A kind of method for preparing iron-base large-block amorphous alloy
Technical field
The present invention relates to a kind of method for preparing iron-base large-block amorphous alloy.
Background technology
Owing to the unique texture that non-crystaline amorphous metal had, have the characteristic of metal and glass concurrently, for example the corrosion resisting property of high-strong toughness, excellence and magnetic property etc. have caused extensive concern in material science.
Amorphous alloy is a metallic glass, has short range order, the unordered feature of long-range when solid-state, is a kind of metastable state structure, and its atom is topological disorder at three-dimensional space to be arranged, and keeps this state relatively stable at certain temperature range.The report of successfully preparing amorphous alloy the earliest is in 1934, adopts the method for hydatogenesis to obtain noncrystal membrane by Kramen.In the prior art, bulk amorphous alloys forms normally by the melt metal alloy is cooled to below the glass transition temp with speed of cooling faster, suppress the formation of nucleus and grow up in this process, directly solidifies to make.Human quick quenching techniques such as nineteen sixty Duwez have successfully prepared Au
75Si
25Band, speed of cooling reaches 10
5-10
6K/s indicates the startup of this novel material research field of non-crystaline amorphous metal.Because the restriction of rate of cooling, amorphous alloy can only be prepared into strip, filament or the fine powder of micro-meter scale always.1974, the Pd-Cu-Si alloy was with 10
3The rate of cooling of K/s can be made into the amorphous bar of 1mm size.The non-crystaline amorphous metal of mm size is commonly called large block amorphous, and the application space of amorphous has been expanded in its appearance, and how to prepare the large block amorphous hot issue that becomes.Early 1990s, T.Masumoto and A.Inoue etc. has found to have the multicomponent alloy series of extremely low critical cooling rate, cooperates the solidifying process of control heterogeneous nucleation, can directly obtain bulk amorphous alloys from liquid phase in the laboratory.1997, people such as the model deep blue of northeastern Japan university and Akihisa Inoue prepared the Pd of 50mm size under the condition of very low rate of cooling 0.1K/s
40Cu
30Ni
10P
20Amorphous.
High-energy ball milling is the solid-state synthetic method commonly used of the various materials of preparation, and the large-scale industrial application of machine-alloying starts from the sixties in 20th century.Machine-alloying obtains amorphous powder by mixing pure metal according to certain proportioning and it being carried out ball milling, and its shortcoming is the well living reaction of hybrid concurrency of alloy system that has, and therefore can not prepare with this method.Mechanochemical synthesis (Mechanochemical Synthesis, be called for short MS) adopts the amorphous powder that makes prealloy in advance, and the method that the prealloy amorphous powder is carried out mixing and ball milling has overcome the problem of machine-alloying again.MS is as a kind of promising method of the bulk iron-based amorphous alloy of preparation,, be particularly useful for preparing in a large number the amorphous nano-crystalline powder, its real application starts from the eighties in 20th century.It is 10mm that human amorphous powder compacting (hot pressing) methods such as J.Degmova are prepared diameter, and thickness is the Fe basic circle dish of 3mm.
Amorphous alloy can make in principle any isotropic phase alloy of composition, and wherein do not have dislocation, phase boundary with second mutually, it is the solid of no lattice defect, all fracture modes of being caused by dislocation can not take place in deformation process, therefore have excellent mechanical property and better solidity to corrosion and wear resistance.Owing to all comprise a large amount of noble metals or rare metal in most noncrystal substrates, the expensive prices of raw and semifnished materials make non-crystaline amorphous metal be difficult to obtain broad practice.The tool using value of Fe base noncrystal alloy wherein, because it is compared with other bulk amorphous alloys system, the prices of raw and semifnished materials reduce greatly, itself have high strength, high rigidity, high anti-corrosion, soft magnetism and higher thermostability preferably again.In recent years, the large block amorphous of FeCrMoCB series come out one after another, for example: Fe
50Cr
15Mo
14C
15B
6Block amorphous alloy can preparation size be the non-crystal bar of 1.5mm, Fe
48Cr
15Mo
14Er
2C
15B
6Block amorphous alloy can be prepared into the non-crystal bar that overall dimension is 9mm.The Fe elements atomic percentage is usually less than 50% when preparing iron-base large-block amorphous alloy in the prior art, and this has just increased raw-material price virtually.In addition purity of raw materials is required to require purity more than 99.9% usually than higher.The size that adopts the fast cold process of melt to prepare bulk amorphous alloys is subjected to the restriction of conditions such as rate of cooling.
Therefore the iron-base large-block amorphous alloy that adopts simple and easy to do preparation method to make excellent performance has become to solve the key of bulk amorphous alloys large-scale application.
Summary of the invention
The present invention provides a kind of easy preparation according to deficiency of the prior art, has good amorphous formation ability, the Fe-based bulk amorphous alloy material that mechanical property and thermal stability are good.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of method for preparing iron-base large-block amorphous alloy is characterized in that, comprises the steps:
A, obtain prealloy FeAlMP and FeCBSi with pure Fe, Al, P, C, Si, M and Fe-B alloy melting, wherein, M is any one in Ga, Cr, the Mo element;
B, prealloy FeAlMP and the FeCBSi that obtains put into ball mill respectively, adopt argon shield to carry out ball milling, clay into power;
C, above-mentioned two kinds of powder mixes that will obtain are put into ball mill, adopt argon shield to carry out ball milling, obtain the FeAlMCBPSi amorphous powder;
Admixture binding agent in the amorphous powder that d, step c obtain;
E, selection proper temperature are suppressed, and this temperature value should be in the amorphous glass invert point of selected component between the crystallization temperature; Pressure is greater than 100MPa.
Wherein, the amorphous glass invert point and the crystallization temperature of this component behind completing steps c, use dsc (DSC) to measure.
Wherein: the chemical formula of described iron-base large-block amorphous alloy is Fe
aAl
bM
cC
dB
eP
fSi
g, wherein a, b, c, d, e, f, g are the atom number, a: b: c: d: e: f: g=(65~80): (2~8): (0.5~5): (4~10): (0.9~8): (5~12): (0.4~3).
Wherein: among the step a, used material purity is more than 99.5%.
Wherein: among the step a, the FeAlMP of preparation and FeCBSi, atom number beguine is determined according to the alloying constituent that seeks out.
Wherein: among step b and the c, select the high-energy planetary ball mill machine of agate jar and abrading-ball for use.
Wherein: among the described step b, the ball material weight ratio during the FeAlMP ball milling is 20~30: 1, and the ball material weight ratio during the FeCBSi ball milling is 10~15: 1.
Wherein: among the described step b, the ball milling time is 10~15h, and rotational speed of ball-mill is 600~1000r/min.
Wherein: among the described step c, the ball material weight ratio during the compound ball milling is 20~30: 1, and rotational speed of ball-mill is 600~700r/min, and the ball milling time is 5~15h.
Wherein: in the steps d, binding agent is a water-soluble binder, is preferably Resins, epoxy or varnish.
Wherein: among the described step e, progressively be pressurized to earlier 100~400MPa pressure stable, be warmed up to the selected amorphous glass invert point (Tg) that is in then to the hot pressing temperature between the crystallization temperature (Tx), be incubated and drop to room temperature after 1~5.5 hour, pressurize to 100 again after the cooling~400MPa, kept 0.1~1.5 hour, and removed pressure then.
The principle of work of overall technical architecture of the present invention is: what alloy raw material adopted is FeAlMP and FeCBSi prealloy, and wherein M is any one in Ga, Cr, the Mo element, earlier prealloy is carried out ball milling, and it is large block amorphous to adopt hot pressing to obtain again.
Pure Fe, the Al, M, the P that adopt when preparing prealloy FeAlMP among the step a of the present invention, its purity is not less than 99.5%, and M is any one in Ga, Cr, the Mo element.Each element makes by vacuum melting furnace after being made into raw material by required atomic percent; The pure Fe that adopts when preparing prealloy FeCBSi among the step a of the present invention, the purity of C, Si are not less than 99.5%.Be made into raw material by required atomic percent, in vacuum melting furnace, make;
Among the step b, prealloy FeAlMP after the precrushing and FeCBSi are put into the high-energy planetary grinding machine respectively, adopt agate jar and abrading-ball, and adopt argon shield.Two kinds of prealloies adopt different material ball ratios, and the ball material weight ratio during ball milling FeAlMP is 20~30: 1, and the ball material weight ratio during ball milling FeCBSi is 10~15: 1.The ball milling time is 10~15h, and rotational speed of ball-mill is 600~1000r/min.The amorphous powder particle diameter that ball milling obtains is 10.2-13.5nm.This step it should be noted that in the mechanical milling process that choosing of ratio of grinding media to material value, ball milling time should be suitable.
Among the step c, the amorphous powder of step b gained is put into grinding machine according to a certain percentage, its concrete numerical value is decided on the designed large block amorphous ultimate constituent.Ball milling adopts agate jar and abrading-ball, and adopts argon shield.Ball material weight ratio is 20~30: 1, and rotational speed of ball-mill is 600~700r/min.The ball milling time is that to obtain particle diameter behind 5~15h be that the composition of 10.4-12.4nm is Fe
aAl
bM
cC
dB
eP
fSi
gAmorphous powder.This step it should be noted that in the mechanical milling process that choosing of ratio of grinding media to material value, ball milling time should be suitable, makes that amorphous powder is unlikely to be brought out crystallization in the mechanical milling process, thereby what guarantee to obtain at last is non-crystalline flour end;
The doping binding agent that uses in the steps d is preferably selected aqueous binders for use, because aqueous binders can well infilter between the powder, thereby it is very tight that powder bonded is got, and improves the sintered density of product, finally reduces the required pressure of follow-up sintering.Preferred binder is a Resins, epoxy;
Hot pressing temperature among the step e must be at amorphous glass invert point (T
g) to crystallization temperature (T
x) scope in, pressure is more than or equal to 100MP.
The existence of amorphous phase can be determined by X-ray diffraction method (XRD).Fully the feature of the X-ray diffractogram of non-crystaline amorphous metal is the diffraction peak with disperse of a broadening, and corresponding on the alloy diffracting spectrum of typical crystalline structure be sharp-pointed Bragg diffraction peak.
The thermodynamical coordinate of non-crystaline amorphous metal obtains by differential thermal analysis, is heated to the non-crystaline amorphous metal fusing with the heating rate of 20K/min.Record glass transition temp Tg, initial crystallization temperature Tx1.According to above calculation of parameter supercooling liquid phase region width Delta T=T
X1-T
g
Amorphous alloy material of the present invention has good soft magnetic performance.The coercive force of Fe base large amorphous alloy can be by the vibration magnetometer survey.
The glass transition temp of the non-crystaline amorphous metal of the present invention's preparation reaches more than the 750K, and initial crystallization temperature reaches more than the 790K, and the supercooling liquid phase region width Delta T is 30-42K.The non-crystaline amorphous metal that preparation is described has good amorphous formation ability.The coercive force of non-crystaline amorphous metal of the present invention is between 9.5-25A/m.The alloy that the present invention obtains has good mechanical performance and thermal property.
Description of drawings
Fig. 1 is the Fe of gained in the embodiments of the invention 1
72Al
5Ga
2C
6B
4P
10Si
1The X-ray diffractogram of bulk amorphous alloys.
Embodiment
Embodiment 1
Purity is not less than 99.5% pure Fe, Al, Ga, P and is made into raw material, in vacuum melting furnace, make prealloy Fe by required atomic percent
66Al
10Ga
4P
20The Fe-B alloy that purity is not less than 99.5% pure Fe, C, Si and industrial use is made into raw material by required atomic percent, makes prealloy Fe in vacuum melting furnace
78C
12B
8Si
2With the prealloy Fe after the precrushing
66Al
10Ga
4P
20Put into the high-energy planetary ball mill machine, ball material weight ratio is 25: 1, and rotational speed of ball-mill is 700r/min, and the ball milling time is 10 hours, adopts argon shield to carry out ball milling.With the prealloy Fe after the precrushing
78C
12B
8Si
2Put into the high-energy planetary ball mill machine, ball material weight ratio is 15: 1, and rotational speed of ball-mill is 700r/min, and the ball milling time is 10 hours, adopts argon shield to carry out ball milling.After two kinds of amorphous powders that obtain are mixed, put into the high-energy planetary ball mill machine, ball material weight ratio is 20: 1, and rotational speed of ball-mill is 600r/min, and obtaining the composition that particle diameter is about 12.4nm behind the ball milling time 12h is Fe
72Al
5Ga
2C
6B
4P
10Si
1Amorphous powder.To the amorphous powder that obtains a small amount of Resins, epoxy that mixes, it is very tight that powder bonded is got, and improves the sintered density of product.At temperature 770K, suppress obtaining diameter 10mm under the pressure 200MPa, the large block amorphous disk of thickness 3mm.As can be seen from Figure 1, behind the ball milling 12h, a roomy diffuse peaks occurred, and the Bragg diffraction peak of crystalline state do not occurred characterizing, proved that prepared sample is a non-crystalline state.Can measure the glass transition temp (T of non-crystaline amorphous metal from the DSC curve
g) be 754K, initial crystallization temperature (T
X1) be 791K, supercooling liquid phase region width (Δ T) is 37K, coercive force is 9.5A/m.
Embodiment 2
Prepare earlier FeAlMP and FeCBSi respectively, and with they difference ball millings, ball material weight ratio during the FeAlMP ball milling is 20: 1, ball material weight ratio during the FeCBSi ball milling is 10: 1, again with FeAlMP and FeCBSi mixing and ball milling, and ball material weight ratio 20: 1, rotational speed of ball-mill is 600r/min, the ball milling time is 5h, and all the other steps are identical with embodiment 1, and prepared composition is Fe
68.3Al
2.1Cr
4.7C
6.9B
6.7P
8.8Si
2.5Bulk amorphous alloys, this alloy is to have replaced the Ga in the alloy with Cr to obtain.Hot pressing temperature is 815K, and pressure is 100MPa.Can be prepared as diameter 10mm with embodiment 1 described technical scheme, thickness is the large block amorphous disk of 4mm.Glass transition temp (the T of this alloy
g) be 795K, initial crystallization temperature (T
X1) be 835K, supercooling liquid phase region width (Δ T) is 40K, coercive force is 12.4A/m.
Embodiment 3
Prepare earlier FeAlMP and FeCBSi respectively, and with they difference ball millings, ball material weight ratio during the FeAlMP ball milling is 30: 1, ball material weight ratio during the FeCBSi ball milling is 20: 1, again with FeAlMP and FeCBSi mixing and ball milling, and ball material weight ratio 30: 1, rotational speed of ball-mill is 650r/min, the ball milling time is 15h, and all the other steps are identical with embodiment 1, and prepared composition is Fe
77Al
2.1Ga
0.9C
5B
4P
8.4Si
2.6Bulk amorphous alloys.Hot pressing temperature is 785K, and pressure is 100MPa.Can be prepared as diameter 10mm with embodiment 1 described technical scheme, thickness is the large block amorphous disk of 4mm, the glass transition temp (T of this alloy
g) be 779K, initial crystallization temperature (T
X1) be 814K, supercooling liquid phase region width (Δ T) is 35K, coercive force is 10.8A/m.
Embodiment 4
Prepare earlier FeAlMP and FeCBSi respectively, and with they difference ball millings, ball material weight ratio during the FeAlMP ball milling is 22: 1, ball material weight ratio during the FeCBSi ball milling is 12: 1, again with FeAlMP and FeCBSi mixing and ball milling, and ball material weight ratio 26: 1, rotational speed of ball-mill is 650r/min, the ball milling time is 10h, and all the other steps are identical with embodiment 1, and prepared composition is Fe
68.3Al
2.1Mo
4.7C
6.9B
6.7P
8.8Si
2.5Bulk amorphous alloys.This alloy substitutes Ga with metal M o and makes.Hot pressing temperature is 800K, and pressure is 100MPa.Can be prepared as diameter 10mm with embodiment 1 described technical scheme, thickness is the large block amorphous disk of 4mm, the glass transition temp (T of this alloy
g) be 782K, initial crystallization temperature (T
X1) be 821K, supercooling liquid phase region width (Δ T) is 39K, coercive force is 16.3A/m.
Embodiment 5
Prepare earlier FeAlMP and FeCBSi respectively, and with they difference ball millings, ball material weight ratio during the FeAlMP ball milling is 27: 1, ball material weight ratio during the FeCBSi ball milling is 13: 1, again with FeAlMP and FeCBSi mixing and ball milling, and ball material weight ratio 23: 1, rotational speed of ball-mill is 700r/min, the ball milling time is 8h, and all the other steps are identical with embodiment 1, and prepared composition is Fe
65.5Al
7.9Cr
3.9C
9.4B
0.9P
11.8Si
0.6Bulk amorphous alloys.This alloy substitutes Ga with Metal Cr and makes.Hot pressing temperature is 780K, and pressure is 100MPa.Can be prepared as diameter 10mm with embodiment 1 described technical scheme, thickness is the large block amorphous disk of 4mm, the glass transition temp (T of this alloy
g) be 762K, initial crystallization temperature (T
X1) be 798K, supercooling liquid phase region width (Δ T) is 36K, coercive force is 24.7A/m.
Embodiment 6
Prepare earlier FeAlMP and FeCBSi respectively, and with they difference ball millings, ball material weight ratio during the FeAlMP ball milling is 23: 1, ball material weight ratio during the FeCBSi ball milling is 17: 1, again with FeAlMP and FeCBSi mixing and ball milling, and ball material weight ratio 27: 1, rotational speed of ball-mill is 630r/min, the ball milling time is 12h, and all the other steps are identical with embodiment 1, and prepared composition is Fe
79.2Al
3.4Mo
0.5C
4.0B
7.2P
5.3Si
0.4Bulk amorphous alloys.This alloy substitutes Ga with metal M o and makes.Hot pressing temperature is 790K, and pressure is 100MPa.Can be prepared as diameter 10mm with embodiment 1 described technical scheme, thickness is the large block amorphous disk of 4mm, the glass transition temp (T of this alloy
g) be 786K, initial crystallization temperature (T
X1) be 818K, supercooling liquid phase region width (Δ T) is 32K, coercive force is 13.3A/m.
Resins, epoxy among the present invention can replace with varnish.
Non-crystaline amorphous metal chemical composition and the thermodynamics and the coercive force parameter list of embodiment 1-6 preparation
Chemical ingredients (at%) |
T
g(K)
|
T
x(K)
|
ΔT(K) |
H
c(A/m)
|
Fe
72Al
5Ga
2C
6B
4P
10Si
1 |
754 |
791 |
37 |
9.5 |
Fe
68.3Al
2.1Cr
4.7C
6.9B
6.7P
8.8Si
2.5 |
795 |
835 |
40 |
12.4 |
Fe
77Al
2.1Ga
0.9C
5B
4P
8.4Si
2.6 |
779 |
814 |
35 |
10.8 |
Fe
68.3Al
2.1Mo
4.7C
6.9B
6.7P
8.8Si
2.5 |
782 |
821 |
39 |
16.3 |
Fe
65.5Al
7.9Cr
3.9C
9.4B
0.9P
11.8Si
0.6 |
762 |
798 |
36 |
24.7 |
Fe
79.2Al
3.4Mo
0.5C
4.0B
7.2P
5.3Si
0.4 |
786 |
818 |
32 |
13.3 |
The foregoing description only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other substantial equivalence means that it may occur to persons skilled in the art that are all in claim scope of the present invention.