CN116575005A - TiZrCo vacuum getter film and preparation method and application thereof - Google Patents

TiZrCo vacuum getter film and preparation method and application thereof Download PDF

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CN116575005A
CN116575005A CN202310523622.1A CN202310523622A CN116575005A CN 116575005 A CN116575005 A CN 116575005A CN 202310523622 A CN202310523622 A CN 202310523622A CN 116575005 A CN116575005 A CN 116575005A
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tizrco
vacuum
titanium alloy
getter film
equal
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CN116575005B (en
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罗成
蒙峻
杨建成
魏宁斐
李长春
刘建龙
万亚鹏
杨伟顺
朱小荣
谢文君
焦纪强
柴振
蔺晓建
马向利
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Institute of Modern Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/03—Press-moulding apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a TiZrCo vacuum getter film and a preparation method and application thereof. The invention provides a TiZrCo getter film, comprising the following components in atomic percent (atomic./%): ti is more than or equal to 42% and less than or equal to 46%, zr is more than or equal to 42% and less than or equal to 46%, and Co is more than or equal to 8% and less than or equal to 16%. The TiZrCo vacuum getter film provided by the invention has the advantages of high activation temperature, large saturated gettering capacity, large activatable times, strong adhesive force, high pumping speed and the like, can be applied to an HIAF titanium alloy lining extremely high vacuum chamber, and meets the requirements of an HIAF extremely high vacuum system.

Description

TiZrCo vacuum getter film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of getter films, and particularly relates to a TiZrCo getter film capable of being used in a heavy ion accelerator, a preparation method thereof and application thereof in the technology of obtaining extremely high vacuum in a titanium alloy lining vacuum chamber.
Background
The high-current heavy ion accelerator device (HIAF) is a new generation of heavy ion accelerator that combines high-current intensity, high-energy, high beam mass power. In the operation process of the high-current accelerator, as the titanium alloy lining vacuum chamber is longer in longitudinal length and cannot be provided with a vacuum pump, a certain number of molecules or ions can be desorbed when the high-energy beam acts with residual gas in the vacuum chamber or with a vacuum tube wall, so that desorption air load is formed. The desorption air load can cause high vacuum pressure gradient in the titanium alloy lining vacuum chamber, further cause dynamic change of the system vacuum degree, reduce the service life of the beam and even cause the accelerator to stop running.
The non-evaporable getter film (NEG) has a certain inhibition effect on dynamic vacuum change of the HIAF device, but the existing NEG film has limited saturated gettering capacity and less activatable times and cannot be applied to the accelerator field on a large scale; CN108531877a discloses a quaternary getter film (with an activation temperature of 160-200 ℃ for 20-24 hours) which can be used for on-line activation of an accelerator, but the activation temperature is low, and it is difficult to satisfy the on-line vacuum baking condition (250-300 ℃ x 48 hours) of a HIAF ultra-high vacuum device.
Disclosure of Invention
The invention aims to provide a TiZrCo getter film which has the advantages of high activation temperature, large saturated gettering capacity, multiple activation times, strong adhesive force, high pumping speed and the like, can be applied to an HIAF titanium alloy lining extremely high vacuum chamber, and meets the requirement of an HIAF extremely high vacuum system.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the present invention provides a TiZrCo getter film comprising, in atomic percent (atomic./%), the following components: ti is more than or equal to 42% and less than or equal to 46%, zr is more than or equal to 42% and less than or equal to 46%, co is more than or equal to 8% and less than or equal to 16%; preferably Ti:42%, zr:42%, co:16%.
The TiZrCo getter film is of a single-layer porous columnar structure, interfaces and gaps exist between columnar tissues, the columnar diameter is 70-300nm, the porosity is 8-16%, preferably 14%, and the aperture is 10-150nm.
