CN1942600A - Method of atomizing alloy crystal grain by hydrogen treatment - Google Patents

Method of atomizing alloy crystal grain by hydrogen treatment Download PDF

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Publication number
CN1942600A
CN1942600A CNA2005800119611A CN200580011961A CN1942600A CN 1942600 A CN1942600 A CN 1942600A CN A2005800119611 A CNA2005800119611 A CN A2005800119611A CN 200580011961 A CN200580011961 A CN 200580011961A CN 1942600 A CN1942600 A CN 1942600A
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alloy
hydrogen
avidity
crystal grain
weight
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冈田益男
高村仁
龟川厚则
高桥淳也
舟山贵郎
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Tohoku Techno Arch Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

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Abstract

A technology for atomizing the crystal grains of alloy whose main constituents are elements exhibiting weak affinity with hydrogen. With respect to the alloy whose main constituents are elements exhibiting weak affinity with hydrogen in which an element exhibiting strong affinity with hydrogen is contained, resulting from attaining of presence of an element exhibiting strong affinity with hydrogen in an alloy whose main constituents are elements exhibiting weak affinity with hydrogen, any crystal grains of the alloy can be super-atomized by subjecting the alloy to heat treatment involving hydrogen absorption and release, thereby realizing super-high strength thereof. Thus, the properties of the alloy can be improved and enhanced.

Description

Utilize hydrogen to handle the method that the crystal grain of alloy is carried out miniaturization
Technical field
The present invention relates to a kind of alloy, the element of this alloy a little less than with hydrogen avidity is the main composition key element, and provides a kind of and utilize hydrogen to handle crystal grain is carried out the method for ultra micro refinement and the alloy with effect of miniaturization.
Background technology
The miniaturization of crystallization particle diameter is to improve the mechanical properties of alloy, the method for processibility.As the crystal grain miniaturization method of alloy, well-known, can implement following method: the combination of cold rolling and recrystallization, ECAP (isometrical corner extruding, EQual CHannel ANgular PRessing) method, high temperature chilling thermal treatments such as strong strain processing, liquid quench method such as ply rolling repeatedly, after mechanical workout, implement heat-treating methods.
But for the crystal grain miniaturization method of these methods of use, the crystallization particle diameter is about 1 μ m, and the raising of the crystal grain micronized effect more than this is limited.On the other hand, by inference,, be that the alloy of main composition key element can reach more high strength (Fig. 1) with the element a little less than the hydrogen avidity by the crystal grain miniaturization.
Method as the crystal grain miniaturization, for with the strong element of hydrogen avidity being Nd-Fe-B compounds magnetite, Ti-Al-V class alloy, Mg-Al class alloy of principal element etc., reported the thermal treatment (hydrogen absorbs rejected heat to be handled) that discharges hydrogen by implementing that described alloy is absorbed, the method for crystal grain being carried out miniaturization.But so far, for being the alloy of principal element with the element a little less than the hydrogen avidity, the validity of described method does not obtain confirming fully.
Summary of the invention
The problem that invention will solve
The purpose of this invention is to provide a kind of technology, this technology can make the alloy based on the element a little less than the hydrogen avidity comprise the strong element of hydrogen avidity, and performance crystal grain micronized effect.
The present inventor carries out various researchs for reaching described purpose, found that, when with T MDuring the fusing point of the metal that representative is represented with absolute temperature (or alloy), for being main composition composition and the alloy that comprises the strong element of hydrogen avidity with the element a little less than the hydrogen avidity, by at 0 ℃～0.8T MTemperature range in described alloy is placed in the nitrogen atmosphere, make described alloy absorpting hydrogen, contained strong element and the described absorbed H-H reaction of hydrogen avidity in the alloy.
Recognize in addition, at 0 ℃～0.8T MTemperature range in, make hydrogen from having absorbed hydrogen according to above-mentioned cognition and being to emit the alloy of main composition key element with the element a little less than the hydrogen avidity, can be below crystallization particle diameter miniaturization to the 1 μ m with described alloy.
That is, the absorption that can use described hydrogen discharges heat treated alloy type and is characterised in that, in the alloy based on the element a little less than the hydrogen avidity, comprises at least a above strong element of hydrogen avidity that is selected from the following elementary composition group: basic metal such as Li, Na; Alkaline-earth metal such as Mg, Ca; Rare earth metal such as La, Ce; With Ti, V etc. is the periodic table of elements 3～5 group 4 transition metals and the Pd of representative.
