CN1088995A - High firmness is inhaled hydrogen and isotropic substance getter thereof - Google Patents
High firmness is inhaled hydrogen and isotropic substance getter thereof Download PDFInfo
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- CN1088995A CN1088995A CN 92114945 CN92114945A CN1088995A CN 1088995 A CN1088995 A CN 1088995A CN 92114945 CN92114945 CN 92114945 CN 92114945 A CN92114945 A CN 92114945A CN 1088995 A CN1088995 A CN 1088995A
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- zirconium
- getter
- intermetallic compound
- hydrogen
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Abstract
The present invention is relevant with the selection hydrogen-absorbing material of high firmness, and it is by the intermetallic compound 5-40 of zirconium, anti-sintering element 1-10, and all the other are that zirconium is formed.The intermetallic compound of said zirconium is ferrozirconium, zirconium aluminium, zirconium nickel intermetallic compound; Said anti-sintering element can be a silicon, also can be graphite.Getter of the present invention has fabulous pumping property and higher firmness.
Description
The invention belongs to getter material, especially relevant with the selection hydrogen-absorbing material of high firmness.
Getter is mainly used in various electron tubes, to improve and to keep the vacuum tightness in the device, the work-ing life of prolongation device; Also can be used in the aeration vessel, to improve the purity of gas.Have and select the getter material of gettering ability also to have special application, batalum getter for example, zircon China ink getter, zirconium vanadium iron getter and lanthanum base getter etc., except general gas being had good pumping property, hydrogen there is excellent especially pumping property, not only can be used for the purifying hydrogen embrittlement, also can be at the metallic hydrogen store battery, hydrogen adsorption formula compressor, heat pump, air-conditioning, robot is with using in the multiple Application Areass such as drive unit and transmitter, along with science and technology development, getter has been proposed new requirement, not only require it that good pumping property is arranged, wish that also getter after inhaling hydrogen hydrogen embrittlement does not take place, and has a high firmness, device is worked under ultra-high voltage or judder condition do not have μ m level dry linting, yet existing getter does not reach these requirements.
The objective of the invention is to design a kind of have high firmness, inhale hydrogen and the good getter of isotropic substance performance thereof.
Getter of the present invention is elementary composition by the intermetallic compound and the sintering of zirconium, zirconium.The intermetallic compound of zirconium is zirconium-iron, zirconium-aluminium, zirconium-nickel.Anti-sintering element can be a graphite, also can be silicon, and the composition of getter (weight %) is the intermetallic compound 5-40 of zirconium, anti-sintering element 1-10, all the other are zirconium.
Air-breathing its gettering rate of nonevaporable getter depends on dominant bulk diffusion or brilliant Jie's diffusion under the high temperature, and the main abutment surface of using at a lower temperature of nonevaporable getter plays getter action, have only the surface reaction of promotion could effectively improve its gettering rate, the most effective way is the porosity that increases material itself under the prerequisite that does not change getter physical dimension, promptly improve the specific surface area of getter, but this method certainly will make the compactness variation of material, it is the intensity variation, in order to make material keep good pumping property, have high intensity and firmness again concurrently, the present invention has adopted new technical scheme, promptly adds the intermetallic compound and the anti-sintering element of zirconium in the active element zirconium simultaneously.
The intermetallic compound of the zirconium that adds among the present invention as the bonding phase, also had been in order to improve its hydrogen sucking function both, and the intermetallic compound of zirconium is zirconium aluminium, ferrozirconium, zirconium nickel.The diffusion activation energy of gas in zirconium alloy is than big many of pure zirconium, for example the diffusion activation energy of hydrogen in zirconium alloy is 8792.3 Jiao Er/mol, and the diffusion activation energy in pure zirconium is 46892.2 Jiao Er/mol, in other intermetallic compounds of zirconium, similar characteristics is arranged also, Fig. 1 is the hydrogen absorption characteristic curve of intermetallic compound under 400 ℃ of conditions of disclosed zirconium aluminium (ZrAl16) zirconium nickel (Zr2Ni) and ferrozirconium (Zr2Fe) in GB2047950, illustrate that these three kinds of intermetallic compounds all are good hydrogen-absorbing materials, join the hydrogen sucking function that removes to help improving alloy material in the active element zirconium in right amount.In addition, Zr2Ni can generate the low melting point eutectic thing with zirconium in the time of 961 ℃, might play the bonding phase under selected sintering temperature.By contain a large amount of Zr2Fe and a small amount of Zr4Fe for example the weight ratio of Zr2Fe and Zr4Fe be 10-30: the 1 heterogeneous ferrozirconium intermetallic compound of forming, wherein the fusing point of Zr4Fe is 937 ℃, also might play the bonding phase under sintering temperature, their adding can play a part favourable to the intensity of alloy material.