The thickness of the TiZrCo getter film is 0.4-5 mu m, and the specific surface area is more than 15 mu m 2 /g。
The fully activated conditions of the TiZrCo getter film are: the temperature is kept for 40 to 48 hours at 220 to 250 ℃ and then is kept for 1 to 2 hours at 280 to 330 ℃.
The TiZrCo getter film takes titanium alloy as a substrate, and preferably takes a titanium alloy ring as a substrate.
In a second aspect, the invention further provides a preparation method of the TiZrCo getter film, comprising the following steps:
s1, ball milling titanium powder, zirconium powder and cobalt powder to obtain TiZrCo powder;
s2, filling the TiZrCo powder into a die, vibrating, compacting, degassing and firing to obtain a target blank; turning the target blank to obtain the TiZrCo planar target;
s3, performing direct current magnetron sputtering deposition on the surface of the substrate by using the TiZrCo planar target material to obtain the TiZrCo getter film.
In step S1, the purity of the titanium powder, zirconium powder and cobalt powder is higher than 99.8%, and the titanium powder, zirconium powder and cobalt powder are sieved by using a sieve, wherein the mesh number of the sieve is 300-500 mesh, preferably 400 mesh.
In step S1, the ball milling conditions are as follows:
the ball milling medium is zirconia ceramic balls; the sphere proportion of the zirconia ceramic balls is D15: d10: d5: d3 =1: (1.5-2): (2.5-3): (2.5-3), preferably 1:1.8:2.7:2.7.
the ball milling speed is 300-500r/min, preferably 400r/min, and the time is 15-20h, preferably 16h.
In step S2, the mold is a rectangular graphite mold, and two ends of the rectangular graphite mold are matched with a graphite bottom plate for sealing a cavity of the rectangular graphite mold.
The conditions of the degassing are as follows: vacuum degree is (0.8-1.2) x 10 -5 mbar, preferably 1X 10 -5 mbar, for a period of 3 to 5 hours, preferably 4 hours.
The firing conditions are as follows: in an inert atmosphere, the temperature is 1350-1450 ℃, preferably 1400 ℃, the pressure is 130-150MPa, preferably 140-150MPa, and the time is 8-10h, preferably 8-9h.
In step S2, the cross section of the TiZrCo planar target is a rectangular structure, and the size is: 300-1000mm long, 20-150mm wide, 2-6mm thick, preferably 810mm long, 58mm wide and 3mm thick.
The TiZrCo planar target consists of a plurality of sections, wherein the number of the sections is 2-6, preferably 3, and the length of each section is 135-405mm, preferably 270mm. The multi-segment combination is more advantageous for improving processability and meeting overall size requirements.
In step S3, the substrate is a titanium alloy ring in a titanium alloy lined vacuum chamber. Before the direct current magnetron sputtering deposition, ultrasonically cleaning the substrate for 15-30min, preferably 20min by using isopropanol, ultrasonically cleaning the substrate for 15-30min, preferably 20min by using deionized water, and drying under vacuum condition; the temperature of the drying is 80-120 ℃, preferably 100 ℃, and the time is 60-120min, preferably 90min.
In step S3, the dc magnetron sputtering deposition is performed according to the following steps:
(1) Placing a plurality of sections of TiZrCo planar targets on a planar target of a magnetron sputtering coating device, mounting the titanium alloy ring on the workpiece frame in the direct current magnetron sputtering device, and closing a furnace door; starting the rough drawing system and the fine drawing system to sequentially carry out rough drawing and fine drawing on the coating device, and closing the rough drawing system when the pressure in the coating chamber reaches a preset value;
(2) High-purity argon is introduced into the coating chamber through the flowmeter; and starting the heating pipe to heat the titanium alloy ring, and starting the ion source to perform plasma bombardment cleaning on the surface of the titanium alloy ring. The plasma bombardment facilitates activation of the surface.
(3) Closing the ion source, starting the magnetron sputtering TiZrCo planar target, and performing TiZrCo film deposition on the surface of the titanium alloy ring;
(4) And closing the magnetron sputtering plane target, the heating pipe and the fine pumping system, and flushing argon to cool to obtain the TiZrCo getter film of the titanium alloy ring substrate.
