CN105568110A - AB type hydrogen storage alloy used for storing tritium and preparation method of AB type hydrogen storage alloy - Google Patents
AB type hydrogen storage alloy used for storing tritium and preparation method of AB type hydrogen storage alloy Download PDFInfo
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Abstract
The invention provides an AB type hydrogen storage alloy used for storing tritium and a preparation method of the AB type hydrogen storage alloy, and relates to the technical field of hydrogen storage alloy. The general formula of components of the AB type hydrogen storage alloy used for storing the tritium is Zr1-xTixCo1-yFey, wherein the x is greater than or equal to 0.1 but smaller than or equal to 0.4, and the y is greater than or equal to 0.1 but smaller than or equal to 0.2. The hydrogen storage alloy provided by the invention has good hydrogen-induced disproportionation resistance, and excellent hydrogen absorption and desorption kinetics performance and indoor-temperature hydride balance pressure, and the preparation method of the hydrogen storage alloy is simple, easy to implement and high in preparation efficiency and practicability.
Description
Technical field
The present invention relates to hydrogen storage alloy technical field, in particular to a kind of for AB type hydrogen storage alloy storing tritium and preparation method thereof.
Background technology
Tritium is a kind of grand strategy resource, and the field important in the energy, national defence etc. all has very important effect.Tritium is as a kind of human nuclide, and only obtain by the nuclear reaction of nuclear reactor and accelerator at present, and tritium can decay into helium 3 by spontaneous β, the transformation period is only 12.33a.The scarcity of tritium, radioactivity and the keying action in the energy and national defence, determine quick, the safe and reliable storage realizing relating to tritium in tritium system, transport, the importance of supply.
Under the hydrogen storage alloy room temperature that the safe handling of tritium, storage and traffic requirements are used, hydrogen (tritium) compound equilibrium pressure is low as far as possible, to ensure the efficient absorption of radioactivity tritium, avoids tritium entered environment in transport process as far as possible, causes the waste of tritium; On the other hand, need hydrogen storage alloy to have good cycle life and lower tritium hold-up, avoid the irreversible delay of tritium in hydrogen storage alloy.Thus, select suitable storage tritium material, the development for controllable nuclear fusion heap is one of very important gordian technique.
Existing storage tritium material is owing to cannot take into account the characteristics such as high storage tritium capacity, high stability, low balanced dissociation pressure, good suction hydrogen desorption kinetics performance and more strong helium ability, and the method that there is no meets technical need completely.But and for the storage of tritium, supply and the storage tritium material reclaimed be restrict controllable nuclear fusion can final one of key technical problem realizing commercial applications, be also that neutron tube etc. relates to tritium technical field and realizes one of safety further, gordian technique of reliably developing simultaneously.
The existing storage tritium material used in tritium system that relates to is generally simple substance uranium, and uranium has suction and puts that hydrogen (tritium) dynamic performance is good, room temperature dissociation equilibrium forces down (10
-3the advantage such as Pa), but it is as a kind of nuclear matter, there is again hydrogen storage capacity (140ml/g) on the low side, easily spontaneous combustion is there is under the easy efflorescence of hydrogenation, emergency conditions, release the shortcomings such as hydrogen (tritium) temperature is high, controlled fusion reactor etc. can not be met completely and relate to the safe storage of tritium in tritium field of engineering technology, transport and plenum system to the technical requirements of storage tritium material.
Intermetallic compound AB type hydrogen storage alloy with ZrCo alloy for representative, there is excellent pressure hydrogen isotropic substance capturing ability, suction is put hydrogen (tritium) dynamic performance, good solid-solid diffusion ability and relatively gentle is released hydrogen condition, is the safety operation that more a kind of of research at present can be used for tritium, the material transporting and store.But hydrogen in use can occur ZrCo alloy causes disproportionation reaction, generate thermodynamically stable ZrH
2phase and ZrCo
2phase, causes the loss of irreversible hydrogen storage capability and the decline of himself service life cycle.
Summary of the invention
The object of the present invention is to provide a kind of AB type hydrogen storage alloy for storing tritium, this hydrogen storage alloy has good resistant to hydrogen and causes disproportionation performance, excellent suction hydrogen desorption kinetics performance and room temperature hydride equilibrium pressure.
Another object of the present invention is to the preparation method that a kind of AB type hydrogen storage alloy for storing tritium is provided, to instruct the preparation of AB type hydrogen storage alloy.
The present invention solves its technical problem and realizes by the following technical solutions:
For storing an AB type hydrogen storage alloy for tritium, its component general formula is Zr
1-xti
xco
1-yfe
y, wherein 0.1≤x≤0.4,0.1≤y≤0.2.
In addition, a kind of preparation method of the above-mentioned AB type hydrogen storage alloy for storing tritium, comprises according to proportioning, the mixing of each raw material is placed on anaerobic, is full of rare gas element, 6 × 10
4~ 8 × 10
4melting under the envrionment conditions of Pa, treats that it is cooled to ingot casting after annealing.
