阅读说明：本技术 一种大规格钼铌合金靶材的轧制制备方法 (Rolling preparation method of large-size molybdenum-niobium alloy target ) 是由 杨景红 耿宏安 张军海 于 2021-07-26 设计创作，主要内容包括：一种大规格钼铌合金靶材的轧制制备方法,具体制备方法为：将靶材合金原料配粉混合均匀,经冷等静压、热等静压、带包套轧制后校平退火,除去包套加工至规定尺寸,其中带包套轧制的开坯温度为1400-1450℃,道次变性量为20-30%,降温轧制至终轧温度为1250℃。本发明可轧制生产钼铌靶坯,根据设备尺寸,可做到大规格尺寸,可轧制2000mm以上长条靶材,相比烧结靶材,轧制靶材致密度高,可达到理论密度。(A rolling preparation method of a large-size molybdenum-niobium alloy target material comprises the following specific steps: uniformly mixing the powder of the alloy raw material of the target material, leveling and annealing after cold isostatic pressing, hot isostatic pressing and rolling with a sheath, removing the sheath and processing to the specified size, wherein the cogging temperature of the rolling with the sheath is 1400-1450 ℃, the pass modification amount is 20-30%, and the temperature is reduced and rolled to the final rolling temperature of 1250 ℃. The invention can roll and produce the molybdenum niobium target blank, can achieve large size according to the size of equipment, can roll the long target material with the size of more than 2000mm, has high density of the rolled target material compared with the sintered target material, and can achieve the theoretical density.)

1. A rolling preparation method of a large-size molybdenum-niobium alloy target is characterized by comprising the following specific steps: the target material alloy raw materials are proportionally mixed and evenly pulverized, and then are subjected to cold isostatic pressing, package sleeve vacuumizing and exhausting, hot isostatic pressing, package sleeve rolling and annealing leveling, the package sleeve is removed and processed to a specified size, wherein the hot isostatic pressing temperature is 1250-.

2. The rolling preparation method of the large-size molybdenum-niobium alloy target material according to claim 1, wherein the target material alloy raw materials Mo and Nb are mixed according to a mass ratio of 9: 1.

3. The rolling preparation method of the large-size molybdenum-niobium alloy target material according to claim 1, wherein the target material alloy is mixed by a vacuum mixer for 18-24 hours.

4. The rolling preparation method of the large-size molybdenum-niobium alloy target material according to claim 1, wherein the sheath preparation method comprises the following steps: designing a sheath according to the shape and size of the cold isostatic pressing blank, blanking and bending by using a 2-3mm titanium plate, wherein the gap between the sheath and the blank is less than 1mm, performing argon arc welding at the connection interface of the titanium plate, and arranging an air suction nozzle.

5. The rolling preparation method of the large-size molybdenum-niobium alloy target material according to claim 1, wherein the method for vacuumizing the sheath comprises the following steps: sealing the cold isostatic pressed compact in a sheath, vacuumizing at room temperature, heating to 0.001Pa slowly, keeping the temperature at 50 ℃ for 0.5-2h, heating to 500-600 ℃, keeping the temperature for 4-8h until the vacuum degree reaches 0.001-0.0001 Pa, and sealing and welding an air suction nozzle of the sheath.

6. The rolling preparation method of the large-size molybdenum-niobium alloy target material according to claim 1, wherein the specific sheath rolling method comprises the following steps: and hot isostatic pressing and then direct tape wrapping and rolling.

7. The rolling preparation method of the large-size molybdenum-niobium alloy target material as claimed in claim 1, wherein the temperature of the post-rolling leveling annealing is 1200-1300 ℃, and the temperature is kept for 0.5-1 h.

Technical Field

The invention belongs to the technical field of target production, and particularly relates to a rolling preparation method of a large-size molybdenum-niobium alloy target.

Background

Molybdenum and molybdenum alloy targets are mainly used for manufacturing thin film transistors, liquid crystal display panels and solar cells, at present, high-end targets are monopolized by large foreign companies, target enterprises in China concentrate on the field of low-end products, molybdenum targets of part of enterprises pass relevant certification at present and are switched into downstream enterprises, molybdenum targets such as molybdenum niobium, molybdenum titanium, molybdenum tantalum and the like are added due to active alloy elements, alloy densification is difficult, oxygen content is difficult to control, in addition, due to the fact that alloy strength is improved, deformation resistance is large, plastic deformation capacity is poor, rolling is difficult, at present, the molybdenum targets are mainly produced by a wire cutting machine after high-temperature sintering, sintering density is low, and grain size and oxygen content are difficult to guarantee.

