阅读说明：本技术 锆系非蒸散型吸气剂及其制备方法与应用 (Zirconium series non-evaporable getter and preparation method and application thereof ) 是由 杨兵 于 2020-06-18 设计创作，主要内容包括：本申请公开一种锆系非蒸散型吸气剂,所述吸气剂包括以质量百分数计的如下组分：锆60％-80％、钒5％-25％、铁2％-15％、钛2％-15％、铝2％-10％；该吸气剂是通过将锆、钒、铁、钛、铝混合均匀后,加热至液化并保温至少30分钟,然后冷却、破碎、球磨并过筛得到200微米以下获得的；该吸气剂抗氧化性能优于传统低温激活锆钒铁吸气剂,燃烧点高于锆钒铁吸气剂,同时吸气性能优于锆钒铁吸气合金；更有利于中高温真空器件的运用,填补了500℃-800℃激活的中温吸气剂的空白。(The application discloses a zirconium-based non-evaporable getter, which comprises the following components in percentage by mass: 60-80% of zirconium, 5-25% of vanadium, 2-15% of iron, 2-15% of titanium and 2-10% of aluminum; the getter is obtained by uniformly mixing zirconium, vanadium, iron, titanium and aluminum, heating until the mixture is liquefied, preserving heat for at least 30 minutes, cooling, crushing, ball-milling and sieving to obtain the getter with the particle size of less than 200 microns; the antioxidant performance of the getter is superior to that of the traditional low-temperature activated zirconium-vanadium-iron getter, the combustion point of the getter is higher than that of the zirconium-vanadium-iron getter, and meanwhile, the gas absorption performance of the getter is superior to that of the zirconium-vanadium-iron getter; the method is more beneficial to the application of medium-high temperature vacuum devices, and fills the blank of the medium-temperature getter activated at 500-800 ℃.)

1. A zirconium-based non-evaporable getter, characterized in that said getter comprises the following components: the weight percentage of the material is as follows: 70-75% of zirconium, 13-18% of vanadium, 4-10% of iron, 2-9% of titanium and 2-8% of aluminum.

2. Non-evaporable getter according to claim 1, characterized in that it comprises, in mass percentage, zirconium 70-72%, vanadium 13-18%, iron 4-6%, titanium 4-8%, aluminium 2-3%.

3. Process for the preparation of a non-evaporable getter according to claim 1 or 2, characterized by the following steps:

uniformly mixing zirconium, vanadium, iron, titanium and aluminum in sequence according to the mass ratio, heating to be liquefied, preserving heat for at least 30 minutes, cooling, crushing, ball-milling and sieving to obtain powder of less than 200 micrometers, namely the zirconium-based non-evaporable getter.

4. Use of a non-evaporable getter according to claim 1 or 2 for the preparation of getter devices.

Technical Field

The application relates to the field of getters, in particular to a zirconium-based non-evaporable getter.

Background

Getters are a generic term for a class of agents or devices that effectively sorb certain gas molecule(s) to obtain or maintain a vacuum and purify the gas. The getter is widely applied to the fields of electric vacuum devices and vacuum science and technology, such as electric light sources, thermal insulation devices (such as heat preservation containers, vacuum glass and the like), electric vacuum devices (such as receiving and amplifying tubes, power transmitting tubes, high-voltage pulse modulation tubes, oscilloscopes, traveling-wave tubes and the like) and basic physical research (such as controlled nuclear fusion devices, positive and negative electron colliders and the like) so as to absorb residual gas in the preparation process and gas emitted by the devices during working, play a role in improving and maintaining the vacuum degree of the devices and stabilizing the devices, and have important influence on the performance and service life of the devices.

The getter is generally classified into an evaporable getter and a non-evaporable getter, and the non-evaporable getter refers to a getter which can directly absorb gas after being activated. The zirconium-based alloy material is the most widely used non-evaporable getter at present, and can be divided into two types of low-temperature activated getters and high-temperature activated getters according to the activation temperature, and the getters which can be effectively activated at a temperature below 500 ℃ are low-temperature activated getters, such as zirconium-vanadium-iron getters; the getter which can be effectively activated at the temperature of more than 800 ℃ is a high-temperature activated getter such as a zirconium-aluminum getter, and a non-evaporable getter suitable for the temperature range of 500-800 ℃ is still blank (the zirconium-vanadium-iron getter is activated at the temperature of 400 ℃ and consumes a part of the gettering performance at the temperature of about 600 ℃), and the zirconium-aluminum is only activated at the temperature of about 40 percent, so the zirconium-vanadium-iron getter is generally used in the temperature range in practice). The non-evaporable getter has large air suction amount and long maintenance time, and applied devices can be repaired, so the non-evaporable getter is widely applied to the preparation of vacuum tubes and vacuum heat-preservation cups at present.

