A method for preparing a molybdenum-titanium alloy target blank

Abstract

The application provides a preparation method of a molybdenum-titanium alloy target blank, and the preparation method comprises the following steps: (1) mixing molybdenum powder, titanium powder and carbon powder, and sequentially performing first ball milling and second ball milling to obtain mixed powder; (2) sequentially performing cold isostatic pressing and vacuum sintering on the mixed powder in step (1) to obtain the molybdenum-titanium alloy target blank. The molybdenum-titanium alloy target blank with low oxygen, high density and uniform element distribution is prepared by adding a certain proportion of carbon powder, combining two high-energy ball millings, and then sequentially performing cold isostatic pressing and vacuum sintering.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of target blank preparation and relates to a preparation method of a molybdenum-titanium alloy target blank. BACKGROUND

[0002] Molybdenum target sputtered film is widely used in the electronic information industry due to its good conductivity and extremely stable chemical properties, and is particularly widely used in the display field, usually as a diffusion barrier layer in wiring, but the pure molybdenum target film is slightly insufficient in adhesion, and adding a certain amount of titanium element in the molybdenum target can effectively improve this defect and make the adhesion and various properties more balanced.

[0003] The preparation of molybdenum-titanium alloy is mostly by casting and powder metallurgy, and the molybdenum-titanium alloy prepared by powder metallurgy has become the mainstream preparation method due to its small and uniform grain size and good element distribution uniformity. The main process of preparing molybdenum-titanium alloy by powder metallurgy is: uniformly mixing powders, pressing and forming, and sintering.

[0004] Sintering is usually divided into hot isostatic pressing sintering, hot pressing sintering and vacuum sintering. Hot isostatic pressing can sinter alloys with high density and fine grain size at a lower temperature due to its high pressure characteristics, but the equipment is expensive and the manufacturing cost is high. Hot pressing sintering can also obtain alloys with high density, and CN111304607A discloses a manufacturing method of molybdenum-titanium alloy target material, which comprises: mixing molybdenum powder and titanium powder under the protection of inert gas; cold isostatic pressing the mixed powder; and pressing and sintering the formed molybdenum-titanium mixed powder to obtain a molybdenum-titanium ingot, but the size is usually affected. Vacuum sintering equipment is simple and has low cost, and is widely used, but when preparing alloys with large differences in melting point, such as molybdenum and titanium with large differences in melting point and molybdenum with a melting point as high as 2620℃, it is usually difficult to meet the requirements of high density and grain size when prepared by vacuum sintering, and has certain defects.

[0005] In addition, due to the strong oxygen affinity of titanium, it is difficult to prepare low-oxygen titanium powder, which leads to a high oxygen content of the sintered molybdenum-titanium alloy, and the performance of the sputtered film is also restricted to a certain extent, therefore, the oxygen content of the molybdenum-titanium target material needs to be optimized.

[0006] In summary, it is an urgent problem for those skilled in the art to provide a preparation method of a molybdenum-titanium alloy target blank with low oxygen content, high density and uniform element distribution. SUMMARY

[0007] The purpose of the present application is to provide a preparation method of a molybdenum-titanium alloy target blank, which adds a certain proportion of carbon powder and combines two high-energy ball milling, and then sequentially performs cold isostatic pressing and vacuum sintering to prepare a molybdenum-titanium alloy target blank with low oxygen content, high density and uniform element distribution.

[0008] To achieve the object of the present application, the present application adopts the following technical solutions:

[0009] The present application provides a preparation method of a molybdenum-titanium alloy target blank, which comprises the following steps:

[0010] (1) mixing molybdenum powder, titanium powder and carbon powder, and sequentially performing first ball milling and second ball milling to obtain mixed powder;

[0011] (2) sequentially performing cold isostatic pressing and vacuum sintering on the mixed powder of step (1) to obtain the molybdenum-titanium alloy target blank.

[0012] In the present application, the atomic ratio of molybdenum to titanium in the molybdenum-titanium alloy target blank is 1:1.

[0013] The preparation method of the molybdenum-titanium alloy target blank provided by the present application adds a certain proportion of carbon powder and combines two high-energy ball millings to obtain MoTi alloy powder with uniform element distribution and high specific surface energy, which has higher density under the same vacuum sintering temperature, and then sequentially performs cold isostatic pressing and vacuum sintering, and oxygen is combined with carbon to volatilize during vacuum sintering, thereby preparing a molybdenum-titanium alloy target blank with low oxygen, high density and uniform element distribution.

