阅读说明：本技术 一种金属离子源及其应用和使用方法 (Metal ion source and application and use method thereof ) 是由 刘锦云 金应荣 贺毅 曹仁发 王梦嘉 曾国兴 张平 万海毅 于 2020-06-02 设计创作，主要内容包括：本发明公开了一种金属离子源及其应用和使用方法,涉及表面工程技术领域。其包括：用作阴极的内芯、用作阳极的外芯和屏蔽管。本发明提供的金属离子源,具有较高的溅射效率,能在管筒状零件内沿轴向均匀地供给金属离子,便于在内表面得到均匀的表面改性层；本发明通过在内芯的双侧开通孔,使得金属离子溅射面积更大,溅射效率更高。将外芯单独设置到屏蔽管外,有利于实现金属离子源整体结构的小型化。从而对更小型的管状工件进行内表面改性,应用范围更广,同时极大程度地简化了结构,提高了可靠性。此外还提供了金属离子源的使用方法和应用。(The invention discloses a metal ion source and an application and a using method thereof, and relates to the technical field of surface engineering. It includes: an inner core serving as a cathode, an outer core serving as an anode, and a shield tube. The metal ion source provided by the invention has higher sputtering efficiency, can uniformly supply metal ions in the tubular part along the axial direction, and is convenient for obtaining a uniform surface modified layer on the inner surface; according to the invention, through holes are formed on two sides of the inner core, so that the metal ion sputtering area is larger and the sputtering efficiency is higher. The outer core is independently arranged outside the shielding pipe, so that the miniaturization of the whole structure of the metal ion source is realized. Therefore, the inner surface of the smaller tubular workpiece is modified, the application range is wider, the structure is greatly simplified, and the reliability is improved. In addition, a use method and application of the metal ion source are also provided.)

1. A metal ion source, comprising:

an inner core serving as a cathode, an outer core serving as an anode, and a shield tube;

the inner core is provided with at least one through hole on the radial peripheral wall, the shielding pipe is sleeved on the periphery of the inner core, the peripheral wall of the shielding pipe is provided with at least two ion through holes, each through hole is opposite to the two ion through holes, and each ion through hole is the same as each through hole which is oppositely arranged in shape and size;

the outer core is arranged on the outer side of the shielding pipe.

2. The metal ion source of claim 1, wherein the inner peripheral wall of the shield tube forms a first gap with the outer peripheral wall of the inner core; the distance between the outer peripheral wall of the shielding pipe and the outer peripheral wall of the outer core is larger than 5 mm;

preferably, the first gap width is 2-5 mm.

3. The metal ion source of claim 2, wherein the through-hole has a width in a radial direction of 5-10 mm.

4. The metal ion source of claim 3, wherein the through-hole and the ion via are each strip-shaped;

the through hole and the ion through hole are both spiral holes which are unfolded along a spiral line.

5. The metal ion source of claim 2, wherein the outer core is an electrically conductive part and the inner core is made of a metal or alloy to be sputtered; preferably, the outer core is a metal rod or a metal wire.

6. The metal ion source of claim 1, further comprising two insulating holders for supporting the inner core and the shielding tube, wherein the two insulating holders are respectively sleeved on the outer periphery of the end portion of the inner core, and the two insulating holders are respectively fixedly connected with two ends of the shielding tube.

7. Use of a metal ion source according to any of claims 1 to 6, comprising:

filling sputtering gas into the metal ion source in a vacuum environment, raising the air pressure, applying bias voltage between the inner core and the outer core, generating hollow cathode discharge in the through hole, and sputtering the material of the inner core out of the through hole to form metal ions;

preferably, the vacuum is applied to a vacuum degree of 10^-3-10^-2After Pa, filling sputtering gas to increase the air pressure to 200-500 Pa;

preferably, a bias voltage of 400 to 1200V is applied between the anode and the cathode.

8. The method of claim 7, wherein the sputtering gas is an inert gas;

preferably, the sputtering gas is argon and/or krypton.

9. The method of claim 7, wherein the sputtering gas is a mixture of argon and a reactive gas, and the reactive gas is used to react with the sputtered metal ions to form a metal compound.

10. Use of a metal ion source according to any of claims 1 to 6 for plasma modification of an inner surface of a workpiece; preferably, the workpiece is an elongated tube.

Technical Field

The invention relates to the technical field of surface engineering, in particular to a metal ion source and an application and a using method thereof.