Add bonding in the getter and be mutually for make obtain between the active element particle certain moistening and bonding arranged slightly on the surface, but do not wish the mutual sintering of active element, otherwise can make it lose getter action, for the sintering of avoiding active element and prevent active element when the sintering gathering and grow up, and suppress the obvious contraction of sintered powder, must add an amount of anti-sintering element, commonly used anti-sintering unit have graphite, silicon etc.
The getter of the present invention's design has following advantage.
1. pumping property is good, and good hydrogen sucking function is especially arranged
Begin to inhale the tenth minute gettering rate of hydrogen after the activation greater than 10m
3/ sec.m
2.
2. operating temperature range is wide
But equal works better in-45 ℃～55 ℃ temperature ranges.
3. hydrogen reaches 13.3m
3Pa/m
2After hydrogen embrittlement does not take place.
4. firmness height.
Fig. 1 is the hydrogen absorption characteristic curves of several compounds under 400 ℃ of conditions, and ordinate is a gettering rate, and abscissa is a gulp capacity, wherein 1 represents ZrAl16, and 2 represent Zr2Ni, and 3 represent Zr2Fe.
Fig. 2 is the synoptic diagram of firmness determinator.
Below in conjunction with embodiment the embodiment and the advantage of getter of the present invention are further described.
One, use the pure iron of atomic level zirconium sponge, zirconium powder, electrovacuum level, specpure Graphite Powder 99, silicon single crystal to be raw material; after pressing earlier zirconium sponge 76 and pure iron 24 weight percents batching; the technology melting pours in the water jacketed copper crucible routinely under the non-consumable arc furnace argon shield, casts to such an extent that the surface temperature of ingot casting was reduced to room temperature after 8 hours.The ferrozirconium ingot obtains the ferrozirconium powder after fragmentation, screening, the X-ray Phase Structure Analysis shows that this ferrozirconium powder is to contain compound between the heterogeneous metal of a large amount of Zr2Fe and a small amount of Zr4Fe, the weight ratio of Zr2Fe and Zr4Fe is 10: 1, ferrozirconium powder, zirconium powder and silica flour that will be by 300 mesh standard sieves is respectively after 75 ± 5 ℃ of bakings under the vacuum, prepare burden in following ratio (weight %): ferrozirconium powder 10, silica flour 4, all the other are zirconium, behind thorough mixing, add fir balsam as binding agent, after the compression moulding, at 650 ℃, vacuum tightness is 1.33 * 10 earlier
-2Low temperature gave sintering 10 minutes under the Pa, and respectively 930,1050 ℃ of differing tempss, vacuum tightness is 1.33 * 10 again
-3High temperature sintering is 10 minutes under the Pa, promptly makes the getter of a kind of composition of the present invention's design.
Use zirconium powder and Graphite Powder 99 to adopt common process to make the Zr-C getter of prior art.