In the step (1), the Roots pump coarse pumping unit is turned on to perform coarse pumping, and when the thermocouple vacuum gauge indication number is smaller than 1×10 -2 Starting a molecular pump coarse pumping unit to perform fine pumping when mbar is reached; when the couple vacuum gauge is at 8 multiplied by 10 -5 And after mbar, closing the Roots pump roughing unit.
In the step (2), the heating temperature is 150-200 ℃, preferably 200 ℃, and the heating time is 120-180min, preferably 120min; when the plasma bombardment cleaning is carried out, the voltage is 1200-1800V, preferably 1800V.
In step S3, the conditions of the dc magnetron sputtering deposition are as follows: the pressure is 1X 10 -3 -2×10 -2 mbar, preferably 2X 10 -2 The current is 5-7A, preferably 5A, the voltage is 400-500V, the time is 10-15h, preferably 12h.
In a third aspect, the present invention further provides a titanium alloy lined vacuum chamber comprising the following composition: and the TiZrCo getter film is arranged on the surface of the titanium alloy ring.
In a fourth aspect, the present invention further provides a method for obtaining a final vacuum of a titanium alloy lined vacuum chamber, comprising the steps of:
step A, exhausting the titanium alloy lining vacuum chamber by using a rough pumping system, and starting a vacuum baking procedure;
and B, in the vacuum baking procedure, the main pump is utilized to pump air out of the titanium alloy lining vacuum chamber, and after the vacuum baking procedure is finished, the system is cooled to normal temperature, so that the extreme vacuum is obtained.
In the step A, the rough pumping system is a molecular pump rough pumping set and is used for system leakage detection, baking and exhausting, high vacuum obtaining and the like.
In the step A, the vacuum degree of the titanium alloy lining vacuum chamber reaches 10 -7 And when the vacuum baking process is within the mbar magnitude range, starting the vacuum baking process.
In the step B, the main pump is a titanium sublimation pump (containing three titanium wires) and a sputtering ion pump, and is used for obtaining and maintaining extremely high vacuum; wherein the pumping speed of the titanium sublimation pump is 3000L/s, and the titanium sublimation pump mainly adsorbs H in a system 2 CO; the pumping speed of the sputtering ion pump is 400L/s, and residual Ar and CH in the system are mainly pumped out 4 。
In step B, the vacuum baking procedure is: heating to 220-250 ℃ (preferably 250 ℃) at the speed of 20-30 ℃/h (preferably 30 ℃/h), preserving heat for 40-48 hours (preferably 48 hours), heating to 280-300 ℃ (preferably 300 ℃) at the same speed, and preserving heat for 2-4 hours (preferably 2 hours).
In the step B, after the vacuum baking procedure is started, degassing is started for each titanium wire of the titanium sublimation pump, the degassing current is 22-28A, preferably 27A, and the titanium wires are switched every 1-2 hours until the procedure is finished.
In the step B, the cooling process is as follows: cooling to 180-210 ℃ at a speed of 20-30 ℃/h (preferably 30 ℃/h), sublimating the titanium sublimation pump, cooling to 40-60 ℃ at the same speed, sublimating the titanium sublimation pump again, cooling to normal temperature (less than 30 ℃), and standing for 48h. The sublimation conditions are as follows: the current is 45-48A, preferably 47A, for 2-4min, preferably 3min.
In step B, the change in the limiting vacuum is measured by a vacuum measuring device; the vacuum measuring equipment is an IE514 separation gauge, and can accurately measure 2 multiplied by 10 -12 mbar-1×10 -4 The pressure varies between mbar.
Furthermore, a plurality of IE514 pipes are arranged at equal intervals on the outer side of the vacuum chamber of the titanium alloy lining, and the pressure distribution of the system under the extremely high vacuum condition can be accurately measured by matching with the IE514 pipes on the testing chambers on the two sides.