Background

The plasma surface modification technology has the advantages of simple process, high processing speed, good treatment effect and the like, and is widely applied at present. This technique generally requires the supply of metal ions, and in the case of a tubular member, if the metal is supplied as a metal vapor-phase compound, there is necessarily a concentration difference between the supply inlet end and the outlet end, thereby making the modified layer uneven. The technology such as plasma immersion ion implantation firstly generates metal ions outside, and then the metal ions are diffused into the tubular part of the tube, and the technology still has concentration difference, so that the modified layer is not uniformly distributed in the axial direction.

CN 108456862B is slotted on the wall of the cathode tube, although hollow cathode discharge can be formed in the direction vertical to the inner surface, the wall thickness of the cathode tube is limited due to the limitation of space position, the sputtering area is small, the sputtering efficiency is low, and the engineering application is difficult.

Thus, surface modification of the interior of elongated tubes has been a challenge in the field of plasma surface modification due to the lack of a means for efficiently and controllably supplying metal ions.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The present invention is directed to a metal ion source and its application and method of use to solve the above-mentioned problems.

The invention is realized by the following steps:

a metal ion source, comprising:

an inner core serving as a cathode, an outer core serving as an anode, and a shield tube;

the inner core is provided with at least one through hole on the radial peripheral wall, the shielding pipe is sleeved on the periphery of the inner core, the peripheral wall of the shielding pipe is provided with at least two ion through holes, each through hole is opposite to two ion through holes, and each ion through hole is the same as each through hole which is arranged oppositely in shape and size;

the outer core is arranged outside the shielding tube.

In one embodiment, the inner core is provided with two through holes on the radial peripheral wall, and the included angle of the two through holes is larger than 30 degrees and smaller than or equal to 90 degrees. Preferably, the angle between the two through holes is 90 degrees. Correspondingly, two pairs of ion through holes are formed in the peripheral wall of the shielding pipe, and each pair of ion through holes corresponds to one through hole in the axial position.

The through-hole is a through-hole.

The invention provides the structure of the through hole, the ion through hole and the shielding tube, so that the hollow cathode discharge process is carried out in the through hole. The outer core used as the anode is arranged on one side of the through hole (spatially, namely on one side of the ion through hole), so that an electric field from the anode to the cathode is generated between the anode and the cathode (inner core), sputtering gas is ionized under the action of the electric field, cations generated by ionization are continuously accelerated under the action of the electric field and bombard the cathode (inner core), and metal ions sputtered from the cathode fly out of the through hole, pass through the ion through hole and are directly incident on the inner surface of the slender pipe part.

The metal ion source provided by the invention can produce the following beneficial effects: when the metal ion source is used for modification of the inner surface of the elongated tube, metal ions can be uniformly supplied along the axial direction of a workpiece (elongated tube); the generated metal ions are directly incident to the inner surface of the part, which is beneficial to improving the film-substrate binding force; the through holes are deep, the ion bombardment area is large, more metal ions can be sputtered in unit axial length of unit time, and the sputtering efficiency can be improved; by changing the arrangement mode and the positions of the through holes and the ion through holes on the cathode and the shielding tube, the modification of the inner surface of the region with various design requirements can be met; the metal ion source provided by the invention avoids large-area glow discharge and is convenient for controlling the temperature of the inner hole part.

In addition, the inner core is provided with the through hole, so that the ion sputtering area in unit axial length is larger, and the sputtering efficiency is higher. The outer core is independently arranged outside the shielding pipe, when the part to be processed is a conductive slender pipe part, the part can be used as an anode, the outer core does not need to be arranged as the anode, and the simplification and miniaturization of the whole structure of the metal ion source are favorably realized. Therefore, the inner surface modification treatment is carried out on the smaller tubular workpiece, and the application range is wider.

In a preferred embodiment of the present invention, a first gap is formed between an inner peripheral wall of the shielding tube and an outer peripheral wall of the inner core; the distance between the outer peripheral wall of the shielding tube and the outer peripheral wall of the outer core is larger than 5 mm;

preferably, the first gap width is 2-5 mm.

In a preferred embodiment of the present invention, the width of the through hole in the radial direction is 5 to 10 mm.

In a preferred embodiment of the present invention, the through hole and the ion through hole are both in the shape of a strip;

preferably, the through-hole and the ion through-hole are both provided in a long strip shape extending in the axial direction.

The through holes and the ion through holes are arranged to be elongated along the axial direction, so that the sputtering area is increased, more metal ions are sputtered in unit time, and the inner surface modification efficiency is improved. It should be noted that specific shapes of the through-hole and the ion through-hole are not limited herein, and it is to be understood that the through-hole and the ion through-hole may be formed in other shapes according to the needs of the user in other embodiments.

