ni-V旋转靶材的制备方法,其特征在于:所述步骤(5)的退火处理具体为:退火温度为840~870℃,保温80~90min。The method for preparing a large-diameter Ni-V rotating target containing trace elements according to claim 2, characterized in that: the annealing treatment in step (5) is specifically: annealing temperature is 840 to 870°C, heat preservation is 80°C. ~90min.
PCT/CN2019/108213 2019-09-12 2019-09-26 Large pipe-diameter ni-v rotary target material containing trace elements and preparation method therefor WO2021046928A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910869200.3 2019-09-12
CN201910869200.3A CN110468382B (en) 2019-09-12 2019-09-12 Large-diameter Ni-V rotary target containing trace elements and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2021046928A1 true WO2021046928A1 (en) 2021-03-18

Family

ID=68515848

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/108213 WO2021046928A1 (en) 2019-09-12 2019-09-26 Large pipe-diameter ni-v rotary target material containing trace elements and preparation method therefor

Country Status (2)

Country Link
CN (1) CN110468382B (en)
WO (1) WO2021046928A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111004985B (en) * 2019-11-25 2021-05-11 有研亿金新材料有限公司 Preparation method of nickel-vanadium sputtering target material
CN111304606A (en) * 2020-03-30 2020-06-19 宁波江丰电子材料股份有限公司 Preparation method of defect-free high-purity nickel-vanadium target blank and target prepared by using defect-free high-purity nickel-vanadium target blank
CN112663006A (en) * 2020-12-18 2021-04-16 宝鸡市亨信稀有金属有限公司 Nickel-vanadium alloy tube target and production method thereof
CN112845659B (en) * 2021-01-05 2022-09-16 太原科技大学 Preparation method of UNS N06600 small-caliber precise seamless pipe

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552820A (en) * 1984-04-25 1985-11-12 Lin Data Corporation Disc media
JP2000313954A (en) * 1999-03-31 2000-11-14 Praxair St Technol Inc Production of nickel/vanadium sputtering target with minimal alpha emission
CN1723292A (en) * 2002-12-09 2006-01-18 霍尼韦尔国际公司 High purity nickel/vanadium sputtering components, and methods of making sputtering components
CN1852998A (en) * 2003-10-07 2006-10-25 株式会社日矿材料 High-purity Ni-V alloy, target therefrom, high-purity Ni-V alloy thin film and process for producing high-purity Ni-V alloy
CN103710577A (en) * 2014-01-16 2014-04-09 南京达迈科技实业有限公司 Vanadium-nickel alloy magnetron sputtering rotating target material containing small amount of rare-earth elements and preparation method thereof
CN104014767A (en) * 2014-06-05 2014-09-03 贵研铂业股份有限公司 Method for preparing NiV alloy target

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105734507B (en) * 2016-04-05 2018-06-19 基迈克材料科技(苏州)有限公司 Form a film uniform fine grain nickel alloy rotary target material and its hot extrusion optimization preparation method
CN107190158B (en) * 2017-05-19 2019-01-11 江苏隆达超合金航材有限公司 Reduce the vacuum induction melting technique of O, N, S content in nickel base superalloy
CN108384992A (en) * 2018-04-20 2018-08-10 温州市赢创新材料技术有限公司 A kind of high-strength corrosion-resisting nickel base superalloy and its manufacturing method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552820A (en) * 1984-04-25 1985-11-12 Lin Data Corporation Disc media
JP2000313954A (en) * 1999-03-31 2000-11-14 Praxair St Technol Inc Production of nickel/vanadium sputtering target with minimal alpha emission
CN1723292A (en) * 2002-12-09 2006-01-18 霍尼韦尔国际公司 High purity nickel/vanadium sputtering components, and methods of making sputtering components
CN1852998A (en) * 2003-10-07 2006-10-25 株式会社日矿材料 High-purity Ni-V alloy, target therefrom, high-purity Ni-V alloy thin film and process for producing high-purity Ni-V alloy
CN103710577A (en) * 2014-01-16 2014-04-09 南京达迈科技实业有限公司 Vanadium-nickel alloy magnetron sputtering rotating target material containing small amount of rare-earth elements and preparation method thereof
CN104014767A (en) * 2014-06-05 2014-09-03 贵研铂业股份有限公司 Method for preparing NiV alloy target

Also Published As

Publication number Publication date
CN110468382B (en) 2021-04-09
CN110468382A (en) 2019-11-19

Similar Documents

Publication Publication Date Title
WO2021046928A1 (en) Large pipe-diameter ni-v rotary target material containing trace elements and preparation method therefor
CN108823472B (en) High-strength and high-toughness Al-Zn-Mg-Cu aluminum alloy and heat treatment method thereof
WO2021174726A1 (en) Nickel-based deformed high-temperature alloy having high aluminum content and preparation method therefor
CN109355530B (en) Preparation method and application of heat-resistant titanium alloy wire
CN100519813C (en) High-strength toughness cold working die steel and method of producing the same
CN112695255B (en) Preparation method of ferrite martensite steel clad tube
CN109161727B (en) Titanium alloy for manufacturing electric arc/electron beam fuse additive and preparation method thereof
CN101654764B (en) Iron-nickel based highly elastic alloy, capillary pipe thereof and method for manufacturing capillary pipe
CN112139415B (en) Method for producing difficult-to-deform nickel-based high-temperature alloy through compensation heating assisted free forging
CN109234554B (en) Preparation method of high-temperature titanium alloy bar
CN108504897A (en) A kind of forging method of near β type titanium alloys and the titanium alloy rod bar
CN114645162A (en) Manufacturing method of fine-grain homogeneous disc forging of high-temperature alloy difficult to deform
CN104372216B (en) A kind of heat top casting technique of 7A04 aluminium alloys and its aluminium alloy
CN111850372A (en) A series of FeCoCrNiW (VC)XPreparation of high-entropy alloy and precipitation strengthening process thereof
CN114107834B (en) High-strength iron-nickel-molybdenum alloy wire and low-cost preparation method thereof
CN108977689B (en) Metastable beta titanium alloy plate and processing method thereof
WO2021046929A1 (en) Large-diameter ni-cr rotating target containing trace elements and preparation method therefor
CN106334883A (en) High-strength corrosion-resistant high-temperature copper-based brazing material and manufacturing method thereof
CN114905188A (en) Corrosion-resistant and high-temperature-resistant nickel-based alloy welding wire and preparation method thereof
CN109778002A (en) A kind of rare earth titanium alloy for silk material 3D printing
CN104404325B (en) A kind of heat top casting technique of 7085 aluminium alloy and its aluminium alloy
CN109182906A (en) A kind of high temperature resistance and high strength nut and its production method
CN111850349B (en) Hot processing method of cobalt-based high-temperature alloy
CN113897513B (en) 1200 MPa-level nitric acid corrosion resistant high-strength titanium alloy and preparation method thereof
CN115404383B (en) High-strength nickel-based alloy wire for nuclear power, manufacturing method and application

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19945357

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19945357

Country of ref document: EP

Kind code of ref document: A1