CN115029670B - Preparation method of chromium-silicon alloy tubular target - Google Patents

Abstract

The invention relates to a preparation method of a chromium silicon alloy tubular target, which comprises the following steps: (1) Mixing polyethylene wax powder and chromium silicon alloy powder to obtain mixed powder; (2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) to obtain a pressed compact; (3) And (3) sequentially performing a first sintering treatment, a second sintering treatment and a cooling treatment on the pressed compact obtained in the step (2) to obtain the chromium silicon alloy tubular target. The preparation method of the chromium silicon alloy tubular target material provided by the invention can be used for preparing the tubular target material with good compactness, high yield and uniform tissue structure, is simple to operate and can be used for industrial production.

Description

Preparation method of chromium-silicon alloy tubular target

Technical Field

The invention relates to the field of targets, in particular to a preparation method of a chromium-silicon alloy tubular target.

Background

With the rapid development of film science and the continuous progress of film technology, people pay more attention to surface treatment to obtain corresponding functional requirements. Among the numerous thin film sputtering processes, physical vapor deposition techniques are widely used in terms of their simplicity of operation, small material source limitations, and environmental friendliness, with magnetron sputtering and arc ion plating techniques being typical representatives of the physical vapor deposition techniques and most widely used. The target material is a material source which bombards atoms in the target material under proper process conditions through a magnetron sputtering and multi-arc ion plating system and then deposits on a substrate to form various functional films. Therefore, the quality of the sputtering target directly influences the performance of the thin film function and the quality of the performance.

The target material is mainly divided into a planar target and a tube target. Compared with a planar target, the tubular target has the characteristics of high utilization rate, uniform coating composition, good continuity and the like, and is converted from the planar target to the rotary tubular target along with the use of the coating industry, so that the tubular target becomes a standard material in the field of magnetron sputtering coating.

The chromium silicon alloy sputtering target is a novel sputtering target, can be widely applied to the fields of electronics, military, decoration, functional films and the like, and has huge market demand. Currently known tube target production methods are thermal spraying, casting and powder metallurgy. The thermal spraying is to spray the metal powder on the workpiece by adopting a plasma thermal spraying mode, and the pipe target prepared by the method has low density, extremely uneven structure, a large number of holes and high oxygen content, and can only be used in the coating industry with low requirements, such as glass. The casting method is to directly cast the target material onto the liner tube, but is only used for the target material with low melting point such as tin, zinc and the like. In addition, the chromium-silicon alloy is hard and brittle in texture, cracks are easy to occur in the processing process, the yield is low, the flowability of the chromium-silicon alloy powder is high, and the chromium-silicon alloy powder is difficult to mold by directly cold pressing.

CN103774101a discloses an ultralow oxygen content thermal spraying tube target and a preparation method thereof, the method comprises the steps of placing thermal spraying equipment and a spraying substrate into an argon protective atmosphere, spraying a workpiece by using metal powder in a plasma thermal spraying mode, and precisely machining the sprayed workpiece to obtain the ultralow oxygen content thermal spraying tube target, wherein the defects of low density, uneven tissue structure, high oxygen content and the like are overcome.

CN111058004a discloses a chromium-silicon alloy sputtering target and a preparation method thereof, wherein the method comprises the steps of filling chromium-silicon alloy powder into a mould, performing hot isostatic pressing, and then machining to obtain the target. However, the target material obtained by the method is a planar target material, the sputtering utilization rate of the target material is only 30%, the sputtering utilization rate of the tubular target material can reach more than 70%, and the sputtering utilization rate is 2-3 times that of the planar target material and is higher.

CN104227000a discloses a method for producing a chromium target, which comprises the steps of uniformly mixing metal chromium powder with granularity of 60-320 meshes and granularity of 320-500 meshes, cold-pressing and molding, and hot-pressing to obtain the chromium target. Because the chromium-silicon alloy powder has good fluidity and is difficult to mold, the method is not suitable for preparing the chromium-silicon alloy target.

Therefore, the preparation method of the chromium silicon alloy tubular target material with good compactness and high yield is of great significance.

Disclosure of Invention

Compared with the prior art, the preparation method provided by the invention can well improve the fluidity of the chromium-silicon alloy powder, and the obtained chromium-silicon alloy tubular target has high density and yield, uniform structure and can be industrially produced.