In one embodiment, the through-hole and the ion passage hole are each provided as a helical hole of the same pitch that extends along a helix.

In a preferred embodiment of the present invention, the outer core is a conductive metal member, and the inner core is made of a metal or an alloy to be sputtered; preferably, the outer core is a metal rod or wire. In other embodiments, the outer core is an electrically conductive elongated rod piece.

The inner core may be made of steel, tungsten alloy, titanium alloy or copper alloy.

In a preferred embodiment of the present invention, the metal ion source further includes two insulation seats for supporting the inner core and the shielding tube, the two insulation seats are respectively sleeved on the periphery of the end portion of the inner core, and the two insulation seats are respectively fixedly connected to two ends of the shielding tube.

In one embodiment, the insulating base is clamped with the shielding pipe through a clamping structure, and in other embodiments, the insulating base can be fixedly connected with the shielding pipe in a threaded manner.

The insulating seat is made of high-temperature-resistant insulating materials, preferably corundum, and the corundum has the characteristics of high temperature resistance, insulation, good chemical stability and the like, so that the use requirement of the insulating seat can be effectively met.

In other embodiments, the insulating base can be made of other materials according to the requirements of users.

A method of using a metal ion source, comprising:

filling sputtering gas into a metal ion source in a vacuum environment, raising the air pressure, applying bias voltage between an inner core and an outer core, generating hollow cathode discharge in a through hole, and sputtering the material of the inner core out of the through hole to form metal ions;

preferably, the vacuum is applied to a vacuum degree of 10^-3-10^-2After Pa, filling sputtering gas to increase the air pressure to 200-500 Pa;

preferably, a bias voltage of 400 to 1200V is applied between the anode and the cathode.

Under the conditions of the vacuum degree, the air pressure rising pressure and the bias pressure, the inner surface modification of the area meeting the design requirement can be realized.

In a preferred embodiment of the present invention, the sputtering gas is an inert gas;

preferably, the sputtering gas is argon and/or krypton.

In a preferred embodiment of the present invention, the sputtering gas is a mixture of argon and a reactive gas, and the reactive gas is used to react with the sputtered metal ions to form a metal compound.

The application of a metal ion source in plasma modification of the inner surface of a workpiece. The metal ion source provided by the invention can be used for plasma deposition coating on the inner surface of the slender pipe.

The invention has the following beneficial effects:

the invention provides a metal ion source and an application and a using method thereof. Wherein the hollow cathode discharge is performed in through-holes in the cathode. The outer core used as the anode is arranged on one side of the through hole, so that an electric field from the anode to the cathode is generated between the anode and the cathode, the sputtering gas is ionized under the action of the electric field, cations generated by ionization are accelerated under the action of the electric field and bombard the cathode, and metal ions sputtered from the cathode fly out of the through hole and directly enter the inner surface of the slender pipe part through the ion through hole.

When the metal ion source is used for modification of the inner surface of the elongated tube, metal ions can be uniformly supplied along the axial direction; the generated metal ions are directly incident to the inner surface of the part, which is beneficial to improving the film-substrate binding force; by changing the arrangement mode and the positions of the through holes and the ion through holes on the cathode and the shielding tube, the modification of the inner surface of the region with various design requirements can be met; when the metal ion source and the slender pipe part rotate relatively, a uniform modified layer can be formed on the inner surface of the slender pipe; the metal ion source also avoids large-area discharge and is convenient for controlling the temperature of the inner hole part.

According to the invention, the inner core is provided with the through hole, so that the metal ion sputtering area in unit axial length is larger, and the sputtering efficiency is higher. The outer core is independently arranged outside the shielding pipe, when the part to be processed is a conductive slender pipe part, the part can be used as an anode, the outer core does not need to be arranged as the anode, and the simplification and miniaturization of the whole structure of the metal ion source are favorably realized. Thereby carrying out the interior surface modification to more miniature tubular work piece, the range of application is wider.

The use method and application of the metal ion source provided by the invention have the beneficial effects based on the metal ion source.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

Fig. 1 is a schematic view of the overall structure of a metal ion source provided in example 1;

fig. 2 is a sectional view of the entire structure of the metal ion source provided in example 1 along an axis;

FIG. 3 is a cross-sectional view perpendicular to the axis of FIG. 2;

FIG. 4 is a cross-sectional view perpendicular to the axis of the metal ion source provided in example 3;

FIG. 5 is a photograph of the coating obtained in example 4;

FIG. 6 is a graph of the coating and substrate locations of FIG. 5 for spectral analysis;

FIG. 7 is a graph of the distribution of copper elements in the substrate at the location shown in FIG. 6;

FIG. 8 is a graph showing the distribution of iron in the coating at the location shown in FIG. 6.

