CN1053476C - Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof - Google Patents
Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof Download PDFInfo
- Publication number
- CN1053476C CN1053476C CN96106343A CN96106343A CN1053476C CN 1053476 C CN1053476 C CN 1053476C CN 96106343 A CN96106343 A CN 96106343A CN 96106343 A CN96106343 A CN 96106343A CN 1053476 C CN1053476 C CN 1053476C
- Authority
- CN
- China
- Prior art keywords
- alloy
- vacuum
- getter
- temperature
- activation
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
The present invention relates to a multi-element non-evapotranspiation type low-temperature activation Zr base getter alloy and a producing method thereof. The Zr base getter alloy comprises zirconium, nickel, vanadium, ferrum and lanthanum group rare earth. The getter is made by melting in a vacuum arc or a vacuum medium frequency induction furnace, and production processes are simple. The activation temperature of the Zr base getter alloy is 450 (+/-) 50 DEG C, and working temperature is from 25 to 350 DEG C. The gas suction performance of the Zr base getter alloy is good, and the gas suction performance to H2 is particularly excellent. Compared with usual not-evapotranspiation low temperature activation getter alloys Zr-V-Fe and Zr-V-Fe-Ti, the performance for sucking the H2 is respectively enhanced by 30 % and 20%. The Zr base getter alloy can be widely used for electric light source components, inert gas purifiers and vacuum devices which only permit heating under moderate temperature. The hetter alloy is more suitable for vacuum insulation cups (bottles), vacuum tube water heaters of solar energy and petroleum exploration heat insulation pipes.
Description
The present invention relates to the zirconium base alloy field, in particular as polynary non-evaporation type low temp activation Zr base getter alloys and method for making thereof.
In some vacuum devices, as vacuum cup (bottle), solar energy vacuum tube water heater, petroleum prospecting instlated tubular etc., it is to utilize in a vacuum that gas is thin, a little less than the conduction of gas to heat, the little principle of loss of heat reaches vessel insulation, heat insulation effect.Vacuum tightness is higher, and insulation, effect of heat insulation are better.Vacuum device is in the life-time service process, and the infiltration of gas takes place in regular meeting, reduces vacuum tightness, makes vacuum device lose efficacy reduction of service life.For the vacuum tightness that improves these vacuum devices with increase the service life, in device, generally all put into a certain amount of non-evaporation type low temp activated degasser alloy.This class getter alloys commonly used has Zr-V-Fe (us-4312669), Zr-V-Fe-Ti (China Patent No. 89106797.3) and low-temp activation Zr-C getter.In these vacuum devices, add a kind of in the above-mentioned getter alloys, played good heat insulating effect, but still unsatisfactory.As everyone knows, guarantee that the key of this class vacuum device quality is a gas clean-up, reduce the conduction of gas heat.Main component in the residual gas is H
2, O
2, N
2, CO
2And H
2O, their thermal conductivity difference is very big, wherein H
2Thermal conductivity the highest, be 0.152, be respectively O
2, N
2, CO
2, H
26.6 times, 6.9 times, 8.4 times and 1.4 times of the thermal conductivity of O.Therefore, H
2Residual content very big to the influence of vacuum device heat-insulating property, even the H of denier
2, also can produce serious harm to the heat-insulating property of device.In addition, H
2Atomic radius less, in the device use, the easiest infiltration.So a kind of getter alloys of invention, it is to H
2Gettering rate and gulp capacity faster, bigger than several non-evaporation type low temp activated degassers now commonly used, be very urgent and the utmost point has realistic meaning.
The objective of the invention is: provide a kind of than existing non-evaporation type low temp activated degasser alloy to H
2Gettering rate and faster, the higher getter alloys of gulp capacity, it also absorbs other reactive gas simultaneously, and its manufacturing process wants simple, easily grasps.
Embodiment of the present invention are, adopt the zirconium base alloy of following Chemical Composition (weight part): zirconium (Zr) 62-75, nickel (Ni) 6.5-10.5, vanadium (V) 16-25, iron (Fe) 2-8, lanthanum family rare earth (M1) 1-6, (wherein the content of lanthanum family rare earth is lanthanum 45-50%, praseodymium 10-15%, cerium 2-5%, neodymium 35-40% weight) just can realize above-mentioned purpose.