The beneficial effects obtained by the invention are as follows:
1. co is added into Zr and Ti, so that the lattice spacing can be obviously increased, and the diffusion rate of gas molecules in the getter is further increased; co can also form intermetallic compound ZrCo with Zr, further improves the binding force of the film, and effectively solves the defects of powder falling, poor adhesiveness and the like; in addition, the TiZrCo getter film prepared by adopting the planar alloy target has a porous columnar structure, has larger porosity and specific surface area, and has strong gettering capability and higher saturation capacity; in addition, the TiZrCo getter film provided by the invention has a wider thickness range which can be between 0.4 and 5 mu m.
2. After the TiZrCo getter film provided by the invention is thermally activated, zr can be formed 3 The Co phase has stronger gettering capability to active gas; the solid solution of Co in the activation process can also change the lattice constant of the film gettering phase, and further improve the gettering performance of the film.
3. The activation temperature range of the TiZrCo getter film provided by the invention is 270-330 ℃, and after the TiZrCo getter film is applied to a titanium alloy lining vacuum chamber, the activation temperature is 270-330 ℃ due to vacuum baking temperature and Zr 3 The Co film activation temperature is within the same area range, the whole vacuum baking process does not influence the air extraction performance and effective activation times of the film, the vacuum pressure gradient in the titanium alloy lining vacuum chamber is greatly reduced, and the vacuum degree value of any point in the titanium alloy vacuum chamber is better than 5 multiplied by 10 -12 mbar, meeting the requirements of HIAF ultra-high vacuum devices.
Drawings
FIG. 1 is a schematic structural diagram of a TiZrCo planar target.
Fig. 2 is an assembly schematic of a rectangular graphite mold.
FIG. 3 is a schematic structural view of a titanium alloy ring.
Fig. 4 is a schematic structural diagram of a magnetron sputtering coating device.
FIG. 5 is a schematic cross-sectional view of a titanium alloy lined thin wall vacuum chamber.
FIG. 6 is a schematic structural diagram of a titanium alloy lined thin wall vacuum chamber rough vacuum test apparatus.
FIG. 7 is a SEM morphology photograph of a cross section and a surface of the TiZrCo thin film provided in example 1; wherein the left graph is a section and the right graph is a surface.
FIG. 8 is a cross-sectional and surface SEM morphology photograph of a TiZr film without Co element added; wherein the left graph is a section and the right graph is a surface.
Fig. 9 is a pressure profile obtained for the extreme vacuum of the titanium alloy lined thin wall vacuum chamber provided in example 2.
The figures are marked as follows:
1-TiZrCo target material; 2-graphite bottom plate; 3-rectangular graphite mold; 4-titanium alloy ring; 5-a molecular pump fine pumping unit; 6-Roots pump roughing unit; 7-a workpiece frame; 8-ion source cleaning; 9-heating the pipe; a 10-TiZrCo planar target; 11-thermocouple vacuum gauge; 12-a gas flow meter; 13-titanium alloy lining vacuum chamber; 14-IE514 rule G 1 The method comprises the steps of carrying out a first treatment on the surface of the 15-IE514 rule G 2 The method comprises the steps of carrying out a first treatment on the surface of the 16-IE514 rule G 3 The method comprises the steps of carrying out a first treatment on the surface of the 17-sputtering an ion pump; 18-titanium sublimation pump; 19-testing pump chambers; 20-waveA bellows; 21-CF150 all-metal gate valve; 22-molecular pump coarse unit; 23-IE514 rule G 4 The method comprises the steps of carrying out a first treatment on the surface of the 24-IE514 rule G 5 。
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples.
The methods are conventional methods unless otherwise specified.
The starting materials are available from published commercial sources unless otherwise specified.