The sample that makes is carried out the mensuration of pumping property, firmness respectively.Wherein pumping property is undertaken by national Specification, employing is of a size of the ring-type sample of 6.3 * 1.5 millimeters of φ 11.5 * φ, the getter exposed area is 0.62 square centimeter, the measuring method of firmness adopts the destructive test method, the synoptic diagram of firmness determinator is seen Fig. 2, this device shaking platform 2, is arranged on metal vessel 3 and compositions such as cover plate 4 and thrust screw 5 on the platform by vibrating device 1.The end of metal vessel is a wire netting 6, and the centre has dividing plate 7 that container is separated into some spaces, and sample to be tested is placed in each space.The frequency of vibrating device and amplitude range can be regulated as required.After on-test, sample is done random motion in the vibration of container internal cause, and sample and wall of container, cover plate, dividing plate and bottom metal net collide, and along with the increasing of test frequency amplitude, it is fierce more to clash into, and time of vibration is long more, and the sample wearing and tearing are serious more.For reduce error as far as possible, need the correlated sample of identical conditions can be contained in the different spaces of same container respectively, adopt the comparability of testing with raising with the method for condition vibration on the same stage, after the off-test, take out respectively and weigh, be calculated as follows the sample rate of weight loss then, per sample the rate of weight loss size, judge the firmness of material, the more little illustrative material firmness of rate of weight loss is big more.
△W＝ (A-B)/(A) ×100%
△ W-sample rate of weight loss (%) in the formula.
Example weight (gram) before the A-vibration.
B-vibration back example weight (gram).
Test sample is the cylinder of 6 * 5 millimeters of φ, and vibrational frequency 38Hz, amplitude are 1.2 millimeters, and time of vibration 40 minutes is weighed on ten thousand/balance.
The pumping property that records, firmness (percentage loss of weight AW), porosity the results are shown in Table 1.
* S10 begins air-breathing the 10th minute gettering rate, the m of unit after material activates
3/ sec.m
2
* Q10 begins air-breathing the 10th minute accumulative total inspiratory capacity, the m of unit after material activates
3Pa/m
2
* Q30 begins air-breathing back the 30th minute accumulative total inspiratory capacity, the m of unit after material activates
3Pa/m
2
Can find out that from table 1 material of the present invention is along with sintering temperature improves, porosity obviously descends, and percentage loss of weight diminishes, and this illustrative material intensity improves.Even but adopting the lesser temps sintering, its hydrogen sucking function and percentage loss of weight are that the strength of materials still improves than having extremely significantly of Zr-C.
To not inhale the H2 sample and be 15.2Pam through 965 ℃ of these examples of agglomerating in suction H2 amount
3/ m
2Two inhale the H2 samples and doing vibration test with under the condition on the same stage, the gained data are listed in table 2.
The percentage loss of weight of inhaling sample behind the hydrogen as seen from the table with do not inhale the same level of being in of hydrogen sample, illustrate that the strength property that this material is inhaled behind hydrogen still can guarantee, hydrogen embrittlement does not take place, can not influence the normal use of material under hydrogen uptake condition.
Two, make use-case one identical raw material and technology, different with example one is cast the surface temperature of ferrozirconium ingot casting after 4 hours, reduce to room temperature, behind the crushing and screening in the ferrozirconium powder weight ratio of Zr2Fe and Zr4Fe be 19: 1.The performance of the various getters that make by different ratio of components (weight %) sees Table 3.
Three, make use-case one identical raw material and technology, different with example one is cast the surface temperature of ferrozirconium ingot casting after 1 hour, reduce to room temperature, behind the crushing and screening in the ferrozirconium powder weight ratio of Zr2Fe and Zr4Fe be 30: 1.The performance of the various getters that make by different ratio of components (weight %) sees Table 4.
Four, the getter that makes of use-case one carries out the tubulature test.6 * 7 millimeters heater types of φ getter is encapsulated in 0.25 liter the Glass tubing, encloses the metallic nickel sheet simultaneously as the venting source, Glass tubing 350 ℃ of bakings 4 hours down, is removed baking oven, vacuum tightness reaches 7 * 10
-5Pa is then to getter heat activation, and heating current is 6.5A, and the interior vacuum tightness of pipe this moment is 4.3 * 10
-3Pa heats and stops activation after 10 minutes, and with the Glass tubing sealed-off, vacuum tightness is 1 * 10 in the pipe on exhaust station
-4Pa, the interior vacuum tightness of pipe goes back up to 2.7 * 10 after 15 minutes
-5Pa is 1.2 * 10 after 20 minutes
-5Pa, heating makes the venting of nickel sheet, makes the interior vacuum tightness of pipe reduce to 10
-3Pa, getter is air-breathing subsequently, calculates and returns to 10
-5The time of Pa, and then heating venting source, air-breathing again, inhaling so repeatedly exits tests, and manages interior vacuum tightness time of recovery and inhale the number of times of exitting to see Table 5.