Icon: 100-an outer core; 200-an insulating base; 110-a second gap; 300-a shielding tube; 310-a first gap; 320-ion via; 400-a cathode; 410-through the hole.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

Referring to fig. 1, 2 and 3, the present embodiment provides a metal ion source. Which includes an outer core 100 serving as an anode, an insulating holder 200, a shield tube 300, and a cathode 400. Wherein, the shielding tube 300 is arranged around the outside of the cathode (inner core) 400, and the cathode 400 is provided with a through hole 410 with a width of 5-10 mm.

Referring to fig. 2 and 3, the shield tube 300 is disposed between the cathode 400 and the outer core 100, a first gap 310 is formed between an inner circumferential wall of the shield tube 300 and an outer circumferential wall of the cathode 400, and a second gap 110 is formed between the outer circumferential wall of the shield tube 300 and the outer core 100.

Two ion through holes 320 are formed on the side wall of the shielding tube 300; the through holes 410 and the ion through holes 320 have the same shape, the same axial dimension and the same radial dimension, and the through holes 410 are opposite to the ion through holes 320 in the axial position. The two ion through holes 320 are respectively opposite to the two ports of the through hole 410.

The distance (second gap 110) between the outer peripheral wall of the shielding tube 300 and the outer core 100 is greater than 5mm, and the distance between the inner peripheral wall of the shielding tube 300 and the outer peripheral wall of the inner core cathode 400 is 2-5 mm.

In this embodiment, a first gap 310 is left between the shielding tube 300 and the cathode 400, and the shielding tube 300 can effectively prevent a large area of glow discharge from being generated between the anode and the cathode, thereby preventing the discharge device from being burned out due to excessive current and high temperature.

The ion through holes 320 corresponding to the through holes 410 of the cathode 400 are formed in the shielding tube 300, so that the discharge between the anode and the cathode is conveniently limited in the through holes 410 of the cathode 400, the energy utilization efficiency is improved, and the temperature is reduced.

In this embodiment, the through-hole 410 and the ion through-hole 320 are both configured as a long strip extending in the axial direction, such that a long modified region can be obtained on the inner surface, and a larger modified region can be obtained on the inner surface when the ion source is rotated relative to the component. Here, specific shapes of the through-hole 410 and the ion through-hole 320 are not limited, and in another embodiment, the through-hole 410 and the ion through-hole 320 may be formed in a square shape and may be spirally spread along a spiral line.

Specifically, in the present embodiment, the width of the through hole 410 and the width of the ion through hole 320 are the same, and are both set to be 5-10 mm.

Specifically, in this embodiment, the metal ion source further includes two insulating bases 200 for supporting the cathode 400 and the shielding tube 300, the two insulating bases 200 are respectively sleeved on the periphery of the end of the cathode 400, and the two insulating bases 200 are respectively fixedly connected to two ends of the shielding tube 300.

In this embodiment, the insulating base 200 is made of corundum, which has the characteristics of high temperature resistance, insulation, and good chemical stability, and can meet the use requirement of the insulating base 200. In addition, in other embodiments, the insulating base 200 may be made of other materials according to the needs of users.

The iron ion source provided by the invention is adopted to deposit the iron-based coating on the inner wall of the copper pipe. In this embodiment, the outer core 100 is made of an iron wire with a diameter of 3mm and a length of 1000mm, the shielding tube 300 is a stainless steel tube with an inner diameter of 24mm, a wall thickness of 1mm and a length of 800mm, two ion through holes 320 on the shielding tube 300 are axially arranged in the middle of the tube wall, and the width of the ion through holes is 6mm and the length of the ion through holes is 500 mm. Referring to fig. 3, the upper and lower ion passing holes 320 have the same size.

The cathode 400 is made of 20 steel with the diameter of 16mm and the length of 1000mm, the through hole 410 in the cathode 400 is formed in the middle of the pipe wall along the axial direction, and the width of the through hole is 6mm and the length of the through hole is 500 mm. Both ends of the shielding tube 300 are supported by an insulating base 200 made of corundum, and the bottom end of the insulating base 200 is fixedly screwed with the cathode 400.