Example 1 preparation of TiZrCo getter film
Step 1, preparing TiZrCo planar magnetron sputtering target material
Firstly, selecting high-quality raw materials, wherein the purity of the raw materials is higher than 99.8%, sieving the raw materials by sieving equipment, selecting 400 meshes, and taking the sieved powder to obtain high-purity simple substance powder.
Secondly, the accurate electronic balance ensures that the sampling is accurate to 0.01g for sampling, and each batch is respectively: titanium powder: 172g, zirconium powder: 249g, cobalt powder: 163g; wherein the atomic number ratio (atomic number/%) of each component is: ti:42%, zr:42%, co:16, 584g total, 3 batches.
Thirdly, performing ball milling and mixing on 584g of finished powder obtained in each batch by a ball mill, wherein the ball milling medium is zirconia ceramic balls, and the ball proportion is d15:d10:d5:d3=1: 1.8:2.7:2.7, the ball milling rotating speed is 400r/min, and the ball milling time is 16h.
Fig. 1 is a schematic diagram of a set of TiZrCo targets, and each batch of powder is required to produce a set of TiZrCo targets 1.
FIG. 2 is a schematic diagram of die assembly during firing of each set of TiZrCo targets, a piece of graphite base plate 2 is placed on a firing platform, a rectangular graphite die 3 is placed on the graphite base plate 2, and prepared powder is filled in a gap between the rectangular graphite die 3 and the graphite base plate 2; vibrating and compacting, and covering a graphite circular plate 2; filling the prefabricated blank with a vacuum degree of 1×10 -5 The hot isostatic pressing apparatus at mbar was degassed for 4 hours and then the temperature was raised to 1400℃and the shielding gas argon was introducedAnd controlling the pressure to 150MPa, and performing a firing process for 8 hours to obtain a fired target blank.
Turning the outer wall of each fired blank by a numerical control machining center, wherein the dimensional tolerance is controlled within the range of 0 to 0.1mm, and thus the finished TiZrCo target 1 is obtained, and the length is multiplied by the width is multiplied by the thickness: 270X 58X 3mm.
Step 2, deposition of TiZrCo film on the surface of the titanium alloy ring
FIG. 3 is a schematic view of a titanium alloy ring.
FIG. 4 is a schematic diagram of a magnetron sputtering coating apparatus, in which 15 titanium alloy rings 4 are assembled and disassembled in one furnace.
The TiZrCo film is deposited according to the following steps:
1) Firstly, 15 titanium alloy rings 4 are pretreated, and the treatment method comprises the steps of ultrasonic cleaning by isopropanol for 20min, ultrasonic cleaning by deionized water for 20min, and drying by a vacuum furnace at 100 ℃ for 90min.
2) Mounting the 15 titanium alloy rings 4 after cleaning on a workpiece frame 7 (capable of automatically rotating), and closing the furnace door; turning on the Roots pump rough pumping unit 6 to carry out rough pumping, and waiting for the thermocouple vacuum gauge 11 to be smaller than 1 multiplied by 10 -2 When mbar is carried out, a molecular pump rough pumping unit 5 is started to carry out fine pumping; when the thermocouple vacuum gauge 11 is below 8×10 -5 After mbar, the Roots pump roughing pump unit 6 is turned off.
3) The gas flow meter 12 was turned on and 100sccm of high purity argon was introduced, and the operating pressure was maintained at 0.2Pa. The heating pipe 9 is opened, and the workpiece is heated for 120min at 200 ℃. Meanwhile, the ion source 8 is turned on, the working voltage is adjusted to 1800V, and plasma bombardment cleaning is carried out on the surface of the workpiece.
4) The ion source 8 and the corresponding baffle are closed, the planar magnetron sputtering target 10 is started, and the pressure is 2 multiplied by 10 -2 And (3) performing TiZrCo film deposition, wherein the current is 5A, the voltage is 400-500V, the deposition time is 12h.
5) And closing the magnetron sputtering planar target 10, the heating pipe 9 and the fine pumping system 5, and flushing argon to cool to obtain the TiZrCo getter film on the substrate of the titanium alloy ring 4.
