CN115449690B - Zr-V series getter material with high strength and high gettering performance and preparation method thereof - Google Patents

Zr-V series getter material with high strength and high gettering performance and preparation method thereof Download PDF

Info

Publication number
CN115449690B
CN115449690B CN202211141908.5A CN202211141908A CN115449690B CN 115449690 B CN115449690 B CN 115449690B CN 202211141908 A CN202211141908 A CN 202211141908A CN 115449690 B CN115449690 B CN 115449690B
Authority
CN
China
Prior art keywords
parts
getter
series
getter material
high strength
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211141908.5A
Other languages
Chinese (zh)
Other versions
CN115449690A (en
Inventor
陈祯力
吴海洋
林�建
罗秋霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Ansune Science & Technology Stock Co ltd
Original Assignee
Zhejiang Ansune Science & Technology Stock Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Ansune Science & Technology Stock Co ltd filed Critical Zhejiang Ansune Science & Technology Stock Co ltd
Priority to CN202211141908.5A priority Critical patent/CN115449690B/en
Publication of CN115449690A publication Critical patent/CN115449690A/en
Application granted granted Critical
Publication of CN115449690B publication Critical patent/CN115449690B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Abstract

The invention relates to the technical field of getter materials, in particular to a Zr-V getter material with high strength and high gettering performance and a preparation method thereof, wherein the material comprises the following raw materials in parts by weight: zr+Hf43.45-43.85 parts, ti20.81-21.21 parts, fe17.69-18.09 parts, V12.96-13.36 parts, S2.28-2.68 parts, cr0.25-0.29 parts, si0.20-0.24 parts, mn0.19-0.23 parts, mo0.15-0.19 parts; according to the invention, zr, hf, ti, fe, V, S, cr, si, mn and Mo are used as raw materials, and the prepared Zr-V getter material has good getter rate and getter total amount and excellent strength performance through high-temperature melting, nitrogen filling, cooling and crushing, reshaping and sintering.