Relative to prior art, the present invention includes following beneficial effect: the present invention is on the basis of AB type ZrCo alloy, Ti element (titanium elements) is used to substitute A side Zr element (zr element) respectively, B side Co element (cobalt element) is substituted with Fe element (ferro element), again by annealing, alloy is made to obtain comparatively uniform isometric system alloy.Wherein, the interpolation of Ti element can change hydrogen (tritium) atom in alloy hydrogen (tritium) compound lattice and distribute in the occupy-place of gap digit, significantly can reduce Zr element and Co element repeatedly inhaling to put there is hydrogen (tritium) in hydrogen (tritium) working cycle or high temperature hydrogen (tritium) atmosphere and causes disproportionation reaction, to generate thermodynamically stable ZrH
2and ZrCo
2mutually institute causes the loss of irreversible hydrogen storage capability, and the resistant to hydrogen (tritium) that the interpolation of Ti element can strengthen ZrCo alloy causes disproportionation performance, the service life cycle of lifting ZrCo alloy.But the increase of Ti element substitution content can cause the lifting of ZrCo alloy hydrogen (tritium) compound level ground platform pressure and inhale the decline of hydrogen (tritium) dynamic performance, so add again Fe element in component materials.The interpolation of Fe element can improve ZrCo alloy hydrogen absorption and desorption (tritium) dynamic performance, reduce ZrCo alloy hydrogen (tritium) compound equilibrium pressure, it effectively can improve the decay of suction hydrogen (tritium) dynamic performance and the thermomechanical property caused because Ti element adds, and supplies gaps and omissions.
Hydrogen storage alloy provided by the invention is the hydrogen storage alloy of low equilibrium pressure, and it has equilibrium at room temperature pressure Ping Tai lower than 10
-1pa, inhale and put that hydrogen (tritium) speed is fast, cycle life is excellent, resistant to hydrogen causes disproportionation and the advantage such as storage hydrogen (tritium) capacity is large.For hydrogen and isotopic safe handling thereof under low equilibrium pressure condition, the operating modes such as storage, transport and recovery, have the application advantage of highly significant.In addition, preparation method of the present invention is simple to operate, be easy to realize, efficiency is high, and cost is low.
Accompanying drawing explanation
In order to the clearer explanation embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is Zr
0.9ti
0.1co
0.9fe
0.1hydrogen storage alloy puts hydrogen P-C-T curve;
Fig. 2 is Zr
0.8ti
0.2co
0.9fe
0.1hydrogen storage alloy puts hydrogen P-C-T curve;
Fig. 3 is Zr
0.7ti
0.3co
0.9fe
0.1hydrogen storage alloy puts hydrogen P-C-T curve;
Fig. 4 is that the 773K hydrogen of hydrogen storage alloy causes disproportion kinetics curve;
Wherein (a), (b), (c), (d) are respectively Zr
0.9ti
0.1co
0.9fe
0.1, Zr
0.8ti
0.2co
0.9fe
0.1, Zr
0.7ti
0.3co
0.9fe
0.1, existing ZrCo alloy hydrogen cause disproportion kinetics curve;
Fig. 5 is Zr
0.8ti
0.2co
1-yfe
yroom temperature (300K) after alloy activation, pressure are 100kPa Dynamic isotherms of hydrogen absorption comparison diagram,
Wherein (a), (b) are respectively Zr
0.8ti
0.2co
0.8fe
0.2alloy, Zr
0.8ti
0.2co
0.9fe
0.1the Dynamic isotherms of hydrogen absorption of alloy;
Fig. 6 is Zr
0.7ti
0.3co
1-yfe
yroom temperature (300K) after alloy activation, pressure are 100kPa Dynamic isotherms of hydrogen absorption comparison diagram,
Wherein (a), (b) are respectively Zr
0.7ti
0.3co
0.8fe
0.2alloy, Zr
0.7ti
0.3co
0.9fe
0.1the Dynamic isotherms of hydrogen absorption of alloy;
Fig. 7 is X-ray diffractogram provided by the invention,
Wherein (a), (b), (c) are respectively Zr
0.9ti
0.1co
0.9fe
0.1, Zr
0.8ti
0.2co
0.8fe
0.2, Zr
0.7ti
0.3co
0.8fe
0.2x-ray diffractogram.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, be clearly and completely described to the technical scheme in the embodiment of the present invention below.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
Being specifically described for AB type hydrogen storage alloy storing tritium and preparation method thereof below to the embodiment of the present invention.
Be Zr for storing the component general formula of the AB type hydrogen storage alloy of tritium
1-xti
xco
1-yfe
y, wherein 0.1≤x≤0.4,0.1≤y≤0.2.
Wherein, x, y preferably meet 0.1≤x≤0.2, and 0.1≤y≤0.15, the material purity of Zr, Ti, Co, Fe is all more than 99%.Produce hydrogen storage alloy with high-purity raw, the high standard of hydrogen storage alloy self can be met, and the hydrogen storage alloy of better performances can also be obtained.