For the present invention, provide following manner.
[1] a kind of crystal grain miniaturization method of alloy is characterized in that, described alloy is to be the alloy of main composition key element with the element a little less than the hydrogen avidity, and comprises the strong element of hydrogen avidity, and described alloy is heat-treated, and this thermal treatment is included in 0 ℃～0.8T MTemperature range (T MThe fusing point of the metal or alloy that expression is represented with absolute temperature) makes described alloy absorpting hydrogen in, then at 0 ℃～0.8T MTemperature range in make described alloy discharge the step of hydrogen.
[2] as the crystal grain miniaturization method of above-mentioned [1] described alloy, it is characterized in that, the absorption that can use hydrogen discharges heat treated alloy type based on following alloy, described alloy comprises following elemental range: the weak element of hydrogen avidity is from being the element (still, except that the Pd element) of the periodic table of elements 6～10 families of representative with Cr, Mn, Fe, Co, Ni and being to select in the element of the periodic table of elements 11～15 families of representative with Cu, Ag, Au, Zn, Al.
[3] as the crystal grain miniaturization method of above-mentioned [1] or [2] described alloy, it is characterized in that the absorption that can use hydrogen discharges heat treated alloy type and comprises at least a above strong element of hydrogen avidity that is selected from the following elementary composition group: basic metal such as Li, Na; Alkaline-earth metal such as Mg, Ca; Rare earth metal such as La, Ce; With Ti, V etc. is the periodic table of elements 3～5 group 4 transition metals and the Pd of representative.
[4] a kind of crystal grain miniaturization alloy is characterized in that, this alloy is that the crystal grain miniaturization method of the described alloy in above-mentioned by implementing [1]～[3] obtains, and by this thermal treatment, the crystal grain of described alloy is by miniaturization.
The invention effect
The invention provides a kind of epoch-making method, for being the alloy of main component with the element a little less than the hydrogen avidity, this method absorbs the process that discharges hydrogen by making it, can reach the crystal grain of tens nanometer～1 that present method can not reach micron.By in processing of the present invention, the crystal grain of alloy can be carried out miniaturization, thereby can obtain high-intensity alloy material, obtain the improved alloy material of processibility.
According to following description, those skilled in the art can understand other purposes of the present invention, feature, superiority and institute and hold viewpoint.But, comprising that the record in this specification sheetss of record of following record and specific embodiment etc. is an optimal way of the present invention, these records just provide in order to describe.According to the knowledge of other parts of following record and this specification sheets, those skilled in the art know that and carry out various variations and/or change (or improvement) in disclosed in this manual the intent of the present invention and the scope.
Description of drawings
Fig. 1 illustrates by crystal grain miniaturization intensity and further strengthens for the correlogram of the crystallization particle diameter and the strength of materials.
Fig. 2 for show Al-7.8 weight %Mg alloy through hydrogen absorb handle after at the x-ray diffractogram of powder of the appearance phase of different treatment temperature.
Fig. 3 for show Al-7.8 weight %Mg alloy through hydrogen absorb handle after at the x-ray diffractogram of powder of the appearance phase of different treatment time.
Fig. 4 is the transmission microscopy photo of Al-7.8 weight %Mg alloy after hydrogen absorbs processing, wherein has fine MgH 2Phase.
Fig. 5 discharges the x-ray diffractogram of powder of the appearance phase in treatment time for showing Al-7.8 weight %Mg alloy in difference after hydrogen absorbs the release processing.
Fig. 6 is that Al-7.8 weight %Mg alloy absorbs the transmission microscopy photo that discharges after handling through hydrogen, and wherein, the alloy structure miniaturization is to about 10nm.
Fig. 7 absorbs the x-ray diffractogram of powder of the appearance phase after handling for showing Al-x weight %Mg alloy (x=3,5,7.8) through hydrogen.All composition all has MgH 2Occur mutually, illustrate that this treatment process is effective.
Fig. 8 shows that Fe-10 weight %V alloy is carried out hydrogen absorbs the V content of processing back parent phase for the different treatment variation of temperature.
