CN103952647A - Magnesium base hydrogen storage nanometer.amorphous alloy preparation method - Google Patents
Magnesium base hydrogen storage nanometer.amorphous alloy preparation method Download PDFInfo
- Publication number
- CN103952647A CN103952647A CN201410112287.7A CN201410112287A CN103952647A CN 103952647 A CN103952647 A CN 103952647A CN 201410112287 A CN201410112287 A CN 201410112287A CN 103952647 A CN103952647 A CN 103952647A
- Authority
- CN
- China
- Prior art keywords
- alloy
- melting
- prealloy
- base hydrogen
- bearing
- 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.)
- Pending
Links
Abstract
The present invention provides a magnesium base hydrogen storage nanometer.amorphous alloy preparation method, which comprises: a mother alloy smelting step: smelting raw materials comprising magnesium, nickel and mixed rare earth to form a mother alloy liquid; and a solidifying step: solidifying the melted mother alloy liquid to obtain the magnesium base hydrogen storage nanometer.amorphous alloy, wherein the mother alloy smelting step comprises a pre-alloy smelting step and an induction smelting step, the pre-alloy smelting step is pre-smelting the nickel and the mixed rare earth in the raw materials to prepare a nickel-rare earth pre-alloy, the induction smelting step is carrying out mixing and induction smelting on the nickel-rare earth pre-alloy and the magnesium to prepare the mother alloy liquid, and the solidifying step adopts the melt spinning method to make the mother alloy liquid be solidified so as to obtain the magnesium based hydrogen storage nanometer.amorphous alloy.
Description
Technical field
The present invention relates to a kind of preparation method of Mg base hydrogen bearing alloy, particularly a kind of preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing that contains nickel and rare earth element.
Background technology
A large amount of exploitation of the fossil energy such as coal, oil had both caused serious environmental problem, again because of resource day by day exhausted and not reusable edible energy dilemma pendulum is being given in face of the whole world, the exploitation of new forms of energy, novel material are extremely urgent.
Because resource many (protiums account for mass of the universe 75%), thermal value are large, (calorific value is about 1.3 * 105kJ/kg H to Hydrogen Energy
2, be three times of gasoline), combustion products is water, the little and reusable edible on the impact of environment and be considered to solve a large green novel energy source of current energy dilemma.
And hydrogen storage technology to be Hydrogen Energy utilize practical key generally acknowledges that one of best hydrogen storage method is the hydrogen storage technology based on metal reversible hydrogen compound at present, this hydride is inhaled and is put hydrogen by changing temperature or pressure condition.
Mg base hydrogen bearing alloy has the high hydrogen storage of 7.6wt.%H because of magnesium, and the features such as density is little, aboundresources, cheap use safety, are acknowledged as and have one of hydrogen storage material of DEVELOPMENT PROSPECT most.
The features such as vapour pressure for Magnuminium is large, volatile, oxidizable, people focus stake on improve Magnuminium technology of preparing.The preparation of Mg base hydrogen bearing alloy generally has following several method: high-temperature vacuum smelting process, mechanical alloying method, hydriding combustion synthesis method, reaction ball milling method and rapid solidification method, set forth respectively the relative merits of these methods below.
High-temperature vacuum smelting process is industrial a kind of prior synthesizing method of preparing Mg base hydrogen bearing alloy, that but melting preparation temperature requires is high (when nickeliferous will higher than 1456 ℃ of the fusing points of Ni), be easy to cause a large amount of volatilizations of magnesium, the composition that very difficult acquisition designs, energy consumption is also very large.
Mechanical alloying method, claim again high-energy ball milling method, though because of solved magnesium alloy vapour pressure large, be difficult to the problem of conventional melting and can guarantee that good hydrogenation property widely applies, but, this method has Ball-milling Time long (10～120h), easily introduces the pollution of oxygen and iron, the problem that is difficult to scale production.
The hydriding combustion synthesis method that Yagi spark gap research group of northeastern Japan university 1997 proposes, although have advantages of that hydrogen-absorbing ability is strong, short without activation treatment and High Purity, generated time, because of being under oxygen free condition, completes Mg in thermal explosion mode
2the burning of Ni is synthetic, so it is large to control difficulty, dangerous large.
Reaction ball milling method feature is, under nitrogen atmosphere, metallic element is carried out to ball milling, obtains metal hydride when can make sample generation mechanical deformation, generation defect.Although this method can generate amorphous phase and nano-scale microtexture, improved hydrogenation kinetics, still there is the shortcomings such as Ball-milling Time is long, the hydrogenation efficiency of magnesium is low.
Rapid solidification method is that the aluminium alloy of melting is clamped to hole, the bottom of a pan roller surfaces directive one high speed rotating, that make with high thermal conductivity coefficient material certainly, and aluminium alloy is solidified as a very thin band (thickness is less than 15～20 μ m left and right) on roll surface.Obviously, roll surface movement velocity is higher, and the flow of aluminium alloy is larger, and the alloy strip that obtained is just thinner.This method can obtain continuous, fine and close alloy strip.But be also a large problem points of this method of restriction as how lower cost provides the aluminium alloy of melting.