Example 2 method for obtaining ultimate vacuum in titanium alloy lined thin wall vacuum Chamber
And step 1, after the work of depositing the TiZrCo film on the surface of the 15 titanium alloy rings 4 is finished, performing assembly welding processing and leakage detection testing according to a titanium alloy lining thin-wall vacuum chamber structure schematic diagram (shown in fig. 5).
Step 2, assembling a titanium alloy lining thin-wall vacuum chamber 13 extreme vacuum obtaining testing device according to the diagram shown in fig. 6, wherein:
the bellows 20 is used for compensating and absorbing the deformation of the titanium alloy lining vacuum chamber 13 during the evacuation and the on-line baking;
the test pump chamber 19 is used to connect vacuum acquisition and vacuum measurement equipment;
the rough pumping system selects a molecular pump rough pumping unit 22 for system leak detection, baking and exhausting, high vacuum acquisition and the like;
the main pump is a titanium sublimation pump 18 (containing three titanium wires) with a pumping speed of 3000L/s and a sputtering ion pump 17 with a pumping speed of 400L/s, which are used for obtaining and maintaining extremely high vacuum;
the vacuum measuring equipment adopts IE514 separating gauge, and can accurately measure 2×10 -12 mbar-1×10 -4 The pressure varies between mbar.
3 IE514 pipes 14-16 are arranged at equal intervals on the outer side of the vacuum chamber of the titanium alloy lining, and the pressure distribution of the system under the extremely high vacuum condition can be accurately measured by matching with IE514 pipes 23 and 24 on the testing chambers on two sides.
Step 3, the method for obtaining the extreme vacuum of the titanium alloy lining vacuum chamber 13 comprises the following steps:
1) After the test system is assembled, the molecular pump all-metal gate valve 21 is opened, the molecular pump rough pumping set 22 is started, and when the vacuum specification of the IE514 gauge 23 or 24 reaches 10 -5 When the Pa magnitude range is within, starting vacuum baking;
2) Starting a vacuum baking procedure, wherein the temperature rising rate is 30 ℃/h, and the baking heat preservation temperature and time are 250 ℃ multiplied by 48 hours; and after the baking and heat preserving stage is finished, starting to fully activate the TiZrCo film, and raising the temperature to 300 ℃ and preserving the heat for 2 hours.
After the baking and heat preserving stage is started, degassing is started to each titanium wire of the titanium sublimation pump 18, the degassing current is 27A, and the titanium wires are switched every 1 hour until the baking and heat preserving stage is finished. Meanwhile, when baking starts, degassing is carried out on the vacuum gauge pipes 14-16, 23 and 24 every 5 hours, and after baking and heat preservation are carried out for 20 hours, the sputtering ion pump 17 is started until normal operation is achieved;
3) The temperature is reduced at the speed of 30 ℃/h, when the temperature of the system is reduced to 200 ℃, the titanium sublimation pump 18 is sublimated, the sublimation current and time are 47A multiplied by 3min, the all-metal valve 21 of the molecular pump is closed after the sublimation is completed, and the molecular pump coarse unit 22 is stopped; when the system is cooled to 45 ℃, the titanium sublimation pump 18 is sublimated again, and the sublimation current and time are 47A multiplied by 3min; after the temperature of the test system had fallen to ambient temperature for 48 hours, the readings of the gauges 14-16, 23 and 24 were 3.3X10 respectively -12 mbar，4.4×10 -12 mbar，4.6×10 -12 mbar，4.5×10 -12 mbar，3.2×10 -12 mbar。
And (3) effect verification:
1. structural features of getter films
FIG. 7 is a cross-sectional and surface SEM topography of a TiZrCo film prepared in example 1.
FIG. 8 is a cross-sectional and surface SEM topography of a TiZr film without Co additions.