Fig. 9 is for showing that Fe-10 weight %V alloy is carried out 250 ℃ of hydrogen absorbs transmission microscopy photos after handling, has the fine V precipitate that contains of about 10nm.
Before Figure 10 was the processing of Fe-10 weight %V alloy, hydrogen absorbed the x-ray diffractogram of powder after processing back and the hydrogen release processing.
Before Figure 11 was the processing of Cu-5 weight %Mg alloy, hydrogen absorbed the x-ray diffractogram of powder after processing back and the hydrogen release processing.
Embodiment
The invention provides a kind of technology, this technology is by to being that the alloy of main composition key element carries out hydrogen and handles with the element a little less than the hydrogen avidity, and the crystal grain of described alloy is carried out miniaturization.In this alloy junction crystal grain miniaturization technology, comprise that the crystallization particle diameter after the miniaturization is 10nm～1 μ m, be the crystal grain ultra micro refinement technology of 10nm～0.5 μ m in some cases.Further comprise the alloy type of this technology of being fit to, promptly the weak element of (A) (1) hydrogen avidity be main composition key element and (2) contain the alloy of the strong element of hydrogen avidity and (B) in the alloy type of described (A), have by this hydrogen absorb, hydrogen release is handled and the alloy of the crystallization particle diameter of miniaturization.This alloy junction crystal grain miniaturization technology also comprises following technology: performance is the characteristic that the alloy of main composition key element has with the element a little less than the hydrogen avidity, mix the strong element of hydrogen avidity, promptly select suitable combined amount, or select suitably should the blended metal species; Select the treatment condition that described hydrogen absorbs, hydrogen release is handled.Main points are, comprise that all are to the element a little less than the hydrogen avidity being the whole of alloy junction crystal grain miniaturization that the alloy of main composition key element the is used explanation in this manual scheme (technology, method etc.) that obtains desirable result.
The alloy absorpting hydrogen that makes the weak element simple substance of hydrogen avidity or only constitute with such element is difficult, still, by making it comprise for example strong element of hydrogen avidity more than the 0.1 weight %, then becomes the alloy that can absorb hydrogen.This alloy usually forms single sosoloid mutually or contain 2 above mutually mixed phase tissues of sosoloid.The invention provides a kind of technology that the crystal grain of alloy is carried out miniaturization, the element of described alloy a little less than with hydrogen avidity is the main composition key element.For being the alloy of main composition key element with the element a little less than the hydrogen avidity, make the strong element of hydrogen avidity and in described alloy, exist, the result, for being the alloy of the strong element of main composition key element and hydrogeneous avidity with the element a little less than the hydrogen avidity, by described alloy being carried out the thermal treatment that hydrogen absorb to discharge, can be with the crystal grain ultra micro refinement in the alloy, and can carry out super-strengthization etc., thereby, can improve the various character of described alloy.
As the element a little less than the hydrogen avidity, can from the group that the scope of following element is formed, select: be the element (still, except that the Pd element) of the periodic table of elements 6～10 families of representative and be the element of the periodic table of elements 11～15 families of representative with Cu, Ag, Au, Zn, Al with Cr, Mn, Fe, Co, Ni.The weak element of the hydrogen avidity of the described alloy of formation that is contained in this alloy can be a kind of, also can be two or more.
As the element of the periodic table of elements 6～10 families, can enumerate Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pt etc.As the element of the periodic table of elements 11～15 families, can enumerate Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi etc.Typically, from the aspect that utilizes as structured material, can enumerate following material, described material is to be selected from element in the following elementary composition group as main composition element: Cr, Mn, Fe, Co, Ni, Cu, Ag, Au, Zn, Al etc.Like this, can comprise Cr base alloy, Mn base alloy, Fe base alloy, Co base alloy, Ni base alloy, Cu base alloy, Zn base alloy, Al base alloy, Ag base alloy, Au base alloy, Ni-Cr base alloy, Ni-Co base alloy, Cr-Mn base alloy, Ni-Fe base alloy etc.
As the strong element of hydrogen avidity, can from the group of forming by the scope of following element, select: rare earth metals such as alkaline-earth metals such as basic metal such as Li, Na, Mg, Ca, La, Ce, be the periodic table of elements 3～5 group 4 transition metals and the Pd of representative with Ti, V etc.The element that hydrogen avidity is strong is blended in the alloy in order to be applicable to this alloy junction crystal grain miniaturization technology, and the strong element of this hydrogen avidity that contains in this alloy can be a kind of, also can be two or more.