The iron ion source of this example was fixed in a copper tube having an inner diameter of 60 mm.

In other embodiments, the outer core 100 may be made in other sizes according to the needs of the user. In other embodiments, the outer core 100 may be made of other materials according to the needs of the user.

In other embodiments, the size and material of the shielding tube 300 can be adaptively adjusted according to the user's needs.

In other embodiments, the size and material of the cathode 400 can be adaptively adjusted according to the user's needs.

The iron ion source provided by the embodiment of the invention utilizes the sputtering effect of the positive ions on the cathode in the hollow cathode discharge process to sputter the cathode material to form the coating. The hollow cathode discharge is performed in the through-hole 410 of the cathode 400. The outer core 100 serving as an anode is disposed at one end of the through-hole 410 so as to generate an electric field from the anode to the cathode between the anode and the cathode, and metal ions generated by sputtering fly out at the other end of the through-hole 410 and may be directly incident on the inner surface of the elongated tube part.

Example 2

This embodiment provides a titanium ion source, which is different from embodiment 1 only in that the through hole 410 and the ion through hole 320 of the titanium ion source of this embodiment are both provided as spiral holes with a pitch of 150mm, which are spread along a right spiral, and the cathode 400 is made of pure titanium.

Example 3

This embodiment provides a tungsten ion source, which is different from embodiment 1 only in that: referring to FIG. 4, in the present embodiment, the outer core 100 is a member to be processed having a hole with a diameter of 100mm and a length of 3500mm, and the shield tube 300 is a tungsten tube with an inner diameter of 80mm, a wall thickness of 3mm and a length of 3000 mm;

the middle part of the pipe wall of the shielding pipe 300 is axially provided with 4 ion through holes 320, and each ion through hole 320 is 8mm wide and 2000mm long and is uniformly arranged along the circumferential direction;

the cathode 400 is made of a tungsten rod with the diameter of 72mm and the length of 3000mm, 2 through holes 410 are uniformly formed in the middle of the cathode 400, each through hole 410 is 8mm wide and 2000mm long, and the through holes are uniformly arranged along the circumferential direction. The included angle of the two through holes 410 is 90 degrees, and the two ends of the shielding tube 300 are arranged in holes with the inner diameter of 100mm and the length of 3500mm on parts after being supported by corundum as an insulating seat 200.

Example 4

The embodiment provides a use method of a metal ion source, which is based on the metal ion source and comprises the following steps:

in this example, 20 steel was used as a cathode, and after electrode leads were led out from both ends of a copper tube and connected to a vacuum system and an intake system, vacuum sealing was performed. Vacuum-pumping to 2 × 10^-2After Pa, argon gas is started to be introduced, and the opening degrees of the air suction valve and the air inlet valve are adjusted to keep the vacuum degree near 400 Pa. And (3) switching on a power supply, gradually increasing the voltage to 800V, gradually reducing the opening degrees of the air inlet valve and the air exhaust valve after a period of arc striking, reducing the gas flow, and gradually stabilizing the discharge of the hollow cathode, wherein the gas pressure at the moment is about 430 Pa. And maintaining the hollow cathode to discharge for 8 hours to form an iron-based coating on the inner wall of the copper pipe.

In this example, a photograph of an iron-based coating formed on the inner wall of a copper tube is shown in FIG. 5, a corresponding graph of a position for energy spectrum analysis is shown in FIG. 6, a graph of the distribution of copper elements in a substrate is shown in FIG. 7, and a graph of the distribution of iron elements in a coating is shown in FIG. 8.

Example 5

In the embodiment, the tungsten ion source provided by the invention is adopted to deposit the tungsten-based coating on the inner wall of the steel pipe. The cathode is made of a tungsten tube, electrode leads are led out of two ends of the steel tube, and vacuum sealing is carried out after the electrode leads are connected with a vacuum system and an air inlet system. Vacuum pumping to 3 × 10^-2And after Pa, beginning to introduce mixed gas of argon and krypton, wherein the mixing ratio of krypton to argon is 1:9, and adjusting the opening degree of the air extraction valve and the air inlet valve to keep the vacuum degree near 400 Pa. And (3) switching on a power supply, gradually increasing the voltage to 1000V, gradually reducing the opening degrees of the air inlet valve and the air exhaust valve after a period of arc striking, reducing the gas flow, and gradually stabilizing the discharge of the hollow cathode, wherein the gas pressure at the moment is about 350 Pa. And maintaining the hollow cathode to discharge for 8 hours to form a tungsten-based coating on the inner wall of the steel pipe.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.