In addition, the preparation method for the AB type hydrogen storage alloy storing tritium comprises, and according to proportioning, the mixing of each raw material is placed on anaerobic, is full of rare gas element, 6 × 10
4~ 8 × 10
4melting under the envrionment conditions of Pa, treats that it is cooled to ingot casting after annealing.
Rare gas element can be helium, neon, argon gas etc., is preferably argon gas.
Due in fusion process, may scaling loss be there is in raw material, so Ti, Co, Fe further comprises compensation material during melting, compensate material to add with raw material simultaneously, the compensation material consumption of Ti is 1 ~ 2% of its raw material dosage, the compensation material consumption of Co is the compensation material consumption of 3 ~ 4%, Fe of its raw material dosage is 2.5 ~ 3.5% of its raw material dosage.When taking raw material and compensation material, first raw material and compensation material can be passed through clean, drying treatment.
Manufacture anaerobic, be full of rare gas element, 6 × 10
4~ 8 × 10
4the method of the envrionment conditions of Pa is: in reaction vessel, put into the metal titanium of purity more than 99.9% and pass into rare gas element, making the air pressure of reaction vessel be 6 × 10
4~ 8 × 10
4pa, then utilize tungsten electrode energising striking, adjustment electric current to 120 ~ 220A, smelting metal titanium, absorbs oxygen.Rare gas element is first utilized to drive oxygen in reaction vessel out of, then oxygen reaction residual in the highly purified metal titanium of melting and reaction vessel is utilized, absorb oxygen, thus avoid in the preparation process of later stage hydrogen storage alloy, the component materials of hydrogen storage alloy is by dioxygen oxidation residual in reaction vessel, and impact is reacted.Certainly, metal zirconium or cobalt metal also can be adopted to absorb oxygen.
Wherein, when after metal titanium fusing, can 1 ~ 2min be left standstill, to ensure that it has sufficient time and residual oxygen reaction, thus absorb oxygen.
Putting into metal titanium and before passing into rare gas element, also comprising the cavity of wash reaction vessels: being evacuated to air pressure to reaction vessel is 10
-3~ 10
-4pa, then passes into rare gas element, makes the air pressure of cavity be 5 × 10
4~ 9 × 10
4pa, repeats this operation 3 ~ 4 times.The cavity of wash reaction vessels repeatedly, can effectively remove the impurity that may contain in cavity, ensure good reaction environment, and reaction is carried out smoothly, and not by the detrimentally affect of other factors.This kind of operation can make reaction more reliable, and the performance of the hydrogen storage alloy that the later stage obtains is better.
The concrete operations of melting are: after utilizing tungsten electrode energising striking, adjustment electric current to 120 ~ 220A, by mixed material melting to changing fluent meterial into completely.If select this kind of mode to carry out melting, then reaction vessel is preferably vacuum non-consumable arc-melting furnace.And in the step absorbing the residual oxygen in reaction vessel, metal titanium is just placed in water jacketed copper crucible and carries out melting, when the mixture of melting hydrogen storage alloy, is also placed in water jacketed copper crucible by mixed material.Certainly, this kind of saying is not contradiction, because general vacuum non-consumable arc-melting furnace comprises multiple chamber, when removing the residual oxygen in cavity, metal titanium is placed in one of them chamber, after abundant absorption oxygen, then the material of the mixing of hydrogen storage alloy is put into other chamber, carry out melting.In this process, the metal titanium absorbed after oxygen can be taken out, also can not take out, multiple chamber coexists in same anaerobic, inert gas environment, but the heating of multiple chamber does not interfere with each other.In addition, because the purity of metal titanium is very high, and the amount of residual oxygen in cavity after cleaning is fewer, so metal titanium can repeatedly Reusability.
In addition, above-mentioned melting mode not as restriction, also can carry out melting material by the mode of electromagnetic induction, as long as in fact in anaerobic, be full of rare gas element, 6 × 10
4~ 8 × 10
4complete melting under the envrionment conditions of Pa, make material change liquid state into completely, and the mode of melting is not limited.
After making material change fluent meterial into completely because of melting, tungsten electrode can be utilized to move 2 ~ 3min around fluent meterial, thus make fluent meterial thermally equivalent.
After fluent meterial is cooled to ingot casting, before the anneal, also comprise: repeat melting 4 ~ 5 times, and all by ingot overturning 180 degree during each repetition.The repeatable operation of energising striking-melting-cooling, can make material thermally equivalent, makes the hydrogen storage alloy obtained obtain uniform tissue.
Complete melting, after obtaining ingot casting, in order to eliminate the unrelieved stress of ingot casting, crystal grain thinning, adjustment tissue, eliminate tissue defects, also carried out anneal, the method for annealing is specially: ingot casting is placed in air pressure 10
-3below Pa, be full of insulation 12 ~ 20h, then furnace cooling in rare gas element, the environment of 900 ~ 1000 DEG C.
Rare gas element said herein is also preferably argon gas, and the equipment that annealing uses is preferably vacuum tube furnace, and certainly, the equipment that annealing uses is not as limit.