As alkali metal, can enumerate Li, Na, K, Rb, Cs etc.As the alkaline-earth metal element, can enumerate Mg, Ca, Sr, Ba etc.As the periodic table of elements 3～5 group 4 transition metals, can enumerate Sc, Y, Ti, Zr, Hf, V, Nb, Ta, rare earth metal, cerium mischmetal etc.Rare earth metal comprises lanthanide series metal, actinide metals, as lanthanide series metal, can enumerate La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, can enumerate Ac, Th etc. as actinide metals.Typically, can from the metal that masterbatch is had no adverse effects, select, perhaps consider suitably to select low-cost metal, metal that the hydrogen affinity is high etc., preferably from for example by following elementary composition group selection: Li, Na, Mg, Ca, La, Ce, cerium mischmetal, Ti, V etc.
As long as the content of element in the alloy type that the present invention can be suitable for, that hydrogen avidity is strong is for just passable more than the 0.1 weight % of total amount.In some cases, the content of the element that described hydrogen avidity is strong can be 0.1 weight %～45 weight %, also can be 0.1 weight %～35 weight % in some cases, or 0.1 weight %～25 weight %, representative is to be 1 weight %～45 weight %, also can be 2 weight %～35 weight % in some cases, or 5 weight %～25 weight %, further be 4 weight %～25 weight %, also can be 5 weight %～20 weight % in some cases, or 5 weight %～15 weight % etc.This tittle is preferred, and this tittle can experimentize according to the record of this specification sheets and determine suitable, suitable value, also can change this tittle according to the object (element that hydrogen avidity is weak) of combination.
Desired purpose, effect or effect can be reached as long as can be suitable for alloy of the present invention, the element that is selected from the group of forming by the element B in the periodic table of elements, C, Si, N, P, As, O, S, Se, Te, F, C, B, I, Be can be comprised.When application the present invention can obtain the alloy of excellent rerum natura, the content of these elements was not particularly limited.
As mentioned above, for Nd-Fe-B compounds magnetite, Ti-Al-V class alloy, Mg-Al class alloy etc. based on the alloy of the strong element of hydrogen avidity or contain the strong intermetallic compound of a large amount of hydrogen avidity, though there is the well known examples of the miniaturization of the crystal grain that relates to the absorption method for releasing that utilizes hydrogen at present, but, also openly do not utilize the specific examples of the absorption method for releasing of hydrogen for alloy based on the element a little less than the hydrogen avidity.
This alloy junction crystal grain miniaturization technology comprises the processing that makes alloy absorpting hydrogen.In order to make described alloy absorpting hydrogen, alloy is placed under at least one nitrogen atmosphere more than the normal atmosphere, and at 0 ℃～0.8T MTemperature range in implement to handle.Preferably carry out in following temperature range, minimum temperature is to be that each alloy phase that is associated with the strong element of hydrogen avidity that contains in the alloy is taking place below the hydrogenant temperature under the hydrogen pressure that applies to have value regulation, top temperature that hydrogen absorbs the speed of response that can fully carry out.As the representational temperature range in this hydrogen absorption step, can enumerate 10 ℃～800 ℃, be 50 ℃～700 ℃ in some cases, or 100 ℃～600 ℃, or 200 ℃～500 ℃ etc., can certainly select suitable scope according to the composition of object alloy.Absorb the example of the temperature range of handling as suitable hydrogen, can enumerate 200 ℃～450 ℃, or 300 ℃～400 ℃ etc.
About described hydrogen, can under at least one nitrogen atmosphere more than the normal atmosphere, carry out hydrogen and absorb handle, but the pressure etc. that wraps hydrogenous atmosphere can usually be selected suitable value according to the strong unit of hydrogen avidity.For example, can adopt following condition: 0.1MPa～20MPa nitrogen atmosphere or 0.1MPa～10MPa nitrogen atmosphere, 0.1MPa～5MPa nitrogen atmosphere, 0.1MPa～1MPa nitrogen atmosphere, 0.2MPa～2MPa nitrogen atmosphere, 5MPa～10MPa nitrogen atmosphere also have preferred situation.