[0014] As a preferred technical solution of the present application, the average particle size of the molybdenum powder in step (1) is 2-6 μm, for example, it can be 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm or 5.5 μm, etc., but is not limited to the listed values, and other values not listed within the value range are also applicable.

[0015] Preferably, the oxygen content of the molybdenum powder in step (1) is 300-2000 ppm, for example, it can be 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 1200 ppm, 1500 ppm, 1600 ppm or 1800 ppm, etc., but is not limited to the listed values, and other values not listed within the value range are also applicable.

[0016] In the present application, the oxygen content is the mass content of oxygen.

[0017] Preferably, the average particle size of the titanium powder in step (1) is 30-50 μm, for example, it can be 32 μm, 34 μm, 35 μm, 38 μm, 40 μm, 42 μm, 44 μm, 45 μm or 48 μm, etc., but is not limited to the listed values, and other values not listed within the value range are also applicable.

[0018] Preferably, the oxygen content of the titanium powder in step (1) is ≥ 3000 ppm, such as 3100 ppm, 3200 ppm, 3300 ppm, 3400 ppm, 3500 ppm, 3600 ppm, 3800 ppm, 4000 ppm, or 4200 ppm, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0019] Preferably, the average particle size of the carbon powder in step (1) is 1-4 μm, such as 1 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.2 μm, 2.5 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, or 3.8 μm, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0020] It is worth noting that, by adding a small amount of carbon powder, the oxygen in the alloy powder is combined with carbon and volatilized during vacuum sintering, thereby reducing the oxygen content in the alloy.

[0021] In the present application, the oxygen content of the carbon powder in step (1) is less than 0.5% of the mass of the carbon powder, and the oxygen content of the carbon powder is negligible relative to the amount of carbon powder added and the oxygen content of the molybdenum powder and titanium powder.

[0022] Preferably, the mass content of the molybdenum powder in the mixed powder obtained in step (1) is 66.7-95 wt%, such as 68 wt%, 70 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, 85 wt%, 88 wt%, 90 wt%, 92 wt%, or 94 wt%, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0023] Preferably, the mass content of the titanium powder in the mixed powder obtained in step (1) is 5-33.3 wt%, such as 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, or 33 wt%, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0024] Preferably, the amount of carbon powder added in step (1) is 55-70% of the oxygen content in the obtained mixed powder, such as 56%, 58%, 60%, 62%, 65%, 66%, or 68%, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0025] Preferably, the medium for the first ball milling in step (1) comprises molybdenum balls.

[0026] Preferably, the ball-to-material ratio of the first ball milling in step (1) is 1:(4-7), for example, it can be 1:4.5, 1:5, 1:5.5, 1:6 or 1:6.5, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0027] Preferably, the rotation speed of the first ball milling in step (1) is 300-400 r / min, for example, it can be 310 r / min, 320 r / min, 330 r / min, 340 r / min, 350 r / min, 360 r / min, 370 r / min, 380 r / min or 390 r / min, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0028] Preferably, the time of the first ball milling in step (1) is 6-8 h, for example, it can be 6.2 h, 6.5 h, 6.8 h, 7 h, 7.2 h, 7.5 h or 7.8 h, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0029] Preferably, the first ball milling in step (1) is carried out in a protective atmosphere.

[0030] In the present application, the protective atmosphere includes argon; the first ball milling is carried out under micro-positive pressure.

[0031] As a preferred technical solution of the present application, the medium of the second ball milling in step (1) includes molybdenum balls.

[0032] Preferably, the ball-to-material ratio of the second ball milling in step (1) is 1:(4-7), for example, it can be 1:4.5, 1:5, 1:5.5, 1:6 or 1:6.5, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0033] Preferably, the rotation speed of the second ball milling in step (1) is 450-550 r / min, for example, it can be 460 r / min, 470 r / min, 480 r / min, 490 r / min, 500 r / min, 510 r / min, 520 r / min, 530 r / min or 540 r / min, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0034] In the present application, by controlling the rotation speed parameter range of the first ball milling and the second ball milling, the use of high-energy ball milling not only ensures a more uniform element distribution, improves the specific surface energy and activation energy of the alloy powder, and at the same time, shortens the ball milling time.

