CN102418053A - Zr-Cu-Ni-Al amorphous alloy containing trace boron and preparation method thereof - Google Patents
Zr-Cu-Ni-Al amorphous alloy containing trace boron and preparation method thereof Download PDFInfo
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- CN102418053A CN102418053A CN2011104070029A CN201110407002A CN102418053A CN 102418053 A CN102418053 A CN 102418053A CN 2011104070029 A CN2011104070029 A CN 2011104070029A CN 201110407002 A CN201110407002 A CN 201110407002A CN 102418053 A CN102418053 A CN 102418053A
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Abstract
The invention provides a Zr-Cu-Ni-Al amorphous alloy containing trace boron and a preparation method thereof. The composition expression of the amorphous alloy is ZraCubAlcNidBe, wherein a, b, c, d and e are respectively the percentage of each element atom in the alloy, a is 50%, b is 24-30%, c is 10%, d is 10% e is 0-6% and a+b+c+d+e is 100%. The preparation method of the amorphous alloy comprises the steps of: carrying out arc melting on a high-purity metal material of each element into master alloy, cutting the master alloy into a master alloy sample with the volume weight required by a copper mold, then cleaning the master alloy sample, placing the master alloy sample in a suction casting crucible, melting the master alloy sample, then sucking to the copper mold, introducing air, and finally dismounting the copper mold. The obtained amorphous alloy has low cooling rate, large size, high hardness, good heat stability, wider supercooling liquid phase region and good amorphous forming capability.
Description
Technical field
The invention belongs to the non-crystaline amorphous metal field, particularly a kind of Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B and preparation method thereof.
Background technology
Non-crystaline amorphous metal is meant that the three-dimensional space of its atom is that topological disorder is arranged when solid-state, and in certain temperature range, keeps the metastable alloy of this state, claims metallic glass (Metallic Glass) again.Because ultra quench solidification, atom has little time the ordered arrangement crystallization during alloy graining, does not have the existence of crystal grain, crystal boundary and the dislocation defects of crystal alloy, thereby demonstrates excellent comprehensive physics, chemistry and mechanical property.Metal that people use the earliest and alloy all are crystalline material, and nineteen thirty-seven roentgen Kramer utilizes evaporation deposition method at first to prepare non-crystalline state Sb film, and nineteen fifty Brenner etc. has prepared the Ni-P amorphous alloy with electrodip process.In the latter stage fifties, professor Turnbull of Harvard University proposes to utilize the method for melt high undercooling to prepare the imagination of amorphous alloy first.At the beginning of the sixties, professor Duwez of California Inst Tech USA has invented spray gun and piston apparatus, and uses sloppy heat body quench (cold scooter 105K/s) to make the Au75Si25 thin film of amorphous alloy first.From then on amorphous alloy has caused people's extensive concern; From the beginning of the sixties to the end of the eighties in nearly 30 years time; Owing to restricted by rate of cooling; The amorphous