Absorb the time of handling as carrying out this hydrogen, as long as reach desired purpose, effect or effect, can select suitable, reasonable time, perhaps can be according to the object alloy type, select suitable, reasonable time, perhaps can select suitable, reasonable time according to as other conditions such as hydrogen-pressure, treatment temps.Consider that also economy, efficiency decide the treatment time, for example, can enumerate 0.1 hour～1 month, 0.5 hour～2 weeks in some cases, or 1 hour～1 week, preference is 1 hour～5 days or 1.5 hours～5 days, and representational example is 10 hours～120 hours or 15 hours～100 hours, 20 hours～75 hours etc.
Described alloy preferably carries out following chemical reaction: by absorbing hydrogen, part or all of the alloy phase that is associated with the strong element of hydrogen avidity forms hydride or hydrogen sosoloid mutually.
This alloy junction crystal grain miniaturization technology comprises the processing that hydrogen is discharged from the alloy that absorbs hydrogen.For example, below the thermodynamic(al)equilibrium pressure that continues, be under 1 condition below the normal atmosphere, in hydrogen-pressure if possible at 0 ℃～0.8T MTemperature range in, make the above-mentioned alloy that has absorbed hydrogen discharge hydrogen.Certainly, also can be at 200 ℃～0.8T MTemperature range in discharge hydrogen.If possible,, perhaps consider the growth of crystal grain, preferably under low temperature, discharge hydrogen as far as possible preferably to the atmosphere vacuum exhaust.
As mentioned above after the preparation, the alloy through absorb discharging hydrogen is preferred partly or entirely form once more with the hydrogen absorption reaction before same appearance mutually.
After the preparation,, in alloy, form hydride or hydrogen sosoloid phase as mentioned above by absorbing hydrogen and since after hydrogen release with the hydrogen absorption reaction before same appearance partly or entirely form once more mutually, thereby crystal grain by miniaturization below 1 μ m.By using technology of the present invention, the crystal grain miniaturization of alloy is arrived the degree of for example about 0.1 μ m of submicron order～0.2 μ m.In some cases, handle in the present invention resulting alloy for example the crystallization particle diameter after the miniaturization be 10nm～1 μ m.Perhaps, as resulting alloy, the crystallization particle diameter that for example can enumerate after the miniaturization is the alloy of 0.1 μ m～0.5 μ m.
Absorption rejected heat as hydrogen of the present invention is handled the alloy type that can be suitable for, and describes for representational example Al-Mg class alloy.In this Al-Mg class alloy, the combined amount of Mg sometimes also can about 3 weight % for for example being set at below the 10 weight %.Like this, the content of Mg is 0.1 weight %～10 weight %, is 3 weight %～8 weight % typically, also can be 3 weight %～5 weight % sometimes, or 2 weight %～4 weight % etc.
Similarly, in Fe-V class alloy, the combined amount of V can be about 5 weight % for for example being set at below the 15 weight % under other situations.Like this, the content of V is 0.1 weight %～15 weight %, is 3 weight %～10 weight % typically, also can be 4 weight %～10 weight % sometimes, or 4 weight %～6 weight % etc.
In addition, in Cu-Mg class alloy, the combined amount of Mg for example can be set at below the 10 weight %, can be about 6 weight % sometimes.Like this, the content of Mg is 0.1 weight %～10 weight %, is 3 weight %～8 weight % typically, also can be 3 weight %～6 weight % sometimes, or 4 weight %～5 weight % etc.
With alloy junction crystal grain footpath miniaturization technology of the present invention, the material that the crystallization particle diameter of alloy can be difficult to miniaturization carries out the miniaturization of crystallization particle diameter, maybe can be prepared into the crystallization particle diameter by the material of extreme miniaturization, can significantly improve mechanical properties, electromagnetic property, processibility and hydrogen and absorb release characteristics etc.In addition, utilization in the following areas is to expect for people: utilization is this feature of microfine, the material that will have described crystal grain through miniaturization is made the nanotechnology material, or utilize ultra micro refinement crystal grain itself, as utilizations such as coating particle, catalyst particle, electrode thin wire material, mixing element materials.In addition, can expect, be object with the near surface of powdered alloy, alloy, thin wire etc., uses alloy junction crystal grain footpath miniaturization technology of the present invention can significantly improve, improve aforesaid proterties, characteristic etc.