In order to achieve the aim of the invention, the invention adopts the following technical scheme:

the invention provides a preparation method of a chromium silicon alloy tubular target, which comprises the following steps:

(1) Mixing polyethylene wax powder and chromium silicon alloy powder to obtain mixed powder;

(2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) to obtain a pressed compact;

(3) And (3) sequentially performing a first sintering treatment, a second sintering treatment and a cooling treatment on the pressed compact obtained in the step (2) to obtain the chromium silicon alloy tubular target.

According to the invention, the chromium-silicon alloy powder and the polyethylene wax powder are mixed, the fluidity of the powder is improved by utilizing the polyethylene wax powder, then cold pressing treatment is carried out, so that the pressed compact is easier to form, then the first sintering treatment and the second sintering treatment are sequentially carried out to sequentially remove the polyethylene wax powder and densify the target, and finally cooling treatment is carried out to obtain the chromium-silicon alloy tubular target. The preparation method of the chromium-silicon alloy tubular target material adopts the polyethylene wax powder and the alloy powder for dry mixing, so that the mobility of the powder can be improved, the density of the target material can be improved, the tissue structure of the target material is more uniform, the yield of the product is higher, and compared with the wet mixing of the chromium-silicon alloy powder, the density and the yield of the target material can be improved.

According to the invention, heating is not performed in the cold pressing treatment process, pressurizing is not performed in the first sintering treatment and the second sintering treatment process, so that the compactness of the target can be effectively improved, and the target is prevented from cracking.

The invention is not particularly limited to the mass ratio of chromium to silicon in the chromium-silicon alloy powder, for example, the mass ratio of chromium to silicon may be 3:7, 7:3, 4:6 or 6:4, etc.

Preferably, the particle size of the chrome silicon alloy powder in the step (1) is 30-45 μm, for example, 30 μm, 32 μm, 34 μm, 36 μm, 38 μm, 40 μm, 42 μm, 44 μm or 45 μm, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.

Preferably, in the powder blend in step (1), the polyethylene wax powder has a mass percentage of 1-6%, for example, 1%, 2%, 3%, 4%, 5% or 6%, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.

In the invention, argon is injected in the mixing process, so that the powder can be prevented from being oxidized.

The invention preferably controls the mass percentage content of the polyethylene wax powder in a specific range, and can improve the density and yield of the target material.

Preferably, the pressure of the cold pressing treatment in the step (2) is 180-250MPa, for example, 180MPa, 190MPa, 200MPa, 210MPa, 220MPa, 230MPa, 240MPa or 250MPa, but the method is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.

Preferably, the cold pressing treatment in step (2) is performed for a period of time ranging from 90 to 150s, for example, 90s, 100s, 110s, 120s, 130s, 140s or 150s, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

According to the invention, the mixed powder is placed into a cold pressing mold for cold pressing treatment, the outer tube of the cold pressing mold adopts the rubber sleeve made of polyurethane material, so that adhesion with chromium and silicon can be prevented, demolding is easier, the inner core tube of the cold pressing mold adopts a chromium-plated high-speed steel tube, and the cold pressing mold needs to be cleaned and dried before use.

Preferably, the temperature rising rate of the first sintering treatment in the step (3) is 4-6 ℃/min, for example, 4 ℃/min, 4.2 ℃/min, 4.4 ℃/min, 4.6 ℃/min, 4.8 ℃/min, 5 ℃/min, 5.2 ℃/min, 5.4 ℃/min, 5.6 ℃/min, 5.8 ℃/min or 6 ℃/min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.

The end temperature of the first sintering process is preferably 840 to 860 ℃, and may be 840, 842, 844, 846, 848, 850, 852, 854, 856, 858, or 860 ℃, for example, but the end temperature is not limited to the values recited, and other values not recited in the numerical range are equally applicable.

The invention preferably controls the end temperature of the first sintering treatment within a specific range, and can improve the compactness and the yield of the target material.

Preferably, the heat preservation time of the first sintering treatment is 3-6h, for example, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.

Preferably, the temperature rising rate of the second sintering treatment in the step (3) is 2-4 ℃/min, for example, 2 ℃/min, 2.2 ℃/min, 2.4 ℃/min, 2.6 ℃/min, 2.8 ℃/min, 3 ℃/min, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min or 4 ℃/min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.