Description

Zr-V series getter material with high strength and high gettering performance and preparation method thereof
Technical Field
The invention relates to the technical field of getter materials, in particular to a Zr-V getter material with high strength and high gettering performance and a preparation method thereof.
Background
The getter material is a material which is applied to vacuum, ultra-high vacuum and ultra-high vacuum environment and can effectively absorb active gas (H) through physical and chemical actions 2 、CO、O 2 、H 2 O、CO 2 Etc.).
The Zr-V getter is a common getter in engineering application, for example, patent application number is CN201711227019.X, which describes in the specification that a Ni coating layer is plated on the surface of the powder of the Zr-V getter, and then the powder of the getter with Ni plated on the surface is pressed, molded and sintered by adopting a powder metallurgy process, so as to obtain the Zr-V getter with high strength and high gettering performance. The preparation method is particularly suitable for preparing Zr-V series getter materials with difficult sintering, and can prepare porous sintering type Zr-V series getter materials with good bonding strength and excellent getter performance at a lower sintering temperature (less than or equal to 700 ℃), and the prepared getter materials are particularly suitable for the field of electric vacuum devices with harsh service conditions, such as a shaking gyroscope, a vehicle-mounted infrared detector and the like. Although the above patent can prepare zr—v based getter materials, the mechanical strength and gettering effect cannot meet the use requirements.
In summary, developing a Zr-V-based getter material with high strength and high gettering performance and a method for preparing the same are key problems to be solved in the technical field of getter materials.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the Zr-V series getter material with high strength and high gettering performance and the preparation method thereof, and the Zr-V series getter material prepared by the invention not only has good gettering rate and total gettering amount, but also has excellent strength performance.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the first aspect of the invention: the Zr-V series getter material with high strength and high gettering performance is provided, and comprises the following raw materials in parts by weight: 43.45-43.85 parts of Zr+Hf, 20.81-21.21 parts of Ti, 17.69-18.09 parts of Fe, 12.96-13.36 parts of V, 2.28-2.68 parts of S, 0.25-0.29 part of Cr, 0.20-0.24 part of Si, 0.19-0.23 part of Mn and 0.15-0.19 part of Mo.
The invention is further provided with: the material comprises the following raw materials in parts by weight: 43.65 parts of Zr+Hf, 21.01 parts of Ti, 17.89 parts of Fe, 13.16 parts of V, 2.48 parts of S, 0.27 parts of Cr, 0.22 parts of Si, 0.21 parts of Mn and 0.17 parts of Mo.
The second aspect of the invention: also provides a preparation method of the Zr-V series getter material with high strength and high gettering performance, which comprises the following steps:
(1) Zr, hf, ti, fe, V, S, cr, si, mn and Mo are weighed and placed in a smelting furnace to be melted in the atmosphere of protective gas;
(2) Cooling the mixed melt in the step (1) to normal temperature, and then crushing and ball milling to obtain mixed powder;
(3) Hot pressing the mixed powder in a die to form a pressed compact;
(4) And sintering the pressed compact in vacuum, taking out and cooling to normal temperature.
The invention is further provided with: in the step (1), the protective gas is nitrogen.
The invention is further provided with: in the step (2), the granularity of the mixed powder is 300-100 meshes.
The invention is further provided with: in the step (3), the hot press molding pressure is 100-260Mpa, the temperature is 1050-1100 ℃, and the pressure maintaining time is 5-10s.
The invention is further provided with: in the step (4), the sintering temperature is 1200-1300 ℃ and the time is 0.2-0.4h.
The invention is further provided with: in the step (4), the vacuum degree of the vacuum sintering is 3-4 multiplied by 10 -3 Pa。
Advantageous effects
Compared with the prior art, the technical proposal provided by the invention has the following advantages that
The beneficial effects are that:
according to the invention, zr, hf, ti, fe, V, S, cr, si, mn and Mo are used as raw materials, and the prepared Zr-V series getter material has good getter rate and getter total amount, excellent strength performance and wide application prospect and is worthy of popularization through high-temperature melting, nitrogen filling, cooling and crushing, reshaping and sintering.
Drawings
FIG. 1 is a graph showing the variation of the gettering rate and the gettering amount of a Zr-V getter material prepared in example 1 in the performance test of the present invention, wherein the horizontal coordinate is the gettering amount and the vertical coordinate is the gettering rate.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further described below with reference to examples.
Example 1:
the invention provides a Zr-V series getter material with high strength and high gettering performance, which comprises the following raw materials in parts by mass: 43.65 parts of Zr+Hf, 21.01 parts of Ti, 17.89 parts of Fe, 13.16 parts of V, 2.48 parts of S, 0.27 parts of Cr, 0.22 parts of Si, 0.21 parts of Mn and 0.17 parts of Mo.
In addition, the invention also provides a preparation method of the Zr-V series getter material with high strength and high gettering performance, which comprises the following steps:
(1) Zr, hf, ti, fe, V, S, cr, si, mn and Mo are weighed and placed in a smelting furnace to be melted under the atmosphere of protective gas.
Further, the shielding gas is nitrogen.
(2) And (3) cooling the mixed melt in the step (1) to normal temperature, and then crushing and ball milling to obtain mixed powder.
Further, the mixed powder had a particle size of 100 mesh.
(3) The mixed powder is hot pressed in a die to form a compact.
Further, the hot press molding pressure was 260Mpa, the temperature was 1100 ℃, and the dwell time was 10s.
(4) And sintering the pressed compact in vacuum, taking out and cooling to normal temperature.
Further, the sintering temperature was 1300℃for 0.4h.
Further, the degree of vacuum of the vacuum sintering was 4X 10 -3 Pa。
Example 2:
the invention provides a Zr-V series getter material with high strength and high gettering performance, which comprises the following raw materials in parts by mass: 43.45 parts of Zr+Hf, 20.81 parts of Ti, 17.69 parts of Fe, 12.96 parts of V, 2.28-2.68 parts of S, 0.25 part of Cr, 0.20 part of Si, 0.19 part of Mn and 0.15 part of Mo.
In addition, the invention also provides a preparation method of the Zr-V series getter material with high strength and high gettering performance, which comprises the following steps:
(1) Zr, hf, ti, fe, V, S, cr, si, mn and Mo are weighed and placed in a smelting furnace to be melted under the atmosphere of protective gas.
Further, the shielding gas is nitrogen.
(2) And (3) cooling the mixed melt in the step (1) to normal temperature, and then crushing and ball milling to obtain mixed powder.
Further, the particle size of the mixed powder was 300 mesh.
(4) The mixed powder is hot pressed in a die to form a compact.
Further, the hot press molding pressure was 100MPa, the temperature was 1050℃and the dwell time was 5s.
(4) And sintering the pressed compact in vacuum, taking out and cooling to normal temperature.
Further, the sintering temperature was 1200℃and the time was 0.2h.
Further, the degree of vacuum of the vacuum sintering was 3X 10 -3 Pa。
Example 3:
the invention provides a Zr-V series getter material with high strength and high gettering performance, which comprises the following raw materials in parts by mass: 43.85 parts of Zr+Hf, 21.21 parts of Ti, 18.09 parts of Fe, 13.36 parts of V, 2.68 parts of S, 0.29 parts of Cr, 0.24 parts of Si, 0.23 parts of Mn and 0.19 parts of Mo.
In addition, the invention also provides a preparation method of the Zr-V series getter material with high strength and high gettering performance, which comprises the following steps:
(1) Zr, hf, ti, fe, V, S, cr, si, mn and Mo are weighed and placed in a smelting furnace to be melted under the atmosphere of protective gas.
Further, the shielding gas is nitrogen.
(2) And (3) cooling the mixed melt in the step (1) to normal temperature, and then crushing and ball milling to obtain mixed powder.
Further, the mixed powder had a particle size of 200 mesh.
(5) The mixed powder is hot pressed in a die to form a compact.
Further, the hot press molding pressure was 180MPa, the temperature was 1070℃and the dwell time was 7s.
(4) And sintering the pressed compact in vacuum, taking out and cooling to normal temperature.
Further, the sintering temperature was 1250℃and the time was 0.3h.
Further, the degree of vacuum of the vacuum sintering was 4X 10 -3 Pa。
And (3) performance detection:
a high-strength high-gettering-performance Zr-V based getter material was prepared according to the method of example 1, example 2 and example 3, respectively.
1) According to the dynamic balance detection method: (H) 2 ) 12.10-3, the gettering rate and the total gettering amount of each group of high-strength and high-gettering performance zr—v based gettering materials were measured, and the data of each group of experiments were recorded in table 1.
Table 1: recording table of each group of Zr-V getter materials
Figure GDA0004128545960000071
As can be seen from fig. 1 and table 1, the Zr-V based getter materials prepared in example 1, example 2 and example 3 each have a good getter rate and a good getter total amount, and the getter rate and the getter total amount of example 1 are optimal. The Zr-V getter material prepared by the invention has good getter rate and getter total amount.
2) The intensity performance of each group of Zr-V getter materials is checked by adopting a random vibration method, the frequency is 10Hz-2000Hz, and the acceleration spectral density is 5 (m/s) 2 ) 2 Data from each set of experiments are recorded in Table 2 for 15min per direction per Hz, X, Y, Z.
Table 2: recording table of each group of Zr-V getter materials
Group of Detection result
Example 1 The surface has no cracking phenomenon
Example 2 The surface has no cracking phenomenon
Example 3 The surface has no cracking phenomenon
As can be seen from Table 2, the Zr-V getter materials prepared in examples 1, 2 and 3 were examined by random vibration method, and the surfaces of the Zr-V getter materials prepared in each group were free from cracking. The Zr-V getter material prepared by the invention has excellent strength performance.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (2)