It is base that the present invention selects with the zirconium, adds other alloying element again, and their effects in alloy system are summarized as follows respectively:
The selection metal zirconium is a base element, is because the zirconium metal is more active, various reactive gass is all had stronger avidity, and form all cpds, and zirconium itself is a kind of getter material of excellence.But on zirconium particulate surface one deck protective oxide layer is arranged all generally, must in high temperature, vacuum, activation treatment remove this layer oxide film, expose the unsalted surface of zirconium after, it just has air-breathing property.This has limited the direct use of zirconium under some conditions.For the broadened application scope, reduce its activationary temperature, must add some other alloying elements.
Metallic nickel: it and zirconium can form intermetallic compound: Zr
2Ni, ZrNi etc., these compounds have adsorptivity preferably to reactive gas, wherein to H
2Adsorptivity particularly excellent.
Vanadium metal, iron: they and zirconium also form multiple intermetallic compound: ZrV
2, ZrFe
2, Zr
2Fe etc.These compounds all have good absorptivity to reactive gas.In addition, add in the time of vanadium, iron, and zirconium can form compound between the accurate binary metal of C15 type cubic structure: Zr (V
1-xFe
x)
2, wherein X ≈ 0.17, and this intermetallic compound has stronger pumping property.In addition, add the activationary temperature that vanadium can also reduce alloy system.
Adding the rare earth element of a certain amount of lanthanum family, can play the crystal boundary that purifies alloy, promote alloy reactivation process and improve the effect of alloy pumping property, is one of prominent feature of the present invention.
The manufacturing process of getter alloys of the present invention is: weigh up granular zirconium, Ni-V-Fe and lanthanum family rare earth respectively.Above-mentioned five kinds of granular starting material bakings are placed crucible respectively except that behind the moisture.Adopt general fusing of vacuum Medium frequency induction or vacuum (argon filling) arc-melting to become ingot.Ingot is got the particle powder of particle less than 500 μ m through fragmentation, grinding, sub-sieve under argon shield.Concrete fabrication process parameters is listed among the embodiment.
The using method of getter alloys is getter alloys will be carried out preactivate to handle, and eliminates the thin protective oxide film of particle surface last layer, exposes unsalted surface.Activation condition is under vacuum, 450 ± 50 ℃ of activationary temperatures, activationary time 10-30min, the working temperature 25-350 of getter alloys ℃.
Relatively listing among Fig. 1-Fig. 8 of the pumping property of polynary non-evaporation type low temp activation Zr base getter alloys of the present invention and the pumping property of getter alloys such as Zr-V-Fe, Zr-V-Fe-Ti:
Fig. 1 alloy suction H at room temperature
2Rational curve.
The suction H of Fig. 2 alloy under 300 ℃
2Rational curve.
Fig. 3 alloy suction N at room temperature
2Rational curve.
Fig. 4 alloy suction CO rational curve at room temperature.
Fig. 5 alloy is at room temperature to H
2Gettering rate and gulp capacity and time relation.
Fig. 6 alloy under 300 ℃ to H
2Gettering rate and gulp capacity and time relation.
Fig. 7 alloy is at room temperature to H
2Gettering rate and gulp capacity and time relation.
Fig. 8 alloy is at room temperature to gettering rate and gulp capacity and the time relation of CO.
Product of the present invention has particle powder, sheet and be compressed on the metal nickel strap band and Ring. This product is used for the electric light source components and parts. Inert gas purge and a permission are in middle temperature In the vacuum device of lower heating, be specially adapted to vacuum cup (bottle), solar energy In vacuum tube water heater and the oil exploration instlated tubular.
Below in conjunction with embodiment the pumping property of getter alloys of the present invention is further specified:
Embodiment 1:
Chemical Composition by getter alloys: take by weighing granular 68.5 the gram Zr, 6.5 the gram Ni, 18 the gram V, 4 the gram Fe, 3 the gram M1 family's rare earths (lanthanum 48%, cerium 3%, praseodymium 13%, neodymium 36% weight) join 100 the gram ingots, melt at general vacuum argon filling electric arc furnace.Vacuum tightness reaches 5 * 10 in stove
-2During Pa, applying argon gas, prepurging is once.Under argon shield, carry out melting in the non-consumable arc furnace, melt temperature is 1500 ℃.In order to make alloy ingredient even, melt back three times.Little ingot through broken, grind to form＜particle powder of 500 μ m, get the small pieces that 0.28g is pressed into 6 * 2mm, with non evaporable getter material and goods pumping property testing method (GB8763-88) measured the getter alloys sheet under room temperature and 300 ℃ to H
2Air-breathing characteristic and gettering rate, the time dependent relation of gulp capacity.To have prepared Zr-V-Fe and Zr-V-Fe-Ti powdered alloy in order relatively using with the quadrat method fusing, and to be pressed into the small pieces of φ 6 * 2mm, carried out performance test on the same stage, testing conditions: test piece activates 10 minutes down at 500 ℃, and operating pressure is 7 * 10
-4Pa, it the results are shown among Fig. 1, Fig. 2, Fig. 5 and Fig. 6.