Disclosure of Invention

The invention provides a rolling preparation method of a large-size molybdenum-niobium alloy target material, which is used for solving the problem that the molybdenum-niobium alloy target material is difficult to produce a large-size target blank through a rolling process.

In order to achieve the purpose, the invention adopts the technical scheme that:

a rolling preparation method of a large-size molybdenum-niobium alloy target material comprises the following specific steps: the target material alloy raw materials are proportionally mixed and evenly pulverized, and then are subjected to cold isostatic pressing, package sleeve vacuumizing and exhausting, hot isostatic pressing, package sleeve rolling and annealing leveling, the package sleeve is removed and processed to a specified size, wherein the hot isostatic pressing temperature is 1250-.

Further optimizing, mixing the target alloy raw materials Mo and Nb according to the mass ratio of 9: 1.

Further optimizing, the target alloy is mixed by a vacuum mixer for 18-24 h.

Further optimizing, the preparation method of the sheath comprises the following steps: designing a sheath according to the shape and size of the cold isostatic pressing blank, blanking and bending by using a 2-3mm titanium plate, wherein the gap between the sheath and the blank is less than 1mm, performing argon arc welding at the connection interface of the titanium plate, and arranging an air suction nozzle.

Further preferably, the method for vacuumizing and exhausting the ladle sleeve comprises the following steps: sealing the cold isostatic pressed compact in a sheath, vacuumizing at room temperature, heating to 0.001Pa slowly, keeping the temperature at 50 ℃ for 0.5-2h, heating to 500-600 ℃, keeping the temperature for 4-8h until the vacuum degree reaches 0.001-0.0001 Pa, and sealing and welding an air suction nozzle of the sheath.

Further optimizing, the specific method for sheath rolling comprises the following steps: and hot isostatic pressing and then direct tape wrapping and rolling.

Further optimizing, wherein the temperature of the leveling annealing after rolling is 1200-1300 ℃, and the temperature is kept for 0.5-1 h.

The invention has the beneficial effects that:

1. compared with the traditional rolling without a sheath, the hot isostatic pressing sintering is directly rolled with the sheath, and because the sheath is vacuum-sealed and compactly combined, the oxygenation in the sintering process is avoided, the purity of the target material is ensured, and the formation of rolling cracks is avoided;

2. the hot isostatic pressing sintering has higher density and low porosity in a sintered blank, and in addition, because the hot isostatic pressing sintering temperature is low, the solid solution amount of alloy elements is less, the deformation resistance is small, and the rolling cracking tendency is greatly reduced;

3. the hot isostatic pressing sintering ensures higher density, has fine grains, and can promote the grains of the rolling target material to be obviously refined, and the average grain size reaches within 5 um;

in conclusion, the molybdenum-niobium target blank can be rolled to produce a large-size blank according to the equipment specification, and a long-strip target with the size of more than 2000mm can be rolled.

Drawings

FIG. 1 is a gold phase diagram of a molybdenum-niobium planar target material prepared by the method of the present invention under 100X;

FIG. 2 is a gold phase diagram of a molybdenum-niobium planar target material prepared by the method of the invention at 500X;

fig. 3 is a gold phase diagram of a conventional molybdenum-niobium planar target 100X;

fig. 4 is a gold phase diagram of a conventional molybdenum-niobium planar target at 500X.

Detailed Description

The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention.

Example 1

A rolling preparation method of a large-size molybdenum-niobium alloy target specifically comprises the following steps: mixing the raw materials Mo and Nb for 18 hours by a vacuum mixer according to the mass ratio of 9:1, uniformly mixing, filling the mixture into a rubber sleeve mold, sealing, keeping the pressure in a cold isostatic press at 160MPa for 3min, and pressing into a green compact; pressing the specification of the blank to manufacture a sheath, placing the pressed blank into the sheath, vacuumizing to 0.001Pa at room temperature, slowly heating, keeping the temperature at 50 ℃ in each gradient stage for 0.5h, keeping the temperature at 500 ℃ for 4h, keeping the vacuum degree at 0.0008Pa, sealing and welding the sheath; hot isostatic pressing is carried out after welding is finished, the hot isostatic pressing temperature is 1250 ℃, and heat preservation is carried out for 3 hours; hot isostatic pressing, direct sheathed rolling, wherein the cogging temperature is 1400 ℃, the pass deformation is 20%, cooling rolling is carried out after cogging, the pass deformation is 20-30%, the final rolling temperature is 1250 ℃, and the thickness of the rolling stage is 35-28-22-18-14mm respectively; and (3) annealing and leveling at 1200 ℃ for 0.5h, machining to remove a sheath, trimming, milling and grinding the surface to finally obtain the molybdenum-niobium planar target material with the size of 125 x 900 x 12 mm.