When adopting vacuum non-consumable arc-melting furnace to carry out melting, cool in water jacketed copper crucible, in cooled and solidified process fast, dendritic structure is there is in cast alloy, rich Zr phase is mingled with distribution with rich Co phase, causes alloy hydrogen storage capability lower than theoretical value, and by long vacuum annealing process, can promote that alloy interior element spreads, obtain comparatively uniform Emission in Cubic structure AB type alloy.
When to above-mentioned vacuum non-consumable arc-melting furnace and electron tubes type stove evacuation, can be realized by the mode of two stage pump coupling, namely first adopt mechanical pump to vacuumize, then adopt diffusion pump or molecular pump to vacuumize.Mechanical pump can realize rough vacuum and extract, and diffusion pump or molecular pump can realize high vacuum and extract.Vacuumized by this kind of coupling mode, can promote and vacuumize efficiency, extend the work-ing life of diffusion pump or molecular pump.
Below in conjunction with embodiment, characteristic sum performance of the present invention is described in further detail:
Embodiment one
Embodiments of the invention one provide a kind of AB type hydrogen storage alloy for storing tritium, and its component general formula is Zr
0.9ti
0.1co
0.9fe
0.1, wherein, the purity of each raw material is 99%.
The present embodiment additionally provides a kind of preparation method of above-mentioned hydrogen storage alloy, comprises the following steps:
(1) each raw material is carried out batching weighing after clean and drying, additionally add 1%, Fe according to each raw material dosage Ti during batching and additionally add 2.5%, Co and additionally add 3%;
(2) raw material prepared is mixed in the water jacketed copper crucible be placed in vacuum non-consumable arc-melting furnace, a reserved water jacketed copper crucible, toward wherein placing high-purity Ti metal (purity is 99.9%), then successively utilize mechanical pump and the furnace chamber of diffusion pump to vacuum non-consumable arc-melting furnace to vacuumize, make the furnace chamber vacuum tightness of smelting furnace reach 10
-3pa magnitude, then passes into high-purity argon gas, makes furnace chamber internal gas pressure reach 5 × 10
4pa, vacuumizes afterwards and reaches 10
-3pa magnitude, more logical argon gas, so repeatedly vacuumize and inflate cleaning furnace chamber 3 times, then passing into high-purity argon gas, making the furnace chamber of smelting furnace reach 6 × 10
4pa;
After the tungsten electrode energising striking of Ti metal position in vacuum non-consumable smelting furnace, electric current is enlarged to 160A, first melting is carried out to the high-purity Ti metal in water jacketed copper crucible, make metal Ti change liquid state into, powered-down, utilizes high-purity Ti ingot to cool and absorbs residual free state oxygen 1min in furnace chamber;
(3) to after the tungsten electrode energising striking of vacuum non-consumable smelting furnace interalloy raw material position, electric current is enlarged to 160A, to the institute's preparing metal raw material melting in water jacketed copper crucible to changing liquid state into completely, holding current 2min, simultaneously adjust tungsten electrode at cast metals edge slowly around;
Powered-down, liquid raw metal cooled and solidified forms cast metals; Repeat above-mentioned energising striking-melting-process of cooling 4 to take turns, and all cooled cast metals is overturn 180 ° during each repetition, then take out alloy cast ingot;
(4) alloy cast ingot is put into vacuum tube furnace, 9 × 10 are evacuated to tube furnace furnace chamber
-4pa, seals after passing into argon gas, and diamond heating to 920 DEG C is also incubated 15h.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy.
Composition through this hydrogen storage alloy of chemical composition analysis meets with the ratio of each chemical element obtained according to above-mentioned chemical general formula.
It is that 300 object particles are (certain that the hydrogen storage alloy prepared by aforesaid method is broken for particle diameter, this particle diameter is not as restriction, hydrogen storage alloy is when carrying out various performance test, the size of its particle diameter can be produced as required), carry out hydrogen storage property test by hydrogen storage property comprehensive tester to preparing the alloy obtained.For the ease of putting hydrogen P-C-T curve and inhaling the test of hydrogen dynamic performance, hydrogen storage alloy particle is first vacuumized 1h under 500 DEG C of heating conditions, is then filled with hydrogen and reaches 100kPa to pressure, make alloy inhale hydrogen activation fast.Heating is found time-inhaled repeatedly, and 2 times extremely activation is complete for hydrogen.
The P-C-T of this alloy at 523K, 573K, 623K temperature as shown in Figure 1, wherein, X-coordinate is hydrogen richness (representing with atomic ratio) in alloy solid phase, ordinate zou is for inhaling hydrogen pressure (logarithmic coordinates, unit is kPa), hydrogen storage capability reaches 1.9wt%, and extrapolation equilibrium at room temperature forces down in 10
-3pa.Fig. 4 (a) causes disproportion kinetics for above-mentioned alloy hydrogen under 723K, and Fig. 4 (d) causes disproportion kinetics for the hydrogen of existing ZrCo hydrogen storage alloy, and the alloy that the present embodiment provides shows as good resistant to hydrogen and causes disproportionation performance.Fig. 7 (a) is the X-ray diffractogram of above-mentioned alloy.Can find out that this alloy has hydrogen storage capability from test result large, the advantage that activation easily, level ground platform slope is low, level ground platform pressure is low, and there is good suction hydrogen desorption kinetics performance and resistant to hydrogen causes disproportionation performance simultaneously.Be suitable for the safe handling of tritium, store and transport.