Comparing fig. 7 and fig. 8, it can be seen that the TiZrCo film particles have a columnar porous structure, and the columnar film has a larger specific surface area to exhibit better air extraction performance, and the presence of pores provides an effective path for gas diffusion; in particular, the pores among the particles are relatively large, which indicates that the addition of Co element is beneficial to increasing the lattice spacing, thereby improving the diffusion rate and the pumping capacity of gas molecules in the getter.
TABLE 1 structural characterization index data for TiZrCo and TiZr films prepared by the same Process
Film type Specific surface area (m) 2 /g) Aperture (nm) Porosity of the porous material Column radial width (nm)
TiZrCo Greater than 15 10～150 14％ 70～300
TiZr 5-7 10～40 5％ 20～200
2. Effect of getter film application
Fig. 9 is a pressure distribution curve obtained by the extreme vacuum of the titanium alloy lining thin-wall vacuum chamber of the example.
As can be seen from the figure, the maximum vacuum degree is 1.4X10 when the TiZrCo getter film is not plated on the titanium alloy ring -11 mbar, this value occurs in the middle of the titanium alloy lined thin-walled vacuum chamber; minimum vacuum of 4.5X10 -12 mbar, at two test pumping chambers 19.
After deposition of the TiZrCo film on the surface of the titanium alloy ring, the gauges 14-16, 23 and 24 read 3.3X10 respectively by activation of the TiZrCo film -12 mbar，4.4×10 -12 mbar，4.6×10 -12 mbar，4.5×10 -12 mbar，3.2×10 -12 mbar。
Compared with the titanium alloy ring which is not plated with the TiZrCo film,the pressure gradient of the titanium alloy lining extremely high vacuum chamber after film plating is greatly improved, the ultimate vacuum degree is further improved, and the ultimate vacuum degree value at any point is better than 5 multiplied by 10 -12 mbar。
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (10)

1. A TiZrCo getter film comprises the following components in atomic percent: ti is more than or equal to 42% and less than or equal to 46%, zr is more than or equal to 42% and less than or equal to 46%, and Co is more than or equal to 8% and less than or equal to 16%.
2. The TiZrCo getter film according to claim 1, wherein: the TiZrCo getter film is of a single-layer porous columnar structure, the columnar diameter is 70-300nm, the porosity is 8-16%, and the aperture is 10-150nm;
the thickness of the TiZrCo getter film is 0.4-5 mu m; specific surface area greater than 15m 2 /g；
The fully activated conditions of the TiZrCo getter film are: the temperature is kept for 40 to 48 hours at 220 to 250 ℃ and then is kept for 1 to 2 hours at 280 to 330 ℃.
3. A method for preparing a TiZrCo getter film according to claim 1 or 2, comprising the steps of:
s1, mixing and ball milling titanium powder, zirconium powder and cobalt powder to obtain TiZrCo powder;
s2, filling the TiZrCo powder into a die, vibrating, compacting, degassing and firing to obtain a target blank; turning the target blank to obtain the TiZrCo planar target;
s3, utilizing the TiZrCo planar target material to perform direct current magnetron sputtering deposition on the surface of the substrate to obtain the TiZrCo getter film.
4. The method for preparing a TiZrCo getter film according to claim 3, wherein: in step S1, the ball milling conditions are as follows:
the ball milling medium is zirconia ceramic balls;
the sphere proportion of the zirconia ceramic balls is D15: d10: d5: d3 =1: (1.5-2): (2.5-3): (2.5-3);
the rotating speed is 300-500r/min, and the time is 15-20h.
5. The method for preparing the TiZrCo getter film according to claim 3 or 4, wherein: in step S2, the mold is a rectangular graphite mold;
the conditions of the degassing are as follows: vacuum degree is (0.8-1.2) x 10 -5 mbar, time is 3-5h;
the firing conditions are as follows: in inert atmosphere, the temperature is 1350-1450 ℃, the pressure is 130-150MPa, and the time is 8-10h;
the cross section size of the TiZrCo planar target is as follows: 300-1000mm long, 20-150mm wide and 2-6mm thick;
the TiZrCo planar target consists of multiple sections, wherein the number of the sections is 2-6, and the length of each section is 135-405mm.