The mechanical properties of alloy (material) in this manual, processibility is meant, the mechanical response that described alloy material demonstrates, use described material to make the simplicity of goods, reliability, the degree of aesthetic property, for example comprise elastic limit, yielding stress, tensile strength, elongation, the cross section decrement, hardness, the shock resistance value, creep rate, safe range of stress etc. also can refer to thermotolerance, hot strength, erosion resistance, superhard property, anti-brittle fracture, resistance to fatigue, low temperature resistant fragility, superplasticity, weldability, weathering resistance, moldability, pattern, printing, anti-finger printing, oilness, cohesiveness, wear resistant, weather resistance, relate to the proterties that improves reliability of material.In addition, electromagnetic property can also comprise electrical conductivity, resistance characteristic, magnetic properties etc.In addition, hydrogen absorption release characteristics can also comprise hydrogen absorption or release rate, hydrogen absorption or release temperature, weather resistance etc.
In this manual, " periodic table of elements " be meant with 1989 international pure applied chemistry federation (International Union of Pure Applied Chemistry:IUPAC) the inorganic chemistry nomenclature correct and the periodic table of elements in the souvenir method that adopts.
Embodiment
Hereinafter, enumerate embodiment, specify the present invention, but described embodiment is for explanation of the present invention, and in order to provide with reference to its concrete mode.The scope of invention that these examples do not limit or limit in this application to be recorded and narrated.About the present invention, the various embodiments that are construed as based on the thought of this specification sheets all are possible.
Except that recording and narrating in detail in addition, whole embodiment is to use standard technique to implement, or can implement, this is that those skilled in the art is known commonly used.
Element a little less than selecting Al as hydrogen avidity, selection Mg for being the main Al-7.8 weight %Mg alloy of forming with Al, make powdered alloy as the strong element of hydrogen avidity.Under the nitrogen atmosphere of 7.5MPa, the hydrogen of in 250 ℃～450 ℃ temperature range resulting metal-powder being implemented 72 hours absorbs to be handled.The result who utilizes powder x-ray diffraction to measure the appearance phase of resulting alloy shown in Figure 2.Can see, provide Al-7.8 weight %Mg alloy, thereby generate MgH by nitrogen atmosphere to 300 ℃～400 ℃ temperature range 2Phase, the Mg of solid solution is hydrogenated to MgH 2, inhomogeneous Al and the MgH of turning to of alloy 2
Then, carrying out the hydrogen absorption processing that 350 ℃ of hydrogenant were implemented down 24 hours～72 hours, try to achieve Best Times.The result who utilizes powder x-ray diffraction to measure the appearance phase of resulting alloy shown in Figure 3.From the variation of the lattice parameter of the Al that causes by the increase time, the Mg content of Al sosoloid phase is also changing as can be seen.Particularly, handle,, can infer Mg amount (table 1) from the lattice parameter of Al alloy though the amount of the Mg in the Al-7.8 weight %Mg alloy has reduced by the nitrogen atmosphere more than 24 hours.
The variation and the Mg solid solution capacity of the lattice parameter of the Al in table 1 different hydro absorption treatment time
The lattice parameter of Al () Mg solid solution capacity (weight %)
Before the hydrogenation 4.0894 8.338
Hydrogenation in 24 hours 4.0615 2.663
Hydrogenation in 36 hours 4.0606 2.487
Hydrogenation in 72 hours 4.0607 2.505
350 ℃ shown in Figure 4,72 hours, the hydrogen of 7.5MPa absorb the transmission electron microscope picture after handling.By MgH 2The MgO that generates disperses mutually imperceptibly, and it is believed that the described MgH in the sample production process that electron microscope observation is used that is mutually 2Mutually oxidized and form.Therefore, MgH as can be known 2Be dispersed among the Al imperceptibly.
After hydrogen absorbs and handles,, carry out the release of the hydrogen in alloy and handle by 350 ℃, 30 minutes～5 hours vacuum exhaust.The result who utilizes powder x-ray diffraction to measure the appearance phase of resulting alloy shown in Figure 5.Can see, become mutually identical more than 2 hours with the appearance before hydrogen absorbs.
The transmission electron microscope picture of the alloy that described hydrogen release handles is implemented in the vacuum exhaust of passing through 350 ℃, 4 hours shown in Figure 6.Can see that the crystallization particle diameter of resulting alloy organizing is arrived tens nanometer by miniaturization.