[0035] Preferably, the second ball milling in step (1) is performed for 8-10 hours, for example, 8.2 hours, 8.5 hours, 8.8 hours, 9 hours, 9.2 hours, 9.5 hours, or 9.8 hours, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0036] Preferably, the second ball milling in step (1) is performed in a protective atmosphere.

[0037] In the present application, the second ball milling is performed under micro-positive pressure.

[0038] As a preferred technical solution of the present application, the cold isostatic pressing in step (2) is performed at a pressure of 200-300 MPa, for example, 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, or 290 MPa, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0039] Preferably, the cold isostatic pressing in step (2) is performed for 5-40 minutes, for example, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, or 35 minutes, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0040] In the present application, before the cold isostatic pressing, a mold is also filled, and then a tamping tool is used for mold tamping to ensure that the thickness in each direction is within the same level range; after the cold isostatic pressing, demolding is also included to obtain a molybdenum-titanium alloy green body.

[0041] As a preferred technical solution of the present application, the vacuum sintering in step (2) is performed at a vacuum degree of <10 -3 Pa, for example, 9x10 -4 Pa, 7x10 -4 Pa, 5x10 -4 Pa, 3x10 -4 Pa, or 10 -4 Pa, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0042] Preferably, the vacuum sintering in step (2) includes first temperature rising, second temperature rising, and furnace cooling in sequence.

[0043] Preferably, the end point of the first temperature rising is 700-1000℃, for example, 720℃, 750℃, 780℃, 800℃, 820℃, 850℃, 870℃, 900℃, 920℃, 950℃, or 980℃, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0044] Preferably, the holding time of the first temperature rising is 1-3h, for example, it can be 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h or 2.8h, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0045] In the present application, by controlling the process parameters of the first temperature rising, the volatile substances in the molybdenum-titanium alloy green body are volatilized, and the impurity content in the target blank after vacuum sintering is reduced.

[0046] Preferably, the end point of the second temperature rising is 1400-1600℃, for example, it can be 1420℃, 1450℃, 1480℃, 1500℃, 1520℃, 1550℃ or 1580℃, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0047] Preferably, the holding time of the second temperature rising is 2-6h, for example, it can be 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0048] In the present application, by controlling the process parameters of the second temperature rising, the densification degree of the molybdenum-titanium alloy target blank is improved, and the carbon and oxygen are combined and volatilized, reducing the oxygen content.

[0049] As a preferred technical solution of the present application, the oxygen content of the molybdenum-titanium alloy target blank in step (2) is <800ppm, for example, it can be 700ppm, 600ppm, 500ppm, 400ppm, 300ppm, 200ppm or 100ppm, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable, preferably <300ppm.

[0050] Preferably, the density of the molybdenum-titanium alloy target blank in step (2) is ≥98%.

[0051] As a preferred technical solution of the present application, the preparation method comprises the following steps:

[0052] (1) mixing molybdenum powder with an average particle size of 2-6μm and an oxygen content of 300-2000ppm, titanium powder with an average particle size of 30-50μm and an oxygen content of ≥3000ppm, and carbon powder with an average particle size of 1-4μm, then first ball milling in a protective atmosphere for 6-8h with a ball-to-material ratio of 1:(4-7) and a rotation speed of 300-400r / min, and then second ball milling in a protective atmosphere for 8-10h with a ball-to-material ratio of 1:(4-7) and a rotation speed of 450-550r / min, to obtain a mixed powder;

[0053] The mass content of the molybdenum powder in the obtained mixed powder is 66.7-95wt%; the mass content of the titanium powder in the obtained mixed powder is 5-33.3wt%; and the added amount of the carbon powder is 55-70% of the oxygen content in the obtained mixed powder.

[0054] (2) cold isostatic pressing the mixed powder in step (1) at a pressure of 200-300MPa and holding for 5-40min, and then vacuum sintering at a vacuum degree of <10 -3 Pa to obtain a molybdenum-titanium alloy target blank with an oxygen content of <800ppm and a density of ≥98%;

[0055] The vacuum sintering comprises sequentially a first temperature rising, a second temperature rising and furnace cooling;

[0056] The end point of the first temperature rising is 700-1000℃, and the holding time is 1-3h;

[0057] The end point of the second temperature rising is 1400-1600℃, and the holding time is 2-6h.

[0058] Compared with the prior art, the present application has the following beneficial effects:

[0059] The preparation method of the molybdenum-titanium alloy target blank provided by the present application adds a certain proportion of carbon powder and combines two high-energy ball-milling processes to obtain MoTi alloy powder with uniform element distribution and high specific surface energy, which has higher density at the same vacuum sintering temperature. Subsequently, cold isostatic pressing and vacuum sintering are sequentially performed. Oxygen is combined with carbon and volatilized during vacuum sintering, thereby reducing the oxygen content in the molybdenum-titanium alloy. At the same time, reasonable process parameters are combined to obtain a molybdenum-titanium alloy target blank with low oxygen content, high density and uniform element distribution. DETAILED DESCRIPTION

[0060] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0061] In the following examples and comparative examples, the atomic ratio of molybdenum to titanium in the molybdenum-titanium alloy target blank is 1:1; the oxygen content refers to the mass content of oxygen element; and the added amount of the carbon powder is determined according to the oxygen content in the obtained mixed powder.

[0062] Example 1

[0063] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank, which comprises the following steps:

[0064] (1) mixing molybdenum powder with purity of 3N, average particle size of 4 μm and oxygen content of 600 ppm, titanium powder with purity of 3N, average particle size of 40 μm and oxygen content of 3000 ppm and carbon powder with average particle size of 2 μm, then first ball milling for 7 h in micro-positive pressure argon, ball-to-material ratio of 1:5, ball milling medium being molybdenum ball and rotating speed being 350 r / min, and then second ball milling for 9 h in micro-positive pressure argon, ball-to-material ratio of 1:5, ball milling medium being molybdenum ball and rotating speed being 500 r / min, to obtain mixed powder;

[0065] The mass content of the molybdenum powder in the obtained mixed powder is 66.7 wt%; the mass content of the titanium powder in the obtained mixed powder is 33.3 wt%; and the addition amount of the carbon powder is 840 ppm;

[0066] (2) loading the mixed powder in step (1) into a cold isostatic pressing mold, then tamping using a tamping tool, cold isostatic pressing at a pressure of 250 MPa and keeping pressure for 20 min, vacuum sintering after demolding at a vacuum degree of 10 -4 Pa, and finally machining to obtain a molybdenum-titanium alloy target blank;

[0067] The vacuum sintering comprises first temperature rising, second temperature rising and furnace cooling in sequence;

[0068] The end point of the first temperature rising is 850 ℃, and the holding time is 2 h;

[0069] The end point of the second temperature rising is 1400 ℃, and the holding time is 4 h.

[0070] Example 2

[0071] The embodiment provides a preparation method of a molybdenum-titanium alloy target blank, and the preparation method comprises the following steps:

[0072] (1) mixing molybdenum powder with purity of 3N, average particle size of 2 μm and oxygen content of 600 ppm, titanium powder with purity of 3N, average particle size of 32 μm and oxygen content of 3300 ppm and carbon powder with average particle size of 1 μm, then first ball milling for 8 h in micro-positive pressure argon, ball-to-material ratio of 1:5, ball milling medium being molybdenum ball and rotating speed being 300 r / min, and then second ball milling for 10 h in micro-positive pressure argon, ball-to-material ratio of 1:5, ball milling medium being molybdenum ball and rotating speed being 450 r / min, to obtain mixed powder;

[0073] The mass content of the molybdenum powder in the obtained mixed powder is 66.7 wt%; the mass content of the titanium powder in the obtained mixed powder is 33.3 wt%; and the addition amount of the carbon powder is 900 ppm;

[0074] (2) The mixed powder of step (1) is loaded into a cold isostatic pressing mold, then tamping is performed using a tamping tool, cold isostatic pressing is performed at a pressure of 200 MPa and pressure is maintained for 35 min, after demolding, vacuum sintering is performed at a vacuum degree of 3 x 10 -4 Pa, and finally machining is performed to obtain a molybdenum-titanium alloy target blank;

[0075] The vacuum sintering comprises a first temperature rise, a second temperature rise and furnace cooling in sequence;

[0076] The end point of the first temperature rise is 700 DEG C, and the holding time is 2.5 h;

[0077] The end point of the second temperature rise is 1500 DEG C, and the holding time is 5 h.