Embodiment two
Embodiments of the invention two provide a kind of AB type hydrogen storage alloy for storing tritium, and its component general formula is Zr
0.8ti
0.2co
0.9fe
0.1, wherein, the purity of each raw material is 99.9%.
The present embodiment additionally provides a kind of preparation method of above-mentioned hydrogen storage alloy, comprises the following steps:
(1) each raw material is carried out batching weighing after clean and drying, additionally add 1%, Fe according to each raw material dosage Ti during batching and additionally add 2.5%, Co and additionally add 3%;
(2) raw material prepared is mixed in the water jacketed copper crucible be placed in vacuum non-consumable arc-melting furnace, a reserved water jacketed copper crucible, toward wherein placing high-purity Ti metal (purity is 99.99%), then successively utilize mechanical pump and the furnace chamber of molecular pump to vacuum non-consumable arc-melting furnace to vacuumize, make the furnace chamber vacuum tightness of smelting furnace reach 10
-4pa magnitude, then passes into high-purity argon gas, makes furnace chamber internal gas pressure reach 9 × 10
4pa, vacuumizes afterwards and reaches 10
-4pa magnitude, more logical argon gas, so repeatedly vacuumize and inflate cleaning furnace chamber 4 times, then passing into high-purity argon gas, making the furnace chamber of smelting furnace reach 8 × 10
4pa;
After the tungsten electrode energising striking of Ti metal position in vacuum non-consumable smelting furnace, electric current is enlarged to 150A, first melting is carried out to the high-purity Ti metal in water jacketed copper crucible, make metal Ti change liquid state into, powered-down, utilizes high-purity Ti ingot to cool and absorbs residual free state oxygen 2min in furnace chamber;
(3) to after the tungsten electrode energising striking of vacuum non-consumable smelting furnace interalloy raw material position, electric current is enlarged to 150A, to the institute's preparing metal raw material melting in water jacketed copper crucible to changing liquid state into completely, holding current 2min, simultaneously adjust tungsten electrode at cast metals edge slowly around;
Powered-down, liquid raw metal cooled and solidified forms cast metals; Repeat above-mentioned energising striking-melting-process of cooling 5 to take turns, and all cooled cast metals is overturn 180 ° during each repetition, then take out alloy cast ingot;
(4) alloy cast ingot is put into vacuum tube furnace, 2 × 10 are evacuated to tube furnace furnace chamber
-4pa, seals after passing into argon gas, and diamond heating to 950 DEG C is also incubated 16h.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy.
Composition through this hydrogen storage alloy of chemical composition analysis meets with the ratio of each chemical element obtained according to above-mentioned chemical general formula.
It is 200 object particles that the hydrogen storage alloy prepared by aforesaid method is broken for particle diameter, carries out hydrogen storage property test by hydrogen storage property comprehensive tester to preparing the alloy obtained.For the ease of putting hydrogen P-C-T curve and inhaling the test of hydrogen dynamic performance, hydrogen storage alloy particle is first vacuumized 1h under 500 DEG C of heating conditions, is then filled with hydrogen and reaches 100kPa to pressure, make alloy inhale hydrogen activation fast.Heating is found time-inhaled repeatedly, and 2 times extremely activation is complete for hydrogen.
The P-C-T of this alloy at 523K, 573K, 623K temperature as shown in Figure 2, wherein, X-coordinate is hydrogen richness (representing with atomic ratio) in alloy solid phase, ordinate zou is for inhaling hydrogen pressure (logarithmic coordinates, unit is kPa), hydrogen storage capability reaches 1.92wt%, and extrapolation equilibrium at room temperature forces down in 10
-2pa.Fig. 5 (b) inhales hydrogen kinetics under the 300K temperature condition of above-mentioned alloy, shows as and inhales hydrogen dynamic performance preferably.Fig. 4 (b) causes disproportion kinetics for above-mentioned alloy hydrogen under 723K, and Fig. 4 (d) causes disproportion kinetics for the hydrogen of existing ZrCo hydrogen storage alloy, and the alloy that the present embodiment provides shows as good resistant to hydrogen and causes disproportionation performance.Can find out that this alloy has hydrogen storage capability from test result large, the advantage that activation easily, level ground platform slope is low, level ground platform pressure is low, and there is good suction hydrogen desorption kinetics performance and resistant to hydrogen causes disproportionation performance simultaneously.Be suitable for the safe handling of tritium, store and transport.
Embodiment three
Embodiments of the invention three provide a kind of AB type hydrogen storage alloy for storing tritium, and its component general formula is Zr
0.7ti
0.3co
0.9fe
0.1, wherein, the purity of each raw material is 99.5%.