As example of the present invention, provided at 350 ℃ of absorption hydrogen, at 350 ℃ of examples that discharge hydrogen, as long as but hydride is disperseed imperceptibly, and make hydrogen release under the low temperature as much as possible, crystal grain is further miniaturization just.
As the example of the minimum effective content of element a little less than the hydrogen avidity of the present invention, the hydrogen that has changed the Al-x weight %Mg alloy (x=3,5,7.8) of Mg amount shown in Figure 7 absorbs the x-ray diffractogram of powder after handling.Whole compositions all has MgH 2Occur mutually, even and in Al, have only the Mg of 3 weight %, it is effective also to demonstrate this treatment process.In addition, from the X-ray diffraction measurement result, by hydrogen release thermal treatment thereafter, the lattice parameter of alloy revert to the value before hydrogen is handled, and therefore as can be known, the Mg element of formation hydride solid solution once more becomes former alloy composition.As can be seen, even Mg is 3 weight %, the present invention is also effective.
Element a little less than selecting Fe as hydrogen avidity, selection V are as the strong element of hydrogen avidity, for with Fe being the main Fe-10 weight %V alloy of forming, under the nitrogen atmosphere of 7.5MPa, the hydrogen of implementing in 100 ℃～450 ℃ temperature range 72 hours absorbs to be handled, with this as hydrogen treatment of the present invention.The V content of the parent phase that the lattice parameter of measuring by the powder x-ray diffraction of resulting alloy shown in Figure 8 is calculated.By Fe-10 weight %V is provided in 250 ℃ nitrogen atmosphere alloy, compare with other treatment temps, the V content of parent phase significantly reduces as can be known.Hence one can see that handles by 250 ℃ hydrogen absorption, contains separating out from Fe-10 weight %V alloy phase of bigger than Fe atomic radius in a large number V.The hydrogen that utilizes shown in Figure 9 absorbs the transmission electron microscope picture of handling the alloy that obtains.Many than in the parent phase of the fine precipitate that has the about 10nm demonstrate white contrast as can be seen, the V that this precipitate comprises.
Before the processing shown in Figure 10 and after 250 ℃ hydrogen handles, and the result who implements to utilize the X-ray diffraction of the alloy that the hydrogen release of forced exhaust handles to measure afterwards.Lattice parameter before handling is 0.2876nm, but as shown in Figure 8, as can be seen, absorbs processing by hydrogen, and lattice parameter reduces, and handles by hydrogen release subsequently, resets into former lattice parameter 0.2876nm.This is an example, and this example explanation absorbs by hydrogen to be handled, and contains separating out mutually of the strong V element of a large amount of hydrogen avidity, and handles by hydrogen release subsequently, and described precipitated phase disappears, and can be recovered to former alloy composition.
Other the example of alloy as above-mentioned example, element a little less than selecting Cu as hydrogen avidity, selection Mg are as the strong element of hydrogen avidity, for with Cu as the main Cu-5 weight %Mg alloy of forming, before the processing shown in Figure 11, hydrogen absorbs the result that the X-ray diffraction after back, the hydrogen release is measured.Before processing, only observe Cu-5 weight %Mg phase, but after hydrogen absorbs processing, as can be seen, lattice parameter also newly occurred than this mutually little phase, handle by hydrogen release then, reset into former alloy phase.Therefore, for described alloy type, also can obtain taking place the example of same phase change.
By implementing the crystal grain miniaturization technology of alloy of the present invention, can be with the crystalline particle miniaturization of aluminium alloy to the submicron order of expecting as the practical alloy of light weight, for example about 0.1 μ m～10 μ m degree, or further about 0.05 μ m～1.0 μ m degree.In addition, by implementing the crystal grain miniaturization technology of alloy of the present invention, can be with the crystalline particle miniaturization of copper alloy to the submicron order of expecting as the practical alloy of function, for example about 0.1 μ m～10 μ m degree, perhaps further about 0.1 μ m～1.5 μ m degree.Similarly, by implementing the crystal grain miniaturization technology of alloy of the present invention, with the crystalline particle miniaturization of iron group alloy to the submicron order of expecting as steel, as various function alloys, superalloy, for example about 0.01 μ m～5 μ m degree, perhaps further about 0.01 μ m～0.2 μ m degree.