As seen from Table 5, this getter is once activated, ten still not at all reductions of air-breathing its gettering rates of venting are only used after the venting just to make order of magnitude of vacuum tightness raising in the pipe 41 seconds (the shortest is 35 seconds) repeatedly, return to the preceding vacuum tightness (10 of venting after 5 minutes again
-5The Pa order of magnitude).
Carried out the device application test of testing laboratory in addition, the measured data of 7 device experiments shows, still can maintain 10 after the device work 500 times
-4The Pa order of magnitude.
Getter of the present invention can repeatedly activate, and activates the back gettering ability again and recovers rapidly, and table 6 has been listed the variation that above-mentioned 5 devices activate front and back vacuum tightness again.
After the data declaration material activates again in the table not only pumping property can recover, and to device withstand voltage also not influence, this illustrates that getter can not emitted the obnoxious flavour of any pollution high voltage electrode in the activated at process.
Five, the getter material various of the present invention that makes in example one～example three is made the heater type getter of 6 * 7 millimeters of φ, be contained in working gas and be in the high pressure vacuum device of deuterium tritium mixed gas and carry out sniff test, the result shows that getter material of the present invention also has the gettering ability to the deuterium tritium, and:
1. inspiratory capacity is big, and (φ 6 * 7mm) once can inhale deuterium or the tritium of (normal conditions) 40ml to a getter heater at least, inhales venting repeatedly, and inspiratory capacity does not reduce.
2. gettering rate height, this getter can bring up to 10 with the vacuum of 2000ml system from several mmhg in 4 minutes
-4MmHg.
3. low temperature (room temperature) pumping property is good, and vacuum was less than 10 in energy long-term (more than half a year) be kept and manage when neutron tube is not worked
-7MmHg.
4. intensity is good, does not have discovery that the slag of falling and damage phenomenon are arranged through long-distance transport and use, can be used for the high pressure vacuum device reliably.
5. activate easily.
Six; use the atomic level zirconium; zirconium powder; electrovacuum level pure nickel and fine aluminium; silicon single crystal and spectroscopically pure graphite powder are raw material; earlier with zirconium sponge and pure nickel; press zirconium 77; nickel 23 weight percents batching; press zirconium 84 with zirconium sponge and fine aluminium; after the aluminium 16 weight percents batching; under the non-consumable arc furnace argon shield, make zirconium nickel ingot and zirconium aluminium ingot respectively; through fragmentation; obtain zirconium nickel powder and zirconium aluminium powder after the screening; the X-ray Phase Structure Analysis shows that this zirconium nickel powder is typical Zr2Ni intermetallic compound; this zirconium aluminium powder is the ZrAl16 intermetallic compound; will be by these two kinds of intermetallic compound powders of 300 mesh standard sieves; zirconium powder; silica flour is respectively under vacuum after 75 ± 5 ℃ of bakings; by the proportion ingredient in the table; behind thorough mixing, add fir balsam as binding agent; make one group of getter after giving sintering and sintering by example one described technology, its relevant performance example is in table 7.
Table 1
Table 4
| Ratio of components | Inhale the H2 performance | Inhale the H2 performance | Inhale the CO performance | Percentage loss of weight % | Heater burns till yield rate % | |||||
| Zirconium | Ferrozirconium | Silicon | S10 | S30 | S10 | S30 | S10 | S30 | ||
| 84 94 55 | 11 5 40 | 5 1 5 | 16.0 11.7 12.9 | 8.12 7.95 8.1 | 2.91 2.52 2.74 | 2.26 1.98 2.12 | 4.00 3.10 3.34 | 2.49 2.21 2.30 | 0.197 0.191 0.180 | 98 97 95 |
Table 5
Table 6
Claims (5)
1, a kind of high firmness getter is characterized in that said getter is elementary composition by the intermetallic compound and the anti-sintering of zirconium, zirconium, and its composition (weight %) is the intermetallic compound 5-40 of zirconium, anti-sintering element 1-10, and all the other are zirconium.