The present embodiment additionally provides a kind of preparation method of above-mentioned hydrogen storage alloy, comprises the following steps:
(1) each raw material is carried out batching weighing after clean and drying, additionally add 1%, Fe according to each raw material dosage Ti during batching and additionally add 2.5%, Co and additionally add 3%;
(2) raw material prepared is mixed in the water jacketed copper crucible be placed in vacuum non-consumable arc-melting furnace, a reserved water jacketed copper crucible, toward wherein placing high-purity Ti metal (purity is 99.95%), then successively utilize mechanical pump and the furnace chamber of diffusion pump to vacuum non-consumable arc-melting furnace to vacuumize, make the furnace chamber vacuum tightness of smelting furnace reach 5 X 10
-4pa magnitude, then passes into high-purity argon gas, makes furnace chamber internal gas pressure reach 7 × 10
4pa, vacuumizes afterwards and reaches 5 X 10
-4pa magnitude, more logical argon gas, so repeatedly vacuumize and inflate cleaning furnace chamber 4 times, then passing into high-purity argon gas, making the furnace chamber of smelting furnace reach 7 × 10
4pa;
After the tungsten electrode energising striking of Ti metal position in vacuum non-consumable smelting furnace, electric current is enlarged to 160A, first melting is carried out to the high-purity Ti metal in water jacketed copper crucible, make metal Ti change liquid state into, powered-down, utilizes high-purity Ti ingot to cool and absorbs residual free state oxygen 2min in furnace chamber;
(3) to after the tungsten electrode energising striking of vacuum non-consumable smelting furnace interalloy raw material position, electric current is enlarged to 160A, to the institute's preparing metal raw material melting in water jacketed copper crucible to changing liquid state into completely, holding current 2min, simultaneously adjust tungsten electrode at cast metals edge slowly around;
Powered-down, liquid raw metal cooled and solidified forms cast metals; Repeat above-mentioned energising striking-melting-process of cooling 4 to take turns, and all cooled cast metals is overturn 180 ° during each repetition, then take out alloy cast ingot;
(4) alloy cast ingot is put into vacuum tube furnace, 7 × 10 are evacuated to tube furnace furnace chamber
-4pa, seals after passing into argon gas, and diamond heating to 950 DEG C is also incubated 16h.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy.
Composition through this hydrogen storage alloy of chemical composition analysis meets with the ratio of each chemical element obtained according to above-mentioned chemical general formula.
It is 250 object particles that the hydrogen storage alloy prepared by aforesaid method is broken for particle diameter, carries out hydrogen storage property test by hydrogen storage property comprehensive tester to preparing the alloy obtained.For the ease of putting hydrogen P-C-T curve and inhaling the test of hydrogen dynamic performance, hydrogen storage alloy particle is first vacuumized 1h under 500 DEG C of heating conditions, is then filled with hydrogen and reaches 100kPa to pressure, make alloy inhale hydrogen activation fast.Heating is found time-inhaled repeatedly, and 2 times extremely activation is complete for hydrogen.
The P-C-T of this alloy at 523K, 573K, 623K temperature as shown in Figure 3, wherein, X-coordinate is hydrogen richness (representing with atomic ratio) in alloy solid phase, ordinate zou is for inhaling hydrogen pressure (logarithmic coordinates, unit is kPa), hydrogen storage capability reaches 1.91wt%, and extrapolation equilibrium at room temperature forces down in 10
-1pa.Fig. 6 (b) inhales hydrogen kinetics under the 300K temperature condition of above-mentioned alloy, shows as and inhales hydrogen dynamic performance preferably.Fig. 4 (c) causes disproportion kinetics for above-mentioned alloy hydrogen under 723K, and Fig. 4 (d) causes disproportion kinetics for the hydrogen of existing ZrCo hydrogen storage alloy, and the alloy that the present embodiment provides shows as good resistant to hydrogen and causes disproportionation performance.Can find out that this alloy has hydrogen storage capability from test result large, the advantage that activation easily, level ground platform slope is low, level ground platform pressure is low, and there is good suction hydrogen desorption kinetics performance and resistant to hydrogen causes disproportionation performance simultaneously.Be suitable for the safe handling of tritium, store and transport.
Embodiment four
Embodiments of the invention four provide a kind of AB type hydrogen storage alloy for storing tritium, and its component general formula is Zr
0.8ti
0.2co
0.8fe
0.2, wherein, the purity of each raw material is 99.2%.