According to the present invention, the material that the crystallization particle diameter of alloy can be difficult to miniaturization carries out the crystal grain miniaturization, its result, therefore can significantly improve mechanical properties, electromagnetic property, processibility etc., can expect that effective realization is difficult to process at present, the utilization of material utilization etc., that application prospect is arranged.
Industrial applicibility
From lightweight, high mechanization, super-strength, attractive in appearance, viewpoint such as sense of touch is good, the exploitation of an urgent demand novel material, and from described viewpoint, for application prospect being arranged and because difficulty such as its manufacturing, processing and the alloy material that can not use and utilize, the miniaturization of the crystallization particle diameter by realizing alloy, can solve described problem, and expand the extensive use that alloy material is used.By the present invention, can improve with the element a little less than the hydrogen avidity is the mechanical properties, processibility etc. of the alloy of main composition key element, therefore can use in various application.
As can be seen, the present invention also can carry out beyond recording and narrating in aforesaid explanation and embodiment.In view of above-mentioned instruction, a lot of change of the present invention and distortion are possible, and therefore, these are also in the scope of the application's appended claims.

Claims (7)

1. the crystal grain miniaturization method of an alloy, it is characterized in that, the element of described alloy a little less than with hydrogen avidity is the main composition key element and comprises the strong element of hydrogen avidity, and described alloy is absorbed the thermal treatment that discharges hydrogen, and this thermal treatment is included in 0 ℃～0.8T MTemperature range in make described alloy absorpting hydrogen, then at 0 ℃～0.8T MTemperature range in make described alloy discharge the process of hydrogen, described T MThe fusing point of the metal or alloy that expression is represented with absolute temperature.
2. the crystal grain miniaturization method of alloy as claimed in claim 1, it is characterized in that, the absorption that is suitable for hydrogen discharges heat treated alloy type based on following alloy, and described alloy comprises following elemental range: the weak element of hydrogen avidity is from being the element of periodic table of elements representative, except that the Pd element 6～10 families with Cr, Mn, Fe, Co, Ni and being to select the element of the periodic table of elements 11～15 families of representative with Cu, Ag, Au, Zn, Al.
3. the crystal grain miniaturization method of alloy as claimed in claim 1 or 2, it is characterized in that the absorption that is suitable for hydrogen discharges heat treated alloy type and comprises at least a above strong element of hydrogen avidity that is selected from by in the following elementary composition group: basic metal such as Li, Na; Alkaline-earth metal such as Mg, Ca; Rare earth metal such as La, Ce; With Ti, V etc. is the periodic table of elements 3～5 group 4 transition metals and the Pd of representative.
4. crystal grain miniaturization alloy, the element of this alloy a little less than with hydrogen avidity is the main composition key element and comprises the strong element of hydrogen avidity, it is characterized in that, this alloy is to obtain by alloy being absorbed the thermal treatment that discharges hydrogen, and with this thermal treatment the crystal grain of described alloy has been carried out miniaturization, described thermal treatment is included in 0 ℃～0.8T MTemperature range in make described alloy absorpting hydrogen, then at 0 ℃～0.8T MTemperature range in make described alloy discharge the process of hydrogen, described T MThe fusing point of the metal or alloy that expression is represented with absolute temperature.
5. alloy as claimed in claim 4, it is characterized in that, the absorption that is suitable for hydrogen discharges heat treated alloy type based on following alloy, and described alloy comprises following elemental range: the weak element of hydrogen avidity is from being the element of periodic table of elements representative, except that the Pd element 6～10 families with Cr, Mn, Fe, Co, Ni and being to select the element of the periodic table of elements 11～15 families of representative with Cu, Ag, Au, Zn, Al.
6. as claim 4 or 5 described alloys, it is characterized in that the absorption that is suitable for hydrogen discharges heat treated alloy type and comprises at least a above strong element of hydrogen avidity that is selected from by in the following elementary composition group: basic metal such as Li, Na; Alkaline-earth metal such as Mg, Ca; Rare earth metal such as La, Ce; With Ti, V etc. is the periodic table of elements 3～5 group 4 transition metals and the Pd of representative.
7. as each described alloy in the claim 4～6, it is characterized in that the crystallization particle diameter after the miniaturization is 10nm～10 μ m.
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