The production of vacuum devices is often in a high-temperature environment, and the existing non-evaporable getter has higher requirements on process guarantee in the application of the high-temperature environment due to lower ignition point, thereby improving the preparation difficulty and the rejection rate. Taking a vacuum heat-insulating cup process as an example, when a traditional zirconium-vanadium-iron getter is adopted, the temperature of the heat-insulating cup is exhausted at high temperature and reaches over 600 ℃, when discharging and charging are finished, the temperature difference exists between a thermocouple and the temperature of a furnace wall, the temperature of the furnace wall is about 300 ℃, a production line takes out a last batch of vacuum heat-insulating cups after baking and exhausting, a new batch of vacuum heat-insulating cups are put into a hearth for exhausting, and because the replaced products are not vacuum, the oxygen concentration around an air absorbent in the heat-insulating cups is high, the temperature in the furnace is uneven, the air absorbent is exposed in a large amount of air at high temperature, the air absorbent in the products close to the furnace wall is strongly oxidized and even burns, the air absorbent or the air absorbent in the products close to the. In addition, in the manufacturing process of some titanium vacuum devices or vacuum devices needing lead-free sealing, the sealing temperature is higher, such as 500-700 ℃, the sealing temperature is kept for more than 1 hour, and the outgassing of the vacuum device material is larger. Some existing products add an antioxidant material to the zirconium vanadium iron getter alloy or reduce the vanadium zirconium content to improve the anti-combustion temperature, but reduce the activity of the getter material, sacrifice the getter performance, and reduce the getter amount and the getter speed. Therefore, the development of a non-evaporable getter with wide activation temperature range, high ignition point and large gas absorption capacity has become a technical problem to be solved in the field.

Disclosure of Invention

In view of the above problems, the present application provides a zirconium-based non-evaporable getter, which has a high ignition point and a large gettering capacity, so as to prolong the lifetime of a vacuum device and improve the safety of a vacuum device manufacturing process.

The application is realized by the following technical scheme:

a zirconium series non-evaporable getter comprises the following raw materials: by mass percentage, zirconium 60-80%, vanadium 5-25%, iron 2-15%, titanium 2-15%, and aluminum 2-10%; the obtained zirconium series non-evaporable getter has powder particle size not higher than 200 microns (including 200 microns) after ball milling.

Further, in the zirconium-based non-evaporable getter, the mass percentages of the components are preferably: 70-72% of zirconium, 13-18% of vanadium, 4-6% of iron, 4-8% of titanium and 2-3% of aluminum.

Secondly, the application also provides a preparation method of the zirconium-based non-evaporable getter, which comprises the following specific steps:

and (2) uniformly mixing zirconium, vanadium, iron, titanium and aluminum element metals according to the mass ratio, melting and heating in a vacuum melting furnace to liquefy (about 1800 ℃), preserving heat for at least 30 minutes, pouring the liquefied alloy into a crucible for cooling, crushing, ball-milling and sieving to obtain powder below 200 micrometers, thus obtaining the zirconium series non-evaporable getter.

Third, the present application provides the use of the non-evaporable getter in the manufacture of getter devices; the zirconium series non-evaporable getter can be pressed into ingots, chips, strips and sheets according to actual requirements, and can be used for various different product types.

The application provides a zirconium system non-evaporable getter can adsorb hydrogen in a large number in the vacuum, can also adsorb oxygen, nitrogen gas, carbon monoxide, vapor etc. simultaneously, and the wide use in vacuum device, for example traditional zirconium vanadium iron, zirconium aluminium getter extensively are used for devices such as gas discharge lamp, vacuum switch tube, travelling wave pipe, vacuum thermos cup, play and adsorb residual gas, guarantee functions such as vacuum degree during system's working life. Compared with the existing non-evaporable adsorbent, the getter material provided by the application has the following beneficial effects:

1. the getter prepared by adopting the Zr-V-Fe-Ti-Al element of the invention has obviously improved initial pumping speed and total getter capacity after activation, and prevents the getter material from premature failure in the preparation of a vacuum device, thereby prolonging the service life of the vacuum device and saving the cost.

2. The getter prepared by the getter alloy has oxidation resistance superior to that of the traditional low-temperature activated zirconium vanadium iron getter, has a combustion point higher than that of the zirconium vanadium iron getter, and has getter performance superior to that of the zirconium vanadium iron getter; in the production process of the vacuum device, the getter is not flammable in a high-temperature process, the risk of combustion failure of the getter in the production process is reduced, and the safety performance of the preparation process of the vacuum device is improved.

3. The getter prepared by the getter alloy has the activation temperature lower than that of the traditional high-temperature activated zirconium-aluminum getter, has the gettering performance equivalent to that of the zirconium-aluminum getter, is more favorable for the application of medium and high temperature vacuum devices, and fills the blank of the medium temperature getter activated at 500-800 ℃.

Drawings

FIG. 1 is a schematic representation of the initial draw rate and draw capacity at 430 deg.C for an example getter;

figure 2 is a graph of the initial pumping rate and the suction capacity at 650 c for example getters.

Detailed Description

The present application is further illustrated with reference to specific embodiments below, wherein the starting materials referred to in the examples below are all commercially available unless otherwise indicated.

The zirconium, vanadium, iron, titanium and aluminum powders referred to in the following examples are all mixed and melted in the form of granules or blocks.

The alloy smelting adopts a vacuum induction smelting furnace, and the equipment model is as follows: TPY/ZKRL/50P;