The present embodiment additionally provides a kind of preparation method of above-mentioned hydrogen storage alloy, comprises the following steps:
(1) each raw material is carried out batching weighing after clean and drying, additionally add 1%, Fe according to each raw material dosage Ti during batching and additionally add 2.5%, Co and additionally add 3%;
(2) raw material prepared is mixed in the water jacketed copper crucible be placed in vacuum non-consumable arc-melting furnace, a reserved water jacketed copper crucible, toward wherein placing high-purity Ti metal (purity is 99.93%), then successively utilize mechanical pump and the furnace chamber of diffusion pump to vacuum non-consumable arc-melting furnace to vacuumize, make the furnace chamber vacuum tightness of smelting furnace reach 9.5 X 10
-4pa magnitude, then passes into high-purity argon gas, makes furnace chamber internal gas pressure reach 6 × 10
4pa, vacuumizes afterwards and reaches 9.5 X 10
-4pa magnitude, more logical argon gas, so repeatedly vacuumize and inflate cleaning furnace chamber 3 times, then passing into high-purity argon gas, making the furnace chamber of smelting furnace reach 7.5 × 10
4pa;
After the tungsten electrode energising striking of Ti metal position in vacuum non-consumable smelting furnace, electric current is enlarged to 150A, first melting is carried out to the high-purity Ti metal in water jacketed copper crucible, make metal Ti change liquid state into, powered-down, utilizes high-purity Ti ingot to cool and absorbs residual free state oxygen 1min in furnace chamber;
(3) to after the tungsten electrode energising striking of vacuum non-consumable smelting furnace interalloy raw material position, electric current is enlarged to 150A, to the institute's preparing metal raw material melting in water jacketed copper crucible to changing liquid state into completely, holding current 2min, simultaneously adjust tungsten electrode at cast metals edge slowly around;
Powered-down, liquid raw metal cooled and solidified forms cast metals; Repeat above-mentioned energising striking-melting-process of cooling 4 to take turns, and all cooled cast metals is overturn 180 ° during each repetition, then take out alloy cast ingot;
(4) alloy cast ingot is put into vacuum tube furnace, 9.5 × 10 are evacuated to tube furnace furnace chamber
-4pa, seals after passing into argon gas, and diamond heating to 960 DEG C is also incubated 18h.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy.
Composition through this hydrogen storage alloy of chemical composition analysis meets with the ratio of each chemical element obtained according to above-mentioned chemical general formula.
It is 180 object particles that the hydrogen storage alloy prepared by aforesaid method is broken for particle diameter, carries out hydrogen storage property test by hydrogen storage property comprehensive tester to preparing the alloy obtained.For the ease of putting hydrogen P-C-T curve and inhaling the test of hydrogen dynamic performance, hydrogen storage alloy particle is first vacuumized 1h under 500 DEG C of heating conditions, is then filled with hydrogen and reaches 100kPa to pressure, make alloy inhale hydrogen activation fast.Heating is found time-inhaled repeatedly, and 2 times extremely activation is complete for hydrogen.
Fig. 5 (a) inhales hydrogen kinetics under the 300K temperature condition of this alloy, shows as and inhales hydrogen dynamic performance preferably.Fig. 7 (b) is the X-ray diffractogram of above-mentioned alloy.Can find out that this alloy has hydrogen storage capability from test result large, the advantage that activation easily, level ground platform slope is low, level ground platform pressure is low, and there is good suction hydrogen desorption kinetics performance and resistant to hydrogen causes disproportionation performance simultaneously.Be suitable for the safe handling of tritium, store and transport.
Embodiment five
Embodiments of the invention five provide a kind of AB type hydrogen storage alloy for storing tritium, and its component general formula is Zr
0.7ti
0.3co
0.8fe
0.2, wherein, the purity of each raw material is 99.05%.
The present embodiment additionally provides a kind of preparation method of above-mentioned hydrogen storage alloy, comprises the following steps:
(1) each raw material is carried out batching weighing after clean and drying, additionally add 1%, Fe according to each raw material dosage Ti during batching and additionally add 2.5%, Co and additionally add 3%;
(2) raw material prepared is mixed in the water jacketed copper crucible be placed in vacuum non-consumable arc-melting furnace, a reserved water jacketed copper crucible, toward wherein placing high-purity Ti metal (purity is 99.98%), then successively utilize mechanical pump and the furnace chamber of diffusion pump to vacuum non-consumable arc-melting furnace to vacuumize, make the furnace chamber vacuum tightness of smelting furnace reach 1 X 10
-4pa magnitude, then passes into high-purity argon gas, makes furnace chamber internal gas pressure reach 8.8 × 10
4pa, vacuumizes afterwards and reaches 1 X 10
-4pa magnitude, more logical argon gas, so repeatedly vacuumize and inflate cleaning furnace chamber 4 times, then passing into high-purity argon gas, making the furnace chamber of smelting furnace reach 6 × 10
4pa;
After the tungsten electrode energising striking of Ti metal position in vacuum non-consumable smelting furnace, electric current is enlarged to 140A, first melting is carried out to the high-purity Ti metal in water jacketed copper crucible, make metal Ti change liquid state into, powered-down, utilizes high-purity Ti ingot to cool and absorbs residual free state oxygen 2min in furnace chamber;
(3) to after the tungsten electrode energising striking of vacuum non-consumable smelting furnace interalloy raw material position, electric current is enlarged to 140A, to the institute's preparing metal raw material melting in water jacketed copper crucible to changing liquid state into completely, holding current 2min, simultaneously adjust tungsten electrode at cast metals edge slowly around;
Powered-down, liquid raw metal cooled and solidified forms cast metals; Repeat above-mentioned energising striking-melting-process of cooling 5 to take turns, and all cooled cast metals is overturn 180 ° during each repetition, then take out alloy cast ingot;
(4) alloy cast ingot is put into vacuum tube furnace, 1 × 10 is evacuated to tube furnace furnace chamber
-4pa, seals after passing into argon gas, and diamond heating to 980 DEG C is also incubated 20h.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy.