1. The Zr-V series getter material with high strength and high gettering performance is characterized by comprising the following raw materials in parts by weight: zr+Hf43.45-43.85 parts, ti20.81-21.21 parts, fe
17.69-18.09 parts, 12.96-13.36 parts of V, 2.28-2.68 parts of S, 0.25-0.29 part of Cr, 0.20-0.24 part of Si, 0.19-0.23 part of Mn and 0.15-0.19 part of Mo;
the preparation method of the Zr-V series getter material with high strength and high gettering performance comprises the following steps:
(1) Zr, hf, ti, fe, V, S, cr, si, mn and Mo are weighed and placed in a smelting furnace to be melted in the atmosphere of protective gas;
(2) Cooling the mixed melt in the step (1) to normal temperature, and then crushing and ball milling to obtain mixed powder;
(3) Hot pressing the mixed powder in a die to form a pressed compact;
(4) Vacuum sintering the pressed compact, taking out and cooling to normal temperature;
in the step (1), the protective gas is nitrogen;
in the step (2), the granularity of the mixed powder is 300-100 meshes;
in the step (3), the hot press molding pressure is 100-260Mpa, the temperature is 1050-1100 ℃, and the pressure maintaining time is 5-10s;
in the step (4), the sintering temperature is 1200-1300 ℃ and the time is 0.2-0.4h;
in the step (4), the vacuum degree of the vacuum sintering is 3-4 multiplied by 10 -3 Pa。
2. The Zr-V series getter material with high strength and high gettering performance according to claim 1, characterized by comprising the following raw materials in parts by weight: 43.65 parts of Zr+Hf, 21.01 parts of Ti, 17.89 parts of Fe, 13.16 parts of V, 2.48 parts of S, 0.27 parts of Cr, 0.22 parts of Si, 0.21 parts of Mn and 0.17 parts of Mo.
CN202211141908.5A 2022-09-20 2022-09-20 Zr-V series getter material with high strength and high gettering performance and preparation method thereof Active CN115449690B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211141908.5A CN115449690B (en) 2022-09-20 2022-09-20 Zr-V series getter material with high strength and high gettering performance and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211141908.5A CN115449690B (en) 2022-09-20 2022-09-20 Zr-V series getter material with high strength and high gettering performance and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115449690A CN115449690A (en) 2022-12-09
CN115449690B true CN115449690B (en) 2023-06-06