[0078] Example 3

[0079] The embodiment provides a preparation method of a molybdenum-titanium alloy target blank, and the preparation method comprises the following steps:

[0080] (1) Molybdenum powder with a purity of 3N, an average particle size of 6 μm and an oxygen content of 1800 ppm, titanium powder with a purity of 3N, an average particle size of 45 μm and an oxygen content of 3900 ppm and carbon powder with an average particle size of 1 μm are mixed, then first ball milling is performed in micro-positive pressure argon for 6 h with a ball-to-material ratio of 1:5, a ball milling medium of molybdenum balls and a rotating speed of 400 r / min, and then second ball milling is performed in micro-positive pressure argon for 8 h with a ball-to-material ratio of 1:5, a ball milling medium of molybdenum balls and a rotating speed of 550 r / min to obtain mixed powder;

[0081] The mass content of the molybdenum powder in the obtained mixed powder is 66.7 wt%; the mass content of the titanium powder in the obtained mixed powder is 33.3 wt%; and the addition amount of the carbon powder is 1500 ppm;

[0082] (2) The mixed powder of step (1) is loaded into a cold isostatic pressing mold, then tamping is performed using a tamping tool, cold isostatic pressing is performed at a pressure of 300 MPa and pressure is maintained for 10 min, after demolding, vacuum sintering is performed at a vacuum degree of 5 x 10 -4 Pa, and finally machining is performed to obtain a molybdenum-titanium alloy target blank;

[0083] The vacuum sintering comprises a first temperature rise, a second temperature rise and furnace cooling in sequence;

[0084] The end point of the first temperature rise is 1000 DEG C, and the holding time is 1.5 h;

[0085] The end point of the second temperature rise is 1600 DEG C, and the holding time is 2 h.

[0086] Example 4

[0087] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the adding amount of the carbon powder in step (1) is adjusted to 400 ppm, other conditions are the same as those in Embodiment 1.

[0088] Embodiment 5

[0089] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the adding amount of the carbon powder in step (1) is adjusted to 2000 ppm, other conditions are the same as those in Embodiment 1.

[0090] Embodiment 6

[0091] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the rotating speed of the first ball milling and the second ball milling in step (1) is adjusted to 200 r / min, other conditions are the same as those in Embodiment 1.

[0092] Embodiment 7

[0093] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the rotating speed of the second ball milling in step (1) is adjusted to 350 r / min, other conditions are the same as those in Embodiment 1.

[0094] Embodiment 8

[0095] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the end point of the first temperature rising in step (2) is adjusted to 500 ℃, other conditions are the same as those in Embodiment 1.

[0096] Embodiment 9

[0097] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the end point of the second temperature rising in step (2) is adjusted to 1200 ℃, other conditions are the same as those in Embodiment 1.

[0098] Embodiment 10

[0099] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the end point of the second temperature rising in step (2) is adjusted to 1800 ℃, other conditions are the same as those in Embodiment 1.

[0100] Embodiment 11

[0101] The present embodiment provides a preparation method of a molybdenum-titanium alloy target blank. Except that the first temperature rising in step (2) is not performed, other conditions are the same as those in Embodiment 1.

[0102] Embodiment 12

[0103] The embodiment provides a preparation method of a molybdenum-titanium alloy target blank, wherein, except that the second temperature rising is not performed in the step (2) vacuum sintering, other conditions are the same as those in the embodiment 1.

[0104] Comparative example 1

[0105] The comparative example provides a preparation method of a molybdenum-titanium alloy target blank, wherein, except that the carbon powder is not added, other conditions are the same as those in the embodiment 1.

[0106] Comparative example 2

[0107] The comparative example provides a preparation method of a molybdenum-titanium alloy target blank, wherein, except that the second ball milling is not performed, other conditions are the same as those in the embodiment 1.

[0108] Performance test

[0109] The molybdenum-titanium alloy target blanks obtained in the above embodiment and comparative examples are determined for actual density according to GB / T3850-2015 'Density measurement method of dense sintered metal materials and hard alloy', the theoretical density is calculated according to a theoretical formula, and the obtained results are shown in Table 1 according to a calculation formula: density = actual density / theoretical density x 100%.

[0110] The oxygen content in the molybdenum-titanium alloy target blanks obtained in the above embodiment and comparative examples is determined by using a LECO oxygen-nitrogen-hydrogen analyzer, and the obtained results are shown in Table 1.