The result of Fig. 1 and Fig. 2 shows, getter alloys of the present invention under room temperature and 300 ℃ to H
2Air-breathing characteristic, all be better than the suction H of existing non-evaporation type low temp activated degasser alloy Zr-V-Fe and Zr-V-Fe-Ti
2Characteristic.Can draw getter alloys of the present invention at room temperature to H from Fig. 5 and Fig. 6 result
2Gettering rate S in the time of 10 minutes
10(ml/sg) and the gulp capacity Q 240 minutes the time
240(mlPa/g) be 1150ml/sg and 6400mlPa/g, than the suction H of Zr-V-Fe and Zr-V-Fe-Ti alloy
2Performance improves 30～35% and 15～25% respectively, getter alloys of the present invention under 300 ℃ to H
2S
10And Q
240Be 1800ml/sg and 12500mlPa/g, than the suction H of Zr-V-Fe and Zr-V-Fe-Ti alloy
2Performance improves 25-30% and 15-20% respectively.
Embodiment 2:
Chemical Composition by getter alloys: take by weighing granulous 3550 gram Zr, 350 gram Ni, 800 gram V, 200 gram Fe, 100 gram M1 (wherein lanthanum 46%, cerium 5%, praseodymium 14%, neodymium 35% weight) join 5000 gram ingots, carry out melting in general vacuum medium frequency induction furnace, vacuum tightness is 5 * 10
-2Pa; 1550 ℃ of melt temperature ≈; liquation burns in water jacketed copper crucible; ingot carries out fragmentation, grinding, sub-sieve under argon shield; take out the particle powder 5.6g of＜500 μ m; be pressed into 20 of the small pieces of 6 * 2mm,, measured small pieces at room temperature to N with used measuring method and testing conditions in the example 1
2With the air-breathing characteristic of CO and gettering rate, the time dependent curve of gulp capacity.In order to compare, carried out test on the same stage with Zr-V-Fe prepared in the example 1 and Zr-V-Fe-Ti alloy slice, it the results are shown among Fig. 3, Fig. 4, Fig. 7 and Fig. 8.
As can be seen, getter alloys of the present invention is at room temperature to N from the result of Fig. 3, Fig. 4, Fig. 7 and Fig. 8
2Pumping property lower slightly than Zr-V-Fe alloy, (low 5-10%), and than Zr-V-Fe-Ti alloy height (high 15-20%).Getter alloys of the present invention at room temperature to the pumping property of CO than Zr-V-Fe alloy slightly high (～5%), and than the high 15-20% of Zr-V-Fe-Ti alloy.
Comparative example:
Add the influence of rare earth element in order to understand to the alloy pumping property, press routine composition and prepared two kinds of alloys No. 1,68.5 gram Zr-6.5 gram Ni-17 gram V-4 gram Fe-4 gram M1 of 71 gram Zr-7 gram Ni-18 gram V-4 gram Fe and No. 2, each alloy is joined 100 grams, carry out melting and powder process by the method described in the embodiment 1, and suppressed the small pieces of φ 6 * 2mm respectively.With pumping property testing method used among the embodiment 1, their suction H have at room temperature been measured
2Performance, the result draws: No. 1 alloy, S
10Be 1080ml/sg, Q
240Be 5800mlPa/g, No. 2 alloys, S
10Be 1150ml/gg, Q
240Be 6350mlPa/g.From test result, behind a certain amount of lanthanum of interpolation family rare earth, the pumping property of alloy improves 10-15% in the alloy.Therefore think that adding lanthanum family rare earth in the alloy has good effect to the alloy pumping property.
Advantage of the present invention: this getter alloys adopts the usual method melting, and manufacturing process is simple, active gases is had good pumping property, to H2Pumping property particularly excellent, in the time of its 240 minutes to H2Gulp capacity than Zr-V-Fe and Zr-V-Fe-Ti alloy respectively raising 30-35% and the 15-25% when the room temperature, in the time of 300 ℃ Improve respectively 25-30% and 15-20%. This excellence of getter alloys of the present invention Suction H2Performance is specially adapted to vacuum cup (bottle), solar energy vacuum tube heat In hydrophone and the oil exploration instlated tubular. It will further improve the quality of products and extender The service life of part.