The end temperature of the second sintering process is preferably 950 to 1250 ℃, and may be 950 to 980 ℃, 1000 ℃, 1050 ℃, 1080 ℃, 1100 ℃, 1150 ℃, 1180 ℃, 1200 ℃, or 1250 ℃, for example, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.

The invention preferably controls the end temperature of the second sintering treatment within a specific range, and can improve the compactness and the yield of the target material.

Preferably, the second sintering treatment has a holding time of 4-8h, for example, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.

Preferably, the cooling rate of the cooling treatment in the step (3) is 9-11 ℃/min, for example, 9 ℃/min, 9.2 ℃/min, 9.4 ℃/min, 9.6 ℃/min, 9.8 ℃/min, 10 ℃/min, 10.2 ℃/min, 10.4 ℃/min, 10.6 ℃/min, 10.8 ℃/min or 11 ℃/min, but the cooling rate is not limited to the recited values, and other values not recited in the numerical range are equally applicable.

Preferably, the final temperature of the cooling treatment in the step (3) is 90 to 110 ℃, for example, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃ or 110 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.

As a preferred technical scheme of the invention, the preparation method comprises the following steps:

(1) Mixing polyethylene wax powder and chromium silicon alloy powder, wherein the particle size of the chromium silicon alloy powder is 30-45 mu m, so as to obtain mixed powder, and the mass percentage of the polyethylene wax powder in the mixed powder is 1-6%;

(2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) for 90-150s under 180-250MPa to obtain a pressed compact;

(3) Heating the pressed compact obtained in the step (2) to 840-860 ℃ at 4-6 ℃/min, preserving heat for 3-6h, performing first sintering treatment, heating to 950-1250 ℃ at 2-4 ℃/min, preserving heat for 4-8h, performing second sintering treatment, and cooling to 90-110 ℃ at 9-11 ℃/min, thereby obtaining the chromium silicon alloy tubular target.

Compared with the prior art, the invention has the following beneficial effects:

(1) The preparation method of the chromium silicon alloy tubular target material provided by the invention can be used for preparing the tubular target material with good compactness, high yield and uniform tissue structure, the compactness can reach more than 92.13%, the yield can reach more than 90.00%, the compactness can reach more than 98.01% under the optimal condition, and the yield can reach more than 98.5%.

(2) The preparation method of the chromium-silicon alloy tubular target material provided by the invention can reduce the content of target material impurities, has higher purity, is simple to operate, is environment-friendly, and can be industrially popularized.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

Example 1

The embodiment provides a preparation method of a chromium silicon alloy tubular target, which comprises the following steps:

(1) Mixing polyethylene wax powder and chromium-silicon alloy powder, wherein the particle size of the chromium-silicon alloy powder is 37 mu m, so as to obtain mixed powder, the mass percentage of the polyethylene wax powder in the mixed powder is 3.5%, the mass percentage of chromium in the chromium-silicon alloy powder is 70%, and the purity of the chromium-silicon alloy powder is 99.95%;

(2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) for 120s under 215MPa to obtain a pressed compact;

(3) Heating the pressed compact obtained in the step (2) to 850 ℃ at a speed of 5 ℃/min, preserving heat for 4.5 hours, performing first sintering treatment, heating to 1100 ℃ at a speed of 3 ℃/min, preserving heat for 6 hours, performing second sintering treatment, and cooling to 100 ℃ at a speed of 10 ℃/min, thereby obtaining the chromium-silicon alloy tubular target.

Example 2

The embodiment provides a preparation method of a chromium silicon alloy tubular target, which comprises the following steps:

(1) Mixing polyethylene wax powder and chromium-silicon alloy powder, wherein the particle size of the chromium-silicon alloy powder is 30 mu m, so as to obtain mixed powder, the mass percentage of the polyethylene wax powder in the mixed powder is 6%, the mass percentage of chromium in the chromium-silicon alloy powder is 70%, and the purity of the chromium-silicon alloy powder is the same as that of the embodiment 1;

(2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) for 150s under 180MPa to obtain a pressed compact;

(3) And (3) heating the pressed compact obtained in the step (2) to 860 ℃ at a speed of 4 ℃/min, preserving heat for 3 hours, performing first sintering treatment, heating to 950 ℃ at a speed of 4 ℃/min, preserving heat for 8 hours, performing second sintering treatment, and cooling to 110 ℃ at a speed of 9 ℃/min, thereby obtaining the chromium-silicon alloy tubular target.