[0111] Table 1

[0112] Density (g / cm3) Oxygen content (ppm) Example 1 98.42 282 Example 2 98.59 276 Example 3 98.66 263 Example 4 98.32 823 Example 5 98.39 279 Example 6 95.37 301 Example 7 96.21 289 Example 8 98.10 650 Example 9 95.20 770 Example 10 98.43 289 Example 11 97.78 870 Example 12 95.24 915 Comparative Example 1 96.85 1120 Comparative Example 2 94.21 326

[0113] It can be known from Table 1 that:

[0114] (1) The preparation method of the molybdenum-titanium alloy target blank provided in the embodiments 1-3 can prepare the molybdenum-titanium alloy target blank with low oxygen content, high density and uniform element distribution by adding a certain proportion of carbon powder, combining twice high-energy ball milling, and then sequentially performing cold isostatic pressing and vacuum sintering;

[0115] (2) It can be known by comparing the embodiment 1 and the embodiments 4-5 that when the amount of the added carbon powder is small, the oxygen in the molybdenum powder and the titanium powder cannot be removed sufficiently, so that the oxygen content of the obtained molybdenum-titanium alloy target blank is high; when the amount of the added carbon powder is large, the carbon content in the obtained molybdenum-titanium alloy target blank is high, which affects the sputtering performance;

[0116] (3) It can be known by comparing the embodiment 1 and the embodiments 6-7 that when the first ball milling and / or the second ball milling is low-energy ball milling, the raw materials cannot be uniformly mixed in the same ball milling time, the specific surface energy of the molybdenum-titanium alloy powder is reduced, and the density of the obtained molybdenum-titanium alloy target blank is reduced;

[0117] (4) By comparing example 1 and examples 8, 11, it can be seen that when the end point temperature of the first temperature rise is low or the first temperature rise is not performed, the volatile substances in the molybdenum-titanium green body are not easily volatilized, resulting in a high impurity content in the obtained molybdenum-titanium alloy target body;

[0118] (5) By comparing example 1 and examples 9-10, 12, it can be seen that when the end point temperature of the second temperature rise is low or the second temperature rise is not performed, the density of the molybdenum-titanium alloy target body decreases, and the carbon and oxygen are not easily combined and volatilized, resulting in a high oxygen content in the obtained molybdenum-titanium alloy target body; when the end point temperature of the second temperature rise is high, although the density and oxygen content of the obtained target body do not change greatly, the composition segregation of the obtained molybdenum-titanium alloy target body is more serious, and the molybdenum-titanium alloy target body has a risk of cracking during processing;

[0119] (6) By comparing example 1 and comparative example 1, it can be seen that when no carbon powder is added, the oxygen in the molybdenum powder and the titanium powder cannot be completely removed, resulting in a high oxygen content and a decreased density of the obtained molybdenum-titanium alloy target body;

[0120] (7) By comparing example 1 and comparative example 2, it can be seen that when the second ball milling is not performed, the raw materials are not easily mixed, the specific surface area of the molybdenum-titanium alloy powder decreases, resulting in a decreased density and a slightly increased oxygen content of the obtained molybdenum-titanium alloy target body.

[0121] The applicant declares that the present application is illustrated by the above examples to explain the detailed structural features of the present application, but the present application is not limited to the above detailed structural features, that is, it does not mean that the present application must rely on the above detailed structural features to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of the components selected by the present application, addition of auxiliary components, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A method of producing a molybdenum-titanium alloy target blank, characterized by, The preparation method comprises the following steps: (1) mixing molybdenum powder, titanium powder and carbon powder, sequentially performing first ball milling and second ball milling to obtain mixed powder; (2) sequentially performing cold isostatic pressing and vacuum sintering on the mixed powder in step (1) to obtain the molybdenum-titanium alloy target blank; The adding amount of the carbon powder in step (1) is 55-70% of the oxygen content in the obtained mixed powder.

2. The production method according to claim 1, characterized by, The average particle size of the molybdenum powder in step (1) is 2-6 μm.

3. The preparation method according to claim 1, characterized in that, The oxygen content of the molybdenum powder in step (1) is 300-2000 ppm.

4. The method of claim 1, wherein, The average particle size of the titanium powder in step (1) is 30-50 μm.

5. The preparation method according to claim 1, characterized in that, The oxygen content of the titanium powder in step (1) is ≥3000 ppm.