Claims (2)
1. polynary non-evaporation type low temp activation Zr base getter alloys is characterized in that: its component ratio, and weight part:
Zirconium: 62-75, nickel: 6.5-10.5, vanadium: 16-25, iron: 2-8, lanthanum family rare earth: 1-6 (wherein lanthanum 45-50%, cerium: 2-5%, praseodymium: 10-15%, neodymium: 35-40% weight).
2. the method for making of a polynary non-evaporation type low temp activation Zr base getter alloys is characterized in that: the component that adopts claim 1 than and under protection of inert gas non-consumable arc furnace or melt in the induction furnace frequently in a vacuum, vacuum tightness is 5 * 10
-2Pa, temperature of fusion is 1550 ± 50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106343A CN1053476C (en) | 1996-06-21 | 1996-06-21 | Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106343A CN1053476C (en) | 1996-06-21 | 1996-06-21 | Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1143686A CN1143686A (en) | 1997-02-26 |
| CN1053476C true CN1053476C (en) | 2000-06-14 |
Family
ID=5119086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106343A Expired - Fee Related CN1053476C (en) | 1996-06-21 | 1996-06-21 | Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053476C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI245308B (en) * | 2002-09-13 | 2005-12-11 | Getters Spa | Non-evaporable getter compositions which can be reactivated at low temperature after exposure to reactive gases at a higher temperature |
| CN101721969B (en) * | 2009-12-21 | 2011-12-14 | 北京有色金属研究总院 | Titanium-based sintered gettering material and preparation method thereof |
| US10354830B2 (en) * | 2016-04-06 | 2019-07-16 | Carl Zeiss Microscopy, Llc | Charged particle beam system |
| CN109680249A (en) * | 2019-01-25 | 2019-04-26 | 苏州大学 | Non-evaporable film getter and preparation method thereof |
| CN114288982A (en) * | 2021-12-14 | 2022-04-08 | 南京恩瑞科技有限公司 | Composite getter and preparation method thereof |
| CN114574721B (en) * | 2022-03-01 | 2022-12-13 | 秦皇岛江龙吸气材料有限公司 | Multi-element non-evaporable low-temp activated getter and its preparing process |
| CN115341120A (en) * | 2022-07-06 | 2022-11-15 | 上海大学 | Non-evaporable low-temperature activated zirconium-based getter alloy and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298130A (en) * | 1988-05-24 | 1989-12-01 | Sumitomo Metal Ind Ltd | Gas absorbing alloy having excellent activation characteristics |
-
1996
- 1996-06-21 CN CN96106343A patent/CN1053476C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298130A (en) * | 1988-05-24 | 1989-12-01 | Sumitomo Metal Ind Ltd | Gas absorbing alloy having excellent activation characteristics |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1143686A (en) | 1997-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2893528B2 (en) | Non-evaporable getter alloy | |
| JP3917514B2 (en) | Evaporative getter alloy | |
| EP1817439B1 (en) | Non-evaporable getter alloys for hydrogen sorption | |
| EP2735015B1 (en) | Non-evaporable getter compositions which can be reactivated at low temperature after exposure to reactive gases at a higher temperature | |
| CN1053476C (en) | Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof | |
| CN104871284B (en) | The non-evaporable getter alloys can being re-activated after being exposed to reactant gas | |
| US20090148635A1 (en) | Non-evaporable getter alloys based on yttrium for hydrogen sorption | |
| US5312606A (en) | Process for the sorption of residual gas by means of a non-evaporated barium getter alloy | |
| WO2007099575A2 (en) | Use of non-evaporable getter alloys for the sorption of hydrogen in vacuum and in inert gases | |
| JPS5947022B2 (en) | Alloy for hydrogen storage | |
| JPH0713274B2 (en) | Reversible storage / release material for hydrogen | |
| JPS5839218B2 (en) | Rare earth metal quaternary hydrogen storage alloy | |
| CA1095879A (en) | Iron-titanium-mischmetal alloys for hydrogen storage | |
| JPH01201401A (en) | Hydrogen storage alloy powder | |
| JPH089748B2 (en) | Gas absorption alloy with excellent activation characteristics | |
| JPS5928549A (en) | Rare earth metal type alloy for occluding hydrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Lv Zhenhe Document name: Notification to Pay the Fees |
|
| DD01 | Delivery of document by public notice |
Addressee: Lv Zhenhe Document name: Notification of Termination of Patent Right |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20000614 Termination date: 20090721 |