Composition through this hydrogen storage alloy of chemical composition analysis meets with the ratio of each chemical element obtained according to above-mentioned chemical general formula.
It is 150 object particles that the hydrogen storage alloy prepared by aforesaid method is broken for particle diameter, carries out hydrogen storage property test by hydrogen storage property comprehensive tester to preparing the alloy obtained.For the ease of putting hydrogen P-C-T curve and inhaling the test of hydrogen dynamic performance, hydrogen storage alloy particle is first vacuumized 1h under 500 DEG C of heating conditions, is then filled with hydrogen and reaches 100kPa to pressure, make alloy inhale hydrogen activation fast.Heating is found time-inhaled repeatedly, and 2 times extremely activation is complete for hydrogen.
Fig. 6 (a) inhales hydrogen kinetics under the 300K temperature condition of this alloy, shows as and inhales hydrogen dynamic performance preferably.Fig. 7 (c) is the X-ray diffractogram of above-mentioned alloy.Can find out that this alloy has hydrogen storage capability from test result large, the advantage that activation easily, level ground platform slope is low, level ground platform pressure is low, and there is good suction hydrogen desorption kinetics performance and resistant to hydrogen causes disproportionation performance simultaneously.Be suitable for the safe handling of tritium, store and transport.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. for storing an AB type hydrogen storage alloy for tritium, it is characterized in that, its component general formula is Zr
1-xti
xco
1-yfe
y, wherein 0.1≤x≤0.4,0.1≤y≤0.2.
2. the AB type hydrogen storage alloy for storing tritium according to claim 1, is characterized in that, wherein 0.1≤x≤0.2,0.1≤y≤0.15.
3. the AB type hydrogen storage alloy for storing tritium according to claim 1, is characterized in that, the material purity of described Zr, described Ti, described Co, described Fe is all more than 99%.
4. a preparation method for the AB type hydrogen storage alloy for storing tritium described in any one of claims 1 to 3, is characterized in that, according to proportioning, the mixing of each raw material is placed on anaerobic, is full of rare gas element, 6 × 10
4~ 8 × 10
4melting under the envrionment conditions of Pa, treats that it is cooled to ingot casting after annealing.
5. the preparation method of the AB type hydrogen storage alloy for storing tritium according to claim 4, is characterized in that, described smelting temperature is 1852 ~ 2860 DEG C.
6. the preparation method of the AB type hydrogen storage alloy for storing tritium according to claim 4, it is characterized in that, the concrete operations of described melting are: after utilizing tungsten electrode energising striking, adjustment electric current to 120 ~ 220A, by mixed material melting to changing fluent meterial into completely.
7. the preparation method of the AB type hydrogen storage alloy for storing tritium according to claim 4, is characterized in that, the method for described annealing is: described ingot casting is placed in air pressure 10
-3below Pa, be full of insulation 12 ~ 20h, then furnace cooling in rare gas element, the environment of 900 ~ 1000 DEG C.
8. the preparation method of the AB type hydrogen storage alloy for storing tritium according to claim 4, is characterized in that, the method manufacturing described envrionment conditions is: in reaction vessel, put into metal and pass into rare gas element, makes the air pressure of described reaction vessel be 6 × 10
4~ 8 × 10
4pa, then smelting metal, absorb oxygen, and described metal is metal titanium or metal zirconium or cobalt metal, preferable alloy titanium.
9. the preparation method of the AB type hydrogen storage alloy for storing tritium according to claim 8, it is characterized in that, putting into described metal titanium and before passing into described rare gas element, also comprising the cavity cleaning described reaction vessel: being evacuated to air pressure to described reaction vessel is 10
-3~ 10
-4pa, then passes into rare gas element, makes the air pressure of described cavity be 5 × 10
4~ 9 × 10
4pa, repeats this operation repeatedly, preferably repeats 3 ~ 4 times.
10. the preparation method of the AB type hydrogen storage alloy for storing tritium according to claim 4, it is characterized in that, during melting, described Ti, described Co, described Fe also comprise compensation material, described compensation material adds with described raw material simultaneously, the compensation material consumption of described Ti is 1 ~ 2% of its raw material dosage, the compensation material consumption of described Co is 3 ~ 4% of its raw material dosage, and the compensation material consumption of described Fe is 2.5 ~ 3.5% of its raw material dosage.
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| CN114918421A (en) * | 2022-04-21 | 2022-08-19 | 北京航空航天大学 | Fiber space limited domain preparation method of ZrCo alloy and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108149070A (en) * | 2016-12-02 | 2018-06-12 | 北京有色金属研究总院 | A kind of Zr-Fe systems alloy stored for tritium and preparation method thereof |
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| CN114918421A (en) * | 2022-04-21 | 2022-08-19 | 北京航空航天大学 | Fiber space limited domain preparation method of ZrCo alloy and application thereof |
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