2, according to the said high firmness getter of claim 1, the intermetallic compound that it is characterized in that said zirconium is the ferrozirconium intermetallic compound, and wherein the weight ratio of Zr2Fe and Zr4Fe is 10-30: 1, and said anti-sintering element is a silicon.
3,, it is characterized in that said anti-sintering element is a graphite according to the said high firmness getter of claim 2.
4, according to the said high firmness getter of claim 1, the intermetallic compound that it is characterized in that said zirconium is zirconium Al intermetallic (ZrAl16), and said anti-sintering element is silicon or graphite.
5, according to the said high firmness getter of claim 1, the metallic compound that it is characterized in that said zirconium is zirconium nickel intermetallic compound (Zr2Ni) and zirconium Al intermetallic (ZrAl16).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92114945 CN1033525C (en) | 1992-12-29 | 1992-12-29 | High-fastness hydrogen adsorption material and isotopic getter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92114945 CN1033525C (en) | 1992-12-29 | 1992-12-29 | High-fastness hydrogen adsorption material and isotopic getter |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95105320A Division CN1034185C (en) | 1995-05-24 | 1995-05-24 | High-firmness hydrogen absorbing and its isotopic absorption agent |
| CN95105321A Division CN1034186C (en) | 1995-05-24 | 1995-05-24 | High firmness hydrogen absorption and other isotope absorption agent |
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| Publication Number | Publication Date |
|---|---|
| CN1088995A true CN1088995A (en) | 1994-07-06 |
| CN1033525C CN1033525C (en) | 1996-12-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92114945 Expired - Lifetime CN1033525C (en) | 1992-12-29 | 1992-12-29 | High-fastness hydrogen adsorption material and isotopic getter |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105783296A (en) * | 2014-12-24 | 2016-07-20 | 北京有色金属研究总院 | Porous hydrogen absorption element and mounting method of porous hydrogen absorption element in solar heat collection pipe |
| CN106800281A (en) * | 2017-01-20 | 2017-06-06 | 中国工程物理研究院材料研究所 | A kind of gas cleaning plant of high-pure helium 3 and purification method |
| CN111540484A (en) * | 2020-04-21 | 2020-08-14 | 上海申核能源工程技术有限公司 | Hydrogen absorption material used under nuclear facility accident environmental condition |
| CN111842917A (en) * | 2020-07-27 | 2020-10-30 | 安徽有研吸气材料有限公司 | Components of high-performance getter alloy and processing method thereof |
-
1992
- 1992-12-29 CN CN 92114945 patent/CN1033525C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105783296A (en) * | 2014-12-24 | 2016-07-20 | 北京有色金属研究总院 | Porous hydrogen absorption element and mounting method of porous hydrogen absorption element in solar heat collection pipe |
| CN105783296B (en) * | 2014-12-24 | 2018-06-15 | 北京有色金属研究总院 | Porous suction hydrogen element and its installation method in solar energy heat collection pipe |
| CN106800281A (en) * | 2017-01-20 | 2017-06-06 | 中国工程物理研究院材料研究所 | A kind of gas cleaning plant of high-pure helium 3 and purification method |
| CN111540484A (en) * | 2020-04-21 | 2020-08-14 | 上海申核能源工程技术有限公司 | Hydrogen absorption material used under nuclear facility accident environmental condition |
| CN111842917A (en) * | 2020-07-27 | 2020-10-30 | 安徽有研吸气材料有限公司 | Components of high-performance getter alloy and processing method thereof |
| CN111842917B (en) * | 2020-07-27 | 2023-11-03 | 安徽有研吸气新材料股份有限公司 | High-performance getter alloy component and processing method thereof |
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| Publication number | Publication date |
|---|---|
| CN1033525C (en) | 1996-12-11 |
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