6. The method for preparing a TiZrCo getter film according to any of claims 3 to 5, wherein: in step S3, the substrate is a titanium alloy ring in a titanium alloy lined vacuum chamber;
the conditions of the direct current magnetron sputtering deposition are as follows: the pressure is 1X 10 -3 -2×10 -2 The current is 5-7A, the voltage is 400-500V, and the time is 10-15h.
7. A titanium alloy lined vacuum chamber comprising: a titanium alloy ring and the TiZrCo getter film according to claim 1 or 2 deposited on the surface of said titanium alloy ring.
8. The method for obtaining the extreme vacuum of the titanium alloy lining vacuum chamber comprises the following steps:
step A, vacuumizing the titanium alloy lining vacuum chamber in claim 7 by using a molecular pump coarse pump set, and starting a vacuum baking procedure;
and B, after the vacuum baking procedure is finished, cooling the system to normal temperature to obtain the extreme vacuum.
9. The method for obtaining the extreme vacuum of the titanium alloy lining vacuum chamber according to claim 8, wherein the method comprises the following steps of: in step a, the vacuum baking procedure is: heating to 220-250 ℃ at the speed of 20-30 ℃/h, preserving heat for 40-48h, heating to 280-300 ℃ at the same speed, and preserving heat for 2-4h.
10. The method for obtaining the extreme vacuum of the titanium alloy lining vacuum chamber according to claim 8 or 9, wherein: in the step B, the cooling process is as follows: firstly, cooling to 200 ℃ at a speed of 20-30 ℃/h, sublimating a titanium sublimation pump, cooling to 40-60 ℃ at the same speed, sublimating the titanium sublimation pump again, cooling to below 30 ℃ and standing;
the sublimation conditions are as follows: the current is 45-48A, and the time is 2-4min.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5101167A (en) * 1989-11-01 1992-03-31 Mitsubishi Denki Kabushiki Kaisha Accelerator vacuum pipe having a layer of a getter material disposed on an inner surface of the pipe
US6468043B1 (en) * 1996-06-19 2002-10-22 European Organization For Nuclear Research Pumping device by non-vaporisable getter and method for using this getter
US20040208752A1 (en) * 2003-02-20 2004-10-21 Mccambridge James D. Method for reducing the partial pressure of undesired gases in a small vacuum vessel
US20050164028A1 (en) * 2002-03-05 2005-07-28 Hartmut Reich-Sprenger Getter metal alloy coating and device and method for the production thereof
CN1715441A (en) * 2005-05-31 2006-01-04 中国科学院近代物理研究所 Vacuum system obtains the baking process of extra-high vacuum
CN115074669A (en) * 2022-06-10 2022-09-20 南京华东电子真空材料有限公司 Low-temperature activated high-capacity air suction film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5101167A (en) * 1989-11-01 1992-03-31 Mitsubishi Denki Kabushiki Kaisha Accelerator vacuum pipe having a layer of a getter material disposed on an inner surface of the pipe
US6468043B1 (en) * 1996-06-19 2002-10-22 European Organization For Nuclear Research Pumping device by non-vaporisable getter and method for using this getter
US20050164028A1 (en) * 2002-03-05 2005-07-28 Hartmut Reich-Sprenger Getter metal alloy coating and device and method for the production thereof
US20040208752A1 (en) * 2003-02-20 2004-10-21 Mccambridge James D. Method for reducing the partial pressure of undesired gases in a small vacuum vessel
CN1715441A (en) * 2005-05-31 2006-01-04 中国科学院近代物理研究所 Vacuum system obtains the baking process of extra-high vacuum
CN115074669A (en) * 2022-06-10 2022-09-20 南京华东电子真空材料有限公司 Low-temperature activated high-capacity air suction film

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