Example 3

The embodiment provides a preparation method of a chromium silicon alloy tubular target, which comprises the following steps:

(1) Mixing polyethylene wax powder and chromium-silicon alloy powder, wherein the particle size of the chromium-silicon alloy powder is 45 mu m, so as to obtain mixed powder, the mass percentage of the polyethylene wax powder in the mixed powder is 1%, the mass percentage of chromium in the chromium-silicon alloy powder is 70%, and the purity of the chromium-silicon alloy powder is the same as that of the embodiment 1;

(2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) for 90s under 250MPa to obtain a pressed compact;

(3) And (3) heating the pressed compact obtained in the step (2) to 840 ℃ at a speed of 6 ℃/min, preserving heat for 6 hours, performing first sintering treatment, heating to 1250 ℃ at a speed of 2 ℃/min, preserving heat for 4 hours, performing second sintering treatment, and cooling to 90 ℃ at a speed of 11 ℃/min, thereby obtaining the chromium-silicon alloy tubular target.

Example 4

The embodiment provides a preparation method of a chromium-silicon alloy tubular target, which is different from embodiment 1 only in that the mass percentage of polyethylene wax powder is 0.5%.

Example 5

The embodiment provides a preparation method of a chromium silicon alloy tubular target, which is different from embodiment 1 only in that the mass percentage of polyethylene wax powder is 10%.

Example 6

This example provides a method for preparing a tubular target of chromium silicon alloy, which differs from example 1 only in that the end temperature of the first sintering process is 820 ℃.

Example 7

This example provides a method for preparing a tubular target of chromium silicon alloy, which differs from example 1 only in that the end temperature of the first sintering process is 880 ℃.

Example 8

This example provides a method for preparing a tubular target of chromium silicon alloy, which differs from example 1 only in that the end temperature of the second sintering process is 900 ℃.

Example 9

This example provides a method for preparing a tubular target of chromium silicon alloy, which differs from example 1 only in that the end temperature of the second sintering process is 1300 ℃.

Comparative example 1

This comparative example provides a method for preparing a tubular target of chromium silicon alloy, which differs from example 1 only in that no polyethylene wax powder is added.

Comparative example 2

This comparative example provides a method for preparing a chromium silicon alloy tubular target, which differs from example 1 only in that the polyethylene wax powder is replaced with polyvinyl alcohol, the mass percentage of which is the same as that of example 1.

Comparative example 3

This comparative example provides a method for producing a chromium silicon alloy tubular target, which differs from example 1 only in that the first sintering treatment is not performed and the compact is directly subjected to the second sintering treatment.

Comparative example 4

This comparative example provides a method for producing a chromium silicon alloy tubular target, which differs from example 1 only in that the second sintering treatment is not performed, and the green compact is subjected to the first sintering treatment and then directly subjected to the cooling treatment.

Comparative example 5

This comparative example provides a method for preparing a tubular target of chromium silicon alloy, which differs from example 1 only in that the cold pressing treatment is not performed, and the mixed powder is charged into a mold to directly perform the first sintering treatment.

The densities of the chromium-silicon alloy tubular targets prepared in examples 1 to 9 and comparative examples 1 to 5 were measured by a drainage method, and the densities=measured density/theoretical density×100%, and the results are shown in table 1.

The tubular targets of chromium-silicon alloy prepared in examples 1 to 9 and comparative examples 1 to 5 were subjected to full inspection to obtain yields of targets, and the results are shown in table 1.

The purities of the tubular targets of chromium-silicon alloys prepared in examples 1 to 9 and comparative examples 1 to 5 were measured by glow discharge mass spectrometry, and the results are shown in table 1.

TABLE 1

From table 1, the following points can be seen:

(1) From the data of examples 1-9, the density of the target material obtained by the preparation method of the chromium silicon alloy tubular target material provided by the invention can reach more than 92.13%, the yield can reach more than 90.00%, the density can reach more than 98.01% under the preferable condition, and the yield can reach more than 98.5%.

(2) As can be seen from the data of examples 1 and 4-5, the polyethylene wax powder in example 1 has a mass percentage of 3.5%, and compared with the polyethylene wax powder in examples 4-5, which is 0.5% and 10% respectively, the polyethylene wax powder in example 1 has higher density and higher yield than those in examples 4-5, so that the polyethylene wax powder is preferably controlled in mass percentage, and the density and yield of the target material can be improved.