6. The method of claim 1, wherein, The average particle size of the carbon powder in step (1) is 1-4 μm.

7. The preparation method according to claim 1, characterized in that, The mass content of the molybdenum powder in the obtained mixed powder in step (1) is 66.7-95 wt%.

8. The method of claim 1, wherein, The mass content of the titanium powder in the obtained mixed powder in step (1) is 5-33.3 wt%.

9. The method of claim 1, wherein, The medium of the first ball milling in step (1) comprises molybdenum balls.

10. The method of claim 1, wherein, The ball-to-material ratio of the first ball milling in step (1) is 1:(4-7).

11. The method of claim 1, wherein, The rotating speed of the first ball milling in step (1) is 300-400 r / min.

12. The method of claim 1, wherein, The time of the first ball milling in step (1) is 6-8 h.

13. The method of claim 1, wherein, The first ball milling in step (1) is performed in a protective atmosphere.

14. The method of claim 1, wherein, The medium of the second ball milling in step (1) comprises molybdenum balls.

15. The method of claim 1, wherein, The ball-to-material ratio of the second ball milling in step (1) is 1:(4-7).

16. The method of claim 1, wherein, The rotating speed of the second ball milling in step (1) is 450-550 r / min.

17. The method of claim 1, wherein, The time of the second ball milling in step (1) is 8-10 h.

18. The method of claim 1, wherein, The second ball milling in step (1) is performed in a protective atmosphere.

19. The method of claim 1, wherein, The pressure of the cold isostatic pressing in step (2) is 200-300 MPa.

20. The method of claim 1, wherein, The pressure maintaining time of the cold isostatic pressing in step (2) is 5-40 min.

21. The method of claim 1, wherein, The vacuum degree of the vacuum sintering in step (2) is <10 -3 Pa.

22. The method of claim 1, wherein, The vacuum sintering in step (2) comprises sequentially performing first temperature rising, second temperature rising and furnace cooling.

23. The method of claim 22, wherein, The terminal temperature of the first temperature rising is 700-1000 ℃.

24. The method of claim 22, wherein, The holding time of the first temperature rising is 1-3 h.

25. The preparation method according to claim 22, characterized in that, The terminal temperature of the second temperature rising is 1400-1600 ℃.

26. The method of claim 22, wherein, The holding time of the second temperature rising is 2-6 h.

27. The method of claim 1, wherein, The oxygen content of the molybdenum-titanium alloy target blank in step (2) is <800 ppm.

28. The method of claim 1, wherein, The oxygen content of the molybdenum-titanium alloy target blank in step (2) is <300 ppm.

29. The method of claim 1, wherein, The density of the molybdenum-titanium alloy target blank in step (2) is ≥98%.

30. The method of making according to any one of claims 1-29, wherein, The preparation method comprises the following steps: (1) mixing molybdenum powder with an average particle size of 2-6 μm and an oxygen content of 300-2000 ppm, titanium powder with an average particle size of 30-50 μm and an oxygen content of ≥3000 ppm, and carbon powder with an average particle size of 1-4 μm, then performing first ball milling in a protective atmosphere at a ball-to-material ratio of 1:(4-7) and a rotating speed of 300-400 r / min for 6-8 h, and then performing second ball milling in a protective atmosphere at a ball-to-material ratio of 1:(4-7) and a rotating speed of 450-550 r / min for 8-10 h to obtain mixed powder; The mass content of the molybdenum powder in the obtained mixed powder is 66.7-95wt%; the mass content of the titanium powder in the obtained mixed powder is 5-33.3wt%; the added amount of the carbon powder is 55-70% of the oxygen content in the obtained mixed powder; (2) The mixed powder of step (1) is cold isostatic pressed at a pressure of 200-300 MPa and held for 5-40 min, and then vacuum sintered at a vacuum degree <10 -3 Pa to obtain a molybdenum-titanium alloy target blank with an oxygen content <800 ppm and a density ≥98%. The vacuum sintering comprises a first temperature rising, a second temperature rising and a furnace cooling in sequence; The terminal temperature of the first temperature rising is 700-1000℃, and the holding time is 1-3h; The terminal temperature of the second temperature rising is 1400-1600℃, and the holding time is 2-6h.