Summary of the invention
In order to overcome the above-mentioned problems in the prior art, goal of the invention of the present invention is with low cost production magnesium-base hydrogen storage material, with low cost, at relatively low temperature, complete the preparation of Mg base hydrogen bearing alloy exactly specifically and guarantee the composition proportion of alloy, a further object of the present invention is to improve the suction hydrogen thermomechanical property of Mg base hydrogen bearing alloy.
In order to realize foregoing invention object, the invention provides following technical scheme.
The preparation method who the invention provides a kind of Mg base hydrogen bearing alloy, comprising: the mother alloy melting step that the raw material melting being comprised of magnesium, nickel and mishmetal is formed to mother alloy liquid; And the mother alloy liquid that makes melting solidifies the coagulation step that obtains Mg base hydrogen bearing alloy, it is characterized in that, described mother alloy melting step comprises:
Nickel in described raw material and mishmetal are prepared to the prealloy melting step of nickel rare earth prealloy by presmelting; And
Described nickel rare earth prealloy is mixed with magnesium and carried out the induction melting step that induction melting is prepared base hydrogenous alloy.
In foregoing invention, preferably: when described nickel rare earth prealloy is mixed with magnesium, described nickel rare earth prealloy is solid-state or liquid, and magnesium is solid-state or liquid.
In foregoing invention, preferably: be provided with the fragmentation treatment step of solid nickel rare earth prealloy fragmentation between described prealloy melting step and described induction melting step.
In foregoing invention, preferably: in described prealloy melting step and/or described induction melting step, atmosphere during melting is inert atmosphere, is more preferably argon gas.
In foregoing invention, preferably: described coagulation step solidifies described mother alloy liquid by naturally cooling or rapid solidification method.
In foregoing invention, preferably: when described coagulation step solidifies described mother alloy liquid by rapid solidification method, described rapid solidification method is the band method of getting rid of, described in to get rid of the cooling roller material of using with method be Cu, stainless steel or graphite.
In foregoing invention, preferably: described rare earth element is selected from least one element in Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
In foregoing invention, preferably: the composition of described raw material and/or described Mg base hydrogen bearing alloy is that the nickel of 14～24 % by weight is, the La of 1～6 % by weight, the Ce of 2～7 % by weight and the Mg of surplus.
In foregoing invention, preferably: described prealloy melting step is in arc-melting furnace; Described induction melting carries out in vacuum induction melting furnace.
In foregoing invention, preferably: described prealloy melting step is heated to the temperature that makes Ni and rare earth element fusing; More than being heated to magnesium fusing point in described induction melting step, below 700 ℃.
Accompanying drawing explanation
Fig. 1 represents the XRD spectrum before as cast condition Mg-Ni-Mm absorption hydrogen.
Fig. 2 represents as cast condition Mg-10Ni-2Mm(B) alloy Mg and Mg
2van ' the t Hoff curve of Ni hydrogenation.
Fig. 3 represents as cast condition Mg-10Ni-2Mm(B) the front XRD spectrum of absorption hydrogen.
Fig. 4 represents the nanocrystalline M g-10Ni-2Mm(Cu1000 obtaining after 10.5m/s gets rid of tape handling) XRD of alloy spectrum.
Fig. 5 represents the amorphous Mg-10Ni-2Mm(Cu2000 obtaining after 20.9m/s gets rid of tape handling) XRD of alloy spectrum.
Fig. 6 represents Van ' the t Hoff curve of the hydrogen storage alloy of various grain forms.
Embodiment
Embodiment 1
In order to realize above-mentioned purpose of the present invention, the present invention has adopted the mother alloy (as cast condition) that utilizes the method for two step meltings to prepare Mg-base hydrogen-bearing alloy material.
Wherein, adopt the method for prealloy melting-induction melting two step meltings to prepare mother alloy, so-called two smelting processes are exactly first Ni and Mm(Mm as adding element to be represented to rare earth element, be selected from least one element in Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, it is example that embodiment below be take La and Ce) carry out prealloy melting, then the prealloy after melting is mixed with Mg and carries out vacuum induction melting.
The prealloy obtaining about presmelting can be that the prealloy that solidifies state mixes with the liquid Mg after solid-state Mg particle or fusing with the hybrid mode of Mg; also can be that after melting, liquid prealloy mixes with the liquid Mg after solid-state Mg particle or fusing, particular case be selected according to actual production.In addition, for the prealloy that solidifies state, can before mixing with magnesium, first carry out prealloy fragmentation processing, more even to mix with Mg.
When the mixture of prealloy and Mg is carried out to vacuum induction melting, because Ni and rare earth element Mm have carried out prealloy melting, so only need to be heated to the temperature on a little higher than Mg fusing point (651 ℃) and be incubated certain hour, be equipped with stirring to a certain degree, with abundant melting, can make Mm and Ni can diffuse into preferably in magnesium melt, generate ternary alloy.
Holding temperature during about induction melting, after Mg fusing point, preferably more low temperature is better, to reduce the volatilization of Mg, more preferably between Mg fusing point～750 ℃, further preferably between Mg fusing point～700 ℃.
Adopt the method for two step meltings like this at relatively low temperature, to complete in short-term the preparation of ternary alloy, at utmost guaranteed the composition proportion of alloy.
In addition, in two smelting processes, in order to control the volatilization of magnesium, during melting, pass into rare gas element, such as argon gas, to avoid the oxidation of magnesium alloy, and suppress the volatilization of magnesium.
Embodiment 2
In addition, in order to realize above-mentioned purpose of the present invention, the present invention also provides the making method of making the nano amorphous alloy of Mg-base hydrogen-bearing, utilizes prealloy melting-induction melting-rapid solidification method (getting rid of band method) to make the nano amorphous alloy of Mg-base hydrogen-bearing.
Specifically be exactly first a small amount of Ni and Mm to be carried out to prealloy melting, then the prealloy after melting is mixed to (hybrid mode is the same) with Mg and carry out vacuum induction melting, then, the mother alloy that utilization is got rid of with the Mg base hydrogen bearing alloy that makes two smelting processes produce in method contacts with adopted cooling roller, control the rotating speed (namely controlling the linear velocity of roll surface motion) of cooling roller, obtain the alloy strip (namely adopting different belt speed to get rid of band) throwing away under friction-motion speed, make thus nanocrystalline, the non-crystalline material of Mg base hydrogen bearing alloy.
Holding temperature selection when the mode of mixing with Mg about the prealloy after presmelting and vacuum induction melting and melting mode are referring to embodiment 1.
Equally, when induction melting, in order to control the volatilization of magnesium, during melting, pass into rare gas element, such as argon gas, to avoid the oxidation of magnesium alloy, and suppress the volatilization of magnesium.
As the material of cooling roller in rapid solidification method, can adopt Cu band, also can adopt Stainless Steel Band or graphite tape, but be not limited to this.
, non-crystalline material nanocrystalline in order to produce, need to adopt the tape handling of getting rid of of different belt speed.Because different material thermal conductivities is different, have influence on the alloy band speed of cooling of getting rid of tape handling process, so need to determine cooling roller roll surface speed according to the material of cooling roller and the mother alloy that will reach rate of cooling, to ensure that the cooling alloy band obtaining throws away with the linear velocity of regulation.Such as, can be with the roll surface speed of 10～25m/s with method based on getting rid of of Cu cooling roller, getting rid of of stainless steel cooling roller can be with the roll surface speed that adopts 20～25m/s with method, and getting rid of of graphite cooling roller can be with the roll surface speed of 35～45m/s with method.
The present invention has prepared the cast alloy of Mg-base hydrogen-bearing alloy material by above-mentioned two step smelting processes, guaranteed to complete in short-term the preparation of ternary alloy at relatively low temperature, at utmost guarantee the composition proportion of alloy, improved the thermomechanical property that cast alloy is inhaled hydrogen.
The present invention is by above-mentioned two step meltings and get rid of with the combination of method and prepare Mg-base hydrogen-bearing alloy material, successfully prepared Mg base hydrogen bearing alloy nanocrystalline, amorphous, not only guaranteed to complete in short-term the preparation of ternary alloy at relatively low temperature, at utmost guarantee the composition proportion of alloy, improved thermomechanical property nanocrystalline, that amorphous alloy is inhaled hydrogen.
Due to the alloy preparation method that prealloy melting is simple, vacuum induction melting method is industrial widespread use; this method cost is low; be suitable for batch production; rapid solidification method is again to prepare amorphous, the nanocrystalline method generally adopting; operation is simple; so be that the invention of above-mentioned embodiment 1 or the invention of above-mentioned embodiment 2 are all the methods that is easy to accomplish scale production, the development and application of the hydrogen storage material of having made greater efforts to promote.
Below in conjunction with specific embodiment and with reference to accompanying drawing, the invention will be further described.Below listed embodiment be only the description to the preferred embodiment of the present invention, do not form any limitation of the invention.
Embodiment 1
The preparation of material
The raw material of melting Mg-Ni-Mm alloy is every general 0.2g of granular Mg(of purity 99.90%), (processed is bulk or shavings shape in the little strip of 99.95%Ni (every general 1g), mishmetal Mm, for example by La and Ce, formed, and with La:Ce=37:63 % by weight) carried out proportioning, the concrete proportioning between them is as table 1.
Table 1Mg-Ni-Mm alloying constituent proportioning table
First the Ni of said ratio and Mm are carried out to prealloy melting with electric arc furnace, after prealloy fragmentation, carry out vacuum induction melting again with Mg with induction melting furnace, then the alloy after naturally cooling vacuum induction melting obtains cast alloy.
In prealloy fusion process, the nickel preparing and mishmetal raw material are put into smelting pot, build lid, be evacuated to 6 * 10
-3below Pa, approximately there is 30min, be filled with argon gas and stop to 0.05MPa.Starting rod, apart from sample 1-2mm place's striking, slowly raises starting rod after the starting the arc, progressively regulates striking electric current, strengthens the intensity of electric arc, after sample fusing, can strengthen magnetic stir current, and stir current is controlled at 10A left and right, and sample is stirred fully.Each melting is complete once after solidifying, and with mechanical manipulator, is overturn, and carries out melting next time.This master alloy melt back three times is substantially even.
Why adopting prealloy melting technology, is for following 2 considerations:
The first point, during induction melting, consider the large 361Pa(923K of vapour pressure of magnesium), induction melting may cause the volatilization of magnesium serious for a long time, to such an extent as to the alloying constituent the obtaining phenomenon large with expection composition deviation, the soaking time of melting again can not be long, require again three kinds of element fusions evenly simultaneously, this has just just had higher requirement for the dispersing uniformity of Mm and Ni, and then expect by prealloy melting first only that Mm and Ni melting on the temperature far above Mg fusing point is even, mix with Mg and carry out induction melting again, guaranteed the dispersing uniformity of Mm and Ni, reached the uniform object of induction melting, and more than no longer needing to be heated to nickel fusing point during due to mixture at induction melting Mg and Ni-Mm prealloy, so a large amount of volatilizations of Mg are avoided.
Second point (being also preferably to adopt the reason that the prealloy fragmentation obtaining is processed), as everyone knows, the metal that Ni is high-melting-point, high rigidity, intensity is large, these characteristics make its very difficult fragmentation, and the nickel in batching is in the form of sheets, infusibility more, the solid solution of Ni in Mg just needs insulation for a long time to reach, otherwise the alloying constituent that can cause melting to obtain is most probably inhomogeneous, and long insulation can cause the volatilization of Mg.
And find that after deliberation Mm has good fragility than Ni, and Mm and Ni be oligo-element with respect to Mg, if these two kinds of metals are carried out to prealloy melting, the prealloy after presmelting be mainly in the middle of phase resultant MmNi
5, this alloy melting point is 1350 ℃, only than 1456 ℃ of Ni, slightly reduces, but this prealloy MmNi
5be highly brittle, be easily ground into powder, cover above Mg particle and carry out follow-up vacuum induction melting technique, can more contribute to obtain the uniform ternary alloy of composition.Therefore, when Mm, Ni are carried out to presmelting preferably can access MmNi
5the material composition of tissue carries out, and before mixing with Mg after presmelting, first solid-state MmNi5 is carried out to fragmentation processing.
In addition, according to the phasor of Mg and Ni and various rare earth elements, can learn, Mm in design mix, Ni has lower eutectic temperature (Mg-La:613 ℃ with Mg, Mg-Ce:590 ℃, Mg-Ni:506 ℃, in addition, Mg and Y, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the eutectic temperature of Lu is respectively 565 ℃, 575 ℃, 548 ℃, 550 ℃, 542 ℃, 571 ℃, 548 ℃, 559 ℃, 561 ℃, 565 ℃, 584 ℃, 592 ℃, 509 ℃, 616 ℃), therefore, when vacuum induction melting, can there is at a lower temperature eutectic reaction with Mg respectively in these elements, and Mm and Ni are a small amount of than Mg, few in prealloy amount, on the large basis of dispersity, because Ni and Mm have carried out prealloy melting, so as long as the insulation of the temperature on a little higher than Mg fusing point (651 ℃) certain hour, be equipped with stirring to a certain degree, can make Mm and Ni can diffuse into preferably in magnesium melt, generate ternary alloy.
Consider the large 361Pa(923K of vapour pressure of magnesium), vacuum induction melting may cause the volatilization of magnesium serious for a long time, so can pass into argon gas during melting, has both avoided magnesium alloy oxidation, has suppressed again the volatilization of Mg.
Prealloy melting can adopt the high vacuum magnetic control arc stove of Shenyang Scientific Instrument Research & Mfg. Center Co., Ltd., C.A.S.
Vacuum induction melting equipment is intermediate frequency vacuum induction furnace ZG-25, and the nominal parameter of this induction furnace is: peak power: 60KW, and standard capacity is 25kg, maximum operating temperature: 1800 ℃, final vacuum: 1.0 * 10-2Pa.Induction furnace is furnished with thermopair, can accurately control temperature.
The sign of material
Alloy after melting adopts X-ray fluorescence spectrometer detection elements composition.Detecting sample is the rectangular parallelepiped of surface size 2cm * 2cm.For fear of the error being oxidized or impurity brings, in glove box, sample surfaces has been carried out to turning processing.
<1> gained alloy component analysis
Alloying constituent detected result is in Table 2, although the elemental composition of alloying constituent and design alloy deviation slightly, generally, the content of Mm element still comparatively approaches, and from alloy the content trend of Ni and Mm, constituent content meets expects variation.Melting sample preparation is comparatively successful, has solved the defect that alloying constituent ratio that independent use vacuum induction melting method is difficult to obtain designing is difficult to obtain, and has farthest guaranteed the composition proportion of alloy, can be used for follow-up hydrogen storage property test.
The Mg-Ni-Mm alloy composition that table 2XRF measures
The preparation method who is the present embodiment has obtained the alloying constituent proportioning of wanting.
<2> gained beneficial effect is analyzed
In addition, because the fusing point of Ni is 1456 ℃, and the fusing point of Ce is 798 ℃, the fusing point of La is 920 ℃, and we first carry out prealloy melting by adopting by Ni and mixed rare-earth elements Mm in arc-melting furnace, Ni after melting and Mm are mixed to the such melting mode of induction melting of carrying out again with Mg, with in existing technique by Mg, Ni compares with the method that rare earth element carries out melting simultaneously together in induction melting furnace, large owing to not needing content, low-melting Mg is heated to the temperature making on Ni fusing point, and only content Ni on the low side and Mm with respect to Mg need to be heated to by presmelting and make Ni, La, the temperature of the fusing such as Ce, so saved the energy and time, that is to say the preparation that has completed in short-term ternary alloy at relatively low temperature.
And during due to vacuum induction melting, adopt lower temperature, so the component segregation of alloy is naturally just few, alloy ratio is more even.
The preparation method who is the present embodiment has reached goal of the invention, has obtained technique effect.
<3> gained alloy material phase analysis
About the thing of cast alloy, we have carried out material phase analysis by X-ray diffraction method XRD, analytical results collection of illustrative plates as shown in Figure 1 mutually.
In collection of illustrative plates, show that this ternary cast alloy includes three thing phase: Mg, Mg
2ni and MmMg
12phase, wherein, Mg and Mg
2there is very high intensity at the corresponding peak of Ni, means that in alloy, the content of this two-phase is higher, is main thing phase, and collection of illustrative plates shows to also have the Mg of a small amount of rich Mm to exist mutually mutually, is demarcated as MmMg
12phase.And these things are inhaled the tissue playing a role while putting hydrogen in Mg base hydrogen bearing alloy mutually just, illustrate that the preparation method of the present embodiment has obtained the tissue of wanting.
The preparation method who is the present embodiment has obtained the tissue of wanting.
The suction hydrogen Thermodynamic Analysis of <4> gained alloy
In addition, we have also carried out inhaling the research of hydrogen thermomechanical property to the tissue of above-mentioned sample B, made as cast condition Mg-10Ni-2Mm(B) alloy Mg and Mg
2van ' the t Hoff curve of Ni hydrogenation, is shown in Fig. 2
According to this Van ' t Hoff curve, calculated MgH
2and Mg
2niH
4enthalpy produced in chemical reaction entropy, list 3 is as follows:
Table 3 as cast condition Mg-10Ni-2Mm(B) MgH in alloy
2and Mg
2niH
4the list of enthalpy produced in chemical reaction entropy
| ? | △H(kJ/mol) | Theoretical value | △S(J/mol·K) | Theoretical value |
| MgH 2 | -74.2 | -74.5 | -133.1 | -135 |
| Mg 2NiH 4 | -56.9 | -64.5 | -110.7 | -122 |
MgH wherein
2Δ H consistent with theoretical value with Δ S value, Mg
2niH
4Δ H and be respectively-56.9kJ/mol of Δ S H
2with-110.7J/mol, far below theoretical value-64.5kJ/molH
2with-122J/mol, the thermomechanical property of absorption hydrogen makes moderate progress.The suction hydrogen thermomechanical property that the preparation method of this explanation the present embodiment goes back alloy makes moderate progress.
Embodiment 2
The preparation of material
According to the raw material identical with embodiment 1, prepare the raw material of sample B in table 1.
First Ni and the Mm of the listed proportioning of sample B in table 1 are carried out to prealloy melting with electric arc furnace, after prealloy fragmentation, with induction melting furnace, carry out vacuum induction melting with Mg again, then, the mother alloy that utilization is got rid of with the Mg base hydrogen bearing alloy that makes two smelting processes produce in method contacts with the cooling roller getting rid of with adopting in method, control the rotating speed (namely controlling the linear velocity of roll surface motion) of cooling roller, obtain the alloy strip (namely adopting different belt speed to get rid of band) throwing away under friction-motion speed, make thus nanocrystalline, the non-crystalline material of Mg base hydrogen bearing alloy.
The Relevant Analysis of prealloy melting and vacuum induction melting can be referring to embodiment 1.
What rapid solidification equipment adopted Chinese Academy of Sciences Shenyang scientific instrument development center company limited gets rid of carrying equipment (cooling roller is Cu roller).Wherein adopt the belt speed of 10.5m/s (Cu1000) and 20.9m/s (Cu2000) to process as cast condition Mg-10Ni-2Mm (B) alloy.
The sign of material
The fabric analysis of <1> gained
Utilize X-ray diffraction technology to carry out material phase analysis to getting rid of the alloy obtaining with method, and by contrasting with congruent cast alloy, the variation of grain-size has been described.
The material phase analysis figure that cast alloy is inhaled before hydrogen shows there is very strong Mg phase peak, inferior strong Mg as shown in Figure 3
2, there is a small amount of MmMg in Ni phase peak simultaneously
12phase, peak shape is comparatively narrow, and intensity is very high.
And there has been obvious broadening at the XRD peak (Fig. 4) of the alloy that gets rid of tape handling of belt speed 10.5m/s, back end strengthens, and illustrates that alloy grain size significantly reduces.In intensity rising explanation alloy, occur privately decrystallized.The peak of (010) crystal face of corresponding Mg disappears substantially, and the corresponding peak value of (002) crystal face also declines to some extent, Mg
2ni and MmMg
12most of peak disappear.In conjunction with displaing microstructure observing below, alloying pellet has reached Nano grade.This alloy should be containing a large amount of nanocrystalline and a small amount of amorphous.
The XRD peak (Fig. 5) of the alloy that gets rid of tape handling of belt speed 20.9m/s shows, most peak all disappears, and residue other peak intensity is also very weak, and two obvious diffuse scattering peaks appear in whole spectral line, illustrate and in this alloy, occurred a large amount of decrystallized phenomenons, but still have a small amount of nanocrystalline existence.Adopt rapid solidification method to prepare amorphous, nanocrystalline very successful, can be used for follow-up hydrogen storage property test.
The Mg base hydrogen bearing alloy obtaining based on embodiment 2 has obtained nanocrystalline, amorphous structure.
The suction hydrogen Thermodynamic Analysis of <2> gained tissue
Fig. 6 shows Van ' the t Hoff curve of the hydrogen storage alloy of various grain forms, from as cast condition to nanocrystalline again to amorphous for Mg
2niH
4, its Van ' t Hoff curve display is along with grain-size diminishes to decrystallized, and the absolute value of rate of curve is reducing, and the absolute value of the △ H value that correspondence calculates also just reduces thereupon.
The occurrence calculating in contrast table 4, its absolute value is all little than theoretical value, and it is a lot of that amorphous entropy enthalpy is all less than theoretical value, visible Mg
2niH
4heat of Formation mechanics had very large improvement, especially for amorphous alloy.For MgH
2phase, as cast condition and nanocrystalline Van ' t Hoff curve approximation, very approaching with theoretical value, and amorphous Van ' t Hoff rate of curve absolute value diminishes, the absolute value of the enthalpy entropy of corresponding calculating place also reduces to some extent, so amorphous alloy is for MgH
2the Heat of Formation mechanics of phase also makes moderate progress, and other two crystalline state improvement effects are little, this may with MgH in the situation that Ni and Mm add
2the fast grain growth of forming core is relevant.In a word, the two kinds of suction hydrogen phase reaction thermodynamics that reduce of grain-size all make moderate progress thereupon, for Mg
2niH
4the effect of phase is especially obvious, and refinement alloying pellet has obtained checking for improving the thermodynamic (al) effect of suction hydrogen phase reaction.
Nanocrystalline, amorphous structure that the Mg base hydrogen bearing alloy obtaining based on embodiment 2 has are inhaled hydrogen thermomechanical property and are approached theoretical value or make moderate progress, and illustrate that preparation method is successful.
The alloy △ H of the hydrogen storage alloy of the various grain forms of table 4, △ S value
The present invention is by above-mentioned two step meltings and get rid of with the combined method of method and prepare Mg-base hydrogen-bearing alloy material, successfully prepared Mg base hydrogen bearing alloy nanocrystalline, amorphous, not only guaranteed to complete in short-term the preparation of ternary alloy at relatively low temperature, at utmost guarantee the composition proportion of alloy, and improved thermomechanical property nanocrystalline, that amorphous alloy is inhaled hydrogen.
From above explanation of the present invention, can find out and can make the present invention have various variations.Such variation can not think and departed from thought of the present invention and scope, for the personnel of all industry all apparent improvement be included in claim scope of the present invention.
Claims (9)
1. a preparation method for the nano amorphous alloy of Mg-base hydrogen-bearing, comprising:
The raw material melting being comprised of magnesium, nickel and mishmetal is formed to the mother alloy melting step of mother alloy liquid; And
Make the described mother alloy liquid of melting solidify the coagulation step that obtains the nano amorphous alloy of Mg-base hydrogen-bearing,
It is characterized in that:
Described mother alloy melting step comprises:
Nickel in described raw material and mishmetal are prepared to the prealloy melting step of nickel rare earth prealloy by presmelting; And
Described nickel rare earth prealloy is mixed with magnesium and is carried out the induction melting step that induction melting is prepared described mother alloy liquid,
Described coagulation step makes described mother alloy liquid solidify to obtain the nano amorphous alloy of Mg-base hydrogen-bearing by getting rid of band method.
2. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 1, is characterized in that,
When described nickel rare earth prealloy is mixed with magnesium, described nickel rare earth prealloy is solid-state or liquid, and magnesium is solid-state or liquid.
3. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 1, is characterized in that,
Between described prealloy melting step and described induction melting step, be provided with the fragmentation treatment step of solid nickel rare earth prealloy fragmentation.
4. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 1, is characterized in that,
In described prealloy melting step and/or described induction melting step, atmosphere during melting is inert atmosphere.
5. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 1, is characterized in that,
Described cooling roller material of getting rid of with method use is Cu, stainless steel or graphite.
6. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 1, is characterized in that,
Described rare earth element is selected from least one element in Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
7. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 6, is characterized in that,
The composition of described raw material and/or described Mg base hydrogen bearing alloy is that the nickel of 14～24 % by weight is, the La of 1～6 % by weight, the Ce of 2～7 % by weight and the Mg of surplus.
8. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 1, is characterized in that,
Described prealloy melting step is in arc-melting furnace; Described induction melting carries out in vacuum induction melting furnace.
9. the preparation method of the nano amorphous alloy of Mg-base hydrogen-bearing as claimed in claim 1, is characterized in that,
Described prealloy melting step is heated to the temperature that makes Ni and rare earth element fusing; More than being heated to magnesium fusing point in described induction melting step, below 700 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410112287.7A CN103952647A (en) | 2011-08-09 | 2011-08-09 | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410112287.7A CN103952647A (en) | 2011-08-09 | 2011-08-09 | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110226094 Division CN102277508A (en) | 2011-08-09 | 2011-08-09 | Preparation method of magnesium-based hydrogen storage alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103952647A true CN103952647A (en) | 2014-07-30 |
Family
ID=51329991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410112287.7A Pending CN103952647A (en) | 2011-08-09 | 2011-08-09 | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103952647A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972010A (en) * | 2019-04-15 | 2019-07-05 | 河北工业大学 | A kind of nano Mg base composite hydrogen storage material and preparation method |
| CN113512674A (en) * | 2021-04-20 | 2021-10-19 | 安泰科技股份有限公司 | Modified Mg-Ni-La nanocrystalline hydrogen storage alloy and preparation method thereof |
| CN113667908A (en) * | 2021-08-30 | 2021-11-19 | 广东省国研科技研究中心有限公司 | Nano TiF3And TiO2Nanotube synergistically modified magnesium-based amorphous alloy hydrogen storage material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0472043A (en) * | 1990-07-11 | 1992-03-06 | Honda Motor Co Ltd | Highly corrosion resistant magnesium alloy |
| CN1502712A (en) * | 2002-11-26 | 2004-06-09 | 有研稀土新材料股份有限公司 | Hydrogen storage alloy and process for preparing quick cooling thick band thereof |
| CN1651587A (en) * | 2005-02-02 | 2005-08-10 | 华南理工大学 | REMg3 type hydrogen storage alloy and its preparation method |
| CN101260492A (en) * | 2008-04-29 | 2008-09-10 | 安泰科技股份有限公司 | Magnesium-base nano hydrogen-storage material and preparing method thereof |
| CN101372735A (en) * | 2008-08-14 | 2009-02-25 | 上海交通大学 | Mg-Ni-(Gd,Nd) bulk amorphous alloy and preparation thereof |
| CN101713055A (en) * | 2009-11-03 | 2010-05-26 | 清华大学 | Mg-Ni-Gd-Ag serial block amorphous alloy and preparation method thereof |
| CN101880840A (en) * | 2010-07-02 | 2010-11-10 | 哈尔滨工程大学 | Preparation method of Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy |
-
2011
- 2011-08-09 CN CN201410112287.7A patent/CN103952647A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0472043A (en) * | 1990-07-11 | 1992-03-06 | Honda Motor Co Ltd | Highly corrosion resistant magnesium alloy |
| CN1502712A (en) * | 2002-11-26 | 2004-06-09 | 有研稀土新材料股份有限公司 | Hydrogen storage alloy and process for preparing quick cooling thick band thereof |
| CN1651587A (en) * | 2005-02-02 | 2005-08-10 | 华南理工大学 | REMg3 type hydrogen storage alloy and its preparation method |
| CN101260492A (en) * | 2008-04-29 | 2008-09-10 | 安泰科技股份有限公司 | Magnesium-base nano hydrogen-storage material and preparing method thereof |
| CN101372735A (en) * | 2008-08-14 | 2009-02-25 | 上海交通大学 | Mg-Ni-(Gd,Nd) bulk amorphous alloy and preparation thereof |
| CN101713055A (en) * | 2009-11-03 | 2010-05-26 | 清华大学 | Mg-Ni-Gd-Ag serial block amorphous alloy and preparation method thereof |
| CN101880840A (en) * | 2010-07-02 | 2010-11-10 | 哈尔滨工程大学 | Preparation method of Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy |
Non-Patent Citations (1)
| Title |
|---|
| WU YING等: "The effect of solidification rate on microstructural evolution of a melt-spun Mg–20Ni–8Mm hydrogen storage alloy", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972010A (en) * | 2019-04-15 | 2019-07-05 | 河北工业大学 | A kind of nano Mg base composite hydrogen storage material and preparation method |
| CN109972010B (en) * | 2019-04-15 | 2020-11-03 | 河北工业大学 | Nano magnesium-based composite hydrogen storage material and preparation method thereof |
| CN113512674A (en) * | 2021-04-20 | 2021-10-19 | 安泰科技股份有限公司 | Modified Mg-Ni-La nanocrystalline hydrogen storage alloy and preparation method thereof |
| CN113667908A (en) * | 2021-08-30 | 2021-11-19 | 广东省国研科技研究中心有限公司 | Nano TiF3And TiO2Nanotube synergistically modified magnesium-based amorphous alloy hydrogen storage material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102277508A (en) | Preparation method of magnesium-based hydrogen storage alloy | |
| Grosjean et al. | Hydrogen production via hydrolysis reaction from ball-milled Mg-based materials | |
| Khan et al. | Hydrogen storage properties of nanocrystalline Mg2Ni prepared from compressed 2MgH2Ni powder | |
| Huang et al. | Electrode properties of melt-spun Mg–Ni–Nd amorphous alloys | |
| Zhang et al. | Superior hydrogen storage kinetics of Mg12YNi alloy with a long-period stacking ordered phase | |
| CN103317128B (en) | A kind of Mg-Ni-La base composite hydrogen storage alloy powder and preparation method thereof | |
| CN105695775B (en) | A kind of yttrium iron base alloy material, preparation method and application | |
| CN105063457B (en) | Nano-graphite compounded high-capacity RE-Mg-Ni-based hydrogen storage material and preparation method thereof | |
| CN110629091B (en) | High-capacity multi-phase hydrogen storage alloy for fuel cell and preparation method thereof | |
| CN110656272B (en) | Magnesium-based hydrogen storage material based on high entropy effect and preparation method thereof | |
| CN105316501B (en) | A kind of rare earth-magnesium base hydrogenous alloy and preparation method thereof | |
| CN106702191B (en) | A kind of ferrotianium yttrium base hydrogen storage material and intermediate alloy and preparation method | |
| CN109175349B (en) | High-performance double-rare-earth solid solution-based hydrogen storage material and preparation method thereof | |
| Yin et al. | A comparative study of NbF5 catalytic effects on hydrogenation/dehydrogenation kinetics of Mg-Zn-Ni and Mg-Cu-Ni systems | |
| CN103952647A (en) | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method | |
| CN103074529A (en) | Magnesium-nickel-yttria hydrogen storage alloy thin belt and preparation method thereof | |
| CN108220728B (en) | A kind of high capacity light graphite alkene catalytic rare earth magnesium-aluminum-based hydrogen storage material and preparation method | |
| CN108097947A (en) | A kind of high capacity Mg-Zn-Ni ternary hydrogen-storage alloys and preparation method thereof | |
| CN101962722A (en) | Method for preparing single-phase SmCo7 nanocrystalline alloy block material without doping elements | |
| CN1208487C (en) | Nano crystal multiphase mixed rare earth-magnesium system hydrogen-storing alloy and its preparation method | |
| Giza et al. | Preparation and electrochemical properties of La2MgNi8Co1− xMx (M= Al or In; x= 0 or 0.2) hydrogen storage alloys | |
| CN104294070B (en) | A kind of low-temperature sintering preparation is containing the method for Mg aluminium alloy | |
| Huang et al. | Effects of microstructure on the electrode properties of melt–spun Mg-based amorphous alloys | |
| Bu et al. | Improved hydrogen storage kinetics of nanocrystalline and amorphous Pr-Mg-Ni-based PrMg12-type alloys synthesized by mechanical milling | |
| CN112387976B (en) | Easily-activated RE-Ti-Fe alloy for fuel cell and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140730 |
|
| RJ01 | Rejection of invention patent application after publication |