(3) As can be seen from a combination of the data of examples 1 and examples 6 to 7, the end point temperature of the first sintering process in example 1 was 850 ℃, and the yield in example 1 was higher than that in examples 6 to 7 compared to 820 ℃ and 880 ℃ in examples 6 to 7, respectively, thus indicating that the invention can improve the yield of the target by preferably controlling the end point temperature of the first sintering process.

(4) As can be seen from a combination of the data of examples 1 and examples 8 to 9, the end point temperature of the second sintering process in example 1 is 1100 ℃, and compared with 900 ℃ and 1300 ℃ in examples 8 to 9, the density and yield in example 1 are higher than those in example 8, and the yield is higher than that in example 9, so that it is shown that the invention can improve the density and yield of the target by preferably controlling the end point temperature of the second sintering process.

(5) From the data of comparative examples 1 and 1-2, it can be seen that the comparative example 1 differs from example 1 only in that no polyethylene wax powder is added, the comparative example 2 differs from example 1 only in that the polyethylene wax powder is replaced with polyvinyl alcohol, and the density and yield in example 1 are much higher than those in comparative examples 1-2, thus indicating that the invention can improve the density and yield of the target material by adding the polyethylene wax powder.

(6) As can be seen from the data of comparative examples 1 and 3 to 5, comparative example 3 differs from example 1 only in that the first sintering treatment is not performed, comparative example 4 differs from example 1 only in that the second sintering treatment is not performed, and comparative example 5 differs from example 1 only in that the cold pressing treatment is not performed, and the density and yield in example 1 are both much higher than those in comparative examples 3 to 5, thereby indicating that the present invention can improve the density and yield of the target by sequentially performing the cold pressing treatment, the first sintering treatment, and the second sintering treatment.

In conclusion, the preparation method provided by the invention can well improve the fluidity of the chromium-silicon alloy powder, and the obtained chromium-silicon alloy tubular target has high density and yield.

The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (7)

1. The preparation method of the chromium silicon alloy tubular target is characterized by comprising the following steps of:

(1) Mixing polyethylene wax powder and chromium silicon alloy powder to obtain mixed powder;

in the mixed powder material in the step (1), the mass percentage of the polyethylene wax powder is 1-6%;

(2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) to obtain a pressed compact;

(3) Sequentially performing first sintering treatment, second sintering treatment and cooling treatment on the pressed compact obtained in the step (2) to obtain the chromium silicon alloy tubular target;

the temperature rising rate of the first sintering treatment in the step (3) is 4-6 ℃/min; the end temperature of the first sintering treatment is 840-860 ℃; the heat preservation time of the first sintering treatment is 3-6h;

the temperature rising rate of the second sintering treatment in the step (3) is 2-4 ℃/min; the end temperature of the second sintering treatment is 950-1250 ℃; the heat preservation time of the second sintering treatment is 4-8h.

2. The method according to claim 1, wherein the chrome silicon alloy powder in the step (1) has a particle size of 30-45 μm.

3. The method according to claim 1, wherein the cold pressing treatment in step (2) is performed at a pressure of 180 to 250MPa.

4. The method of claim 1, wherein the cold press treatment in step (2) is performed for a period of 90 to 150 seconds.

5. The method according to claim 1, wherein the cooling rate of the cooling treatment in the step (3) is 9-11 ℃/min.

6. The method according to claim 1, wherein the final temperature of the cooling treatment in step (3) is 90 to 110 ℃.

7. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:

(1) Mixing polyethylene wax powder and chromium silicon alloy powder, wherein the particle size of the chromium silicon alloy powder is 30-45 mu m, so as to obtain mixed powder, and the mass percentage of the polyethylene wax powder in the mixed powder is 1-6%;

(2) Carrying out cold pressing treatment on the mixed powder obtained in the step (1) for 90-150s under 180-250MPa to obtain a pressed compact;

(3) Heating the pressed compact obtained in the step (2) to 840-860 ℃ at 4-6 ℃/min, preserving heat for 3-6h, performing first sintering treatment, heating to 950-1250 ℃ at 2-4 ℃/min, preserving heat for 4-8h, performing second sintering treatment, and cooling to 90-110 ℃ at 9-11 ℃/min, thereby obtaining the chromium silicon alloy tubular target.