Example 2

A rolling preparation method of a large-size molybdenum-niobium alloy target specifically comprises the following steps: mixing the raw materials Mo and Nb by a vacuum mixer according to the mass ratio of 9:1 for 20h, uniformly mixing, filling the mixture into a rubber sleeve mold, sealing, keeping the pressure in a cold isostatic press at 180MPa for 6min, and pressing into a green compact; pressing the specification of the blank to manufacture a sheath, placing the pressed blank into the sheath, vacuumizing to 0.001Pa at room temperature, slowly heating, keeping the temperature at 50 ℃ in each gradient stage for 0.5h, keeping the temperature at 550 ℃ for 6h, keeping the vacuum degree at 0.0005Pa, sealing and welding the sheath; hot isostatic pressing is carried out after welding is finished, the hot isostatic pressing temperature is 1320 ℃, and heat preservation is carried out for 3 hours; hot isostatic pressing, direct sheathed rolling, wherein the cogging temperature is 1425 ℃, the deformation is 25%, cooling rolling is carried out after cogging, the finish rolling temperature is 1250 ℃, the deformation of rolling passes is 15-30%, and the thickness of the rolling stages is 35-26-22-18-14mm respectively; and (3) annealing and leveling at 1250 ℃ for 0.8h, machining to remove a sheath, trimming, milling and grinding the surface to finally obtain the molybdenum-niobium planar target material with the size of 125 x 900 x 12 mm.

Example 3

A rolling preparation method of a large-size molybdenum-niobium alloy target specifically comprises the following steps: mixing Mo and Nb raw materials for 24 hours by a vacuum mixer according to the mass ratio of 9: 1; mixing, placing into a rubber sleeve mold, sealing, maintaining the pressure in a cold isostatic press at 200MPa for 10min, and pressing into a green compact; pressing the specification of the blank to manufacture a sheath, placing the pressed blank into the sheath, vacuumizing to 0.001Pa, slowly heating, keeping the temperature at 50 ℃ in each gradient stage for 0.5h, keeping the temperature at 600 ℃ for 8h, keeping the vacuum degree at 0.0004Pa, sealing and welding the sheath; hot isostatic pressing is carried out after welding is finished, the hot isostatic pressing temperature is 1400 ℃, and heat preservation is carried out for 3 hours; hot isostatic pressing, direct sheathed rolling, wherein the cogging temperature is 1450 ℃, the deformation is 30%, cooling rolling is carried out after cogging, the finish rolling temperature is 1250 ℃, the pass deformation is 15-30%, and the thickness in the rolling stage is 35-24-20-17-14mm respectively; and (3) annealing and leveling at 1300 ℃ for 1h, machining to remove the sheath, trimming, milling and grinding the surface to finally obtain the molybdenum-niobium planar target material with the size of 125 x 900 x 12 mm.

Comparative example 1

The density of the molybdenum-niobium planar target prepared in the example 1 and the density of the molybdenum-niobium planar target rolled without a sheath in the traditional market are detected by a drainage method, and the density of the molybdenum-niobium target in the example 1 is 10.02g/cm³The density of the traditional commercial molybdenum niobium sintered planar target material reaches 9.2 to 9.6g/cm³(ii) a Metallographic observation is respectively carried out on the molybdenum-niobium planar target material prepared in the embodiment 1 and the traditional commercially available molybdenum-niobium planar target material by 100X and 500X under an optical microscope, and the test results are shown in fig. 1, fig. 2, fig. 3 and fig. 4, wherein the average grain size of the molybdenum-niobium target material in the embodiment 1 is less than 5um, and the average grain size of the traditional commercially available molybdenum-niobium planar target material rolled without a sheath is more than 10 um; oxygen content analysis was performed on the molybdenum-niobium planar target prepared in example 1 and the molybdenum-niobium planar target rolled without a sheath in the conventional market, and the oxygen content of the molybdenum-niobium planar target in example 1 was 480ppm, and the oxygen content of the molybdenum-niobium planar target rolled without a sheath in the conventional market was 1080 ppm. In conclusion, the average crystal grain of the molybdenum-niobium planar target material prepared by the method is far smaller than that of the traditional target material, the compactness of the molybdenum-niobium planar target material is higher than that of the traditional target material, and the oxygen content is extremely low.

The foregoing illustrates and describes the principal features, utilities, and principles of the invention, as well as advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to explain the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as expressed in the following claims. The scope of the invention is defined by the appended claims and equivalents thereof.