Family

ID=84305447

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211141908.5A Active CN115449690B (en) 2022-09-20 2022-09-20 Zr-V series getter material with high strength and high gettering performance and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115449690B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1015645B (en) * 1989-09-07 1992-02-26 安守环 Non-evaporation type low temp. activated degasser and process thereof
IL96391A (en) * 1989-11-24 1995-05-26 Energy Conversion Devices Inc Catalytic hydrogen storage electrode materials for use in electrochemical cells
CN109834263A (en) * 2017-11-29 2019-06-04 北京有色金属研究总院 A kind of preparation method of high intensity high pumping property Zr-V system gettering material
CN108531877B (en) * 2018-06-06 2020-01-10 中国科学院高能物理研究所 TiZrVHf quaternary getter film
CN110616388A (en) * 2019-10-16 2019-12-27 上海晶维材料科技有限公司 Preparation method of anti-pulverization block getter
CN110614361B (en) * 2019-10-16 2022-10-14 上海晶维材料科技有限公司 Method for preparing block getter by microwave sintering
CN112095035A (en) * 2020-09-14 2020-12-18 张心强 Non-evaporable low-temperature activated high-temperature getter alloy and preparation method thereof
CN114150202A (en) * 2021-11-02 2022-03-08 南京恩瑞科技有限公司 Preparation method of five-membered titanium alloy non-evaporable getter

Also Published As

Publication number Publication date
CN115449690A (en) 2022-12-09

Similar Documents

Publication Publication Date Title
US20220288683A1 (en) Method of making cermet or cemented carbide powder
US9434003B2 (en) Process for producing an interconnector of a high-temperature fuel cell
US20020106297A1 (en) Co-base target and method of producing the same
JP4080133B2 (en) High density nonmagnetic alloy and method for producing the same
CN101240382A (en) Method for preparing high dense TiAl-base alloy
CN108330408B (en) A kind of high intensity alferric ferritic ODS steel and preparation method thereof
JP2009544841A (en) Iron-based powder
CN105063394A (en) Titanium or titanium alloy material preparing method
CN115449690B (en) Zr-V series getter material with high strength and high gettering performance and preparation method thereof
CN106498220B (en) Nickelous carbonate is used for the method for improving sintering copper-manganese damping alloy performance
CN110394450B (en) Method for promoting densification of metal blank by utilizing hydrogen absorption and expansion of metal
JP2007027320A (en) Soft magnetic material, method of manufacturing the same and dust core
JP2007048902A (en) Powder magnetic core and its manufacturing method
CN106424716A (en) Method for modifying performance of sintered Mn-Cu damping alloy with ferrous oxalate
CN112453384B (en) Preparation method of diffusion bonding titanium powder
CN102605278B (en) High-temperature alloy and hot isostatic pressing sintering method thereof
CN111101020B (en) Zircon graphene getter material and preparation method thereof
CN111266570B (en) Sn-xAl sintering agent for TiAl-based alloy and preparation method thereof, preparation method of TiAl-based alloy and product
CN114192800A (en) Method for preparing high-density, high-toughness and high-entropy alloy by selective electron beam melting technology
CN109852901B (en) High-specific-gravity alloy steel and preparation method thereof
US20200168376A1 (en) Magnetic powder, compressed powder core, method of preparation thereof
GB829640A (en) Improvements relating to the manufacture of alloy strip
CN114160786B (en) Mixed powder type getter and preparation method thereof
KR100262488B1 (en) Method of manufacturing sintered fe-si type soft magnets
CN109338249A (en) A kind of iron base amorphous magnetically-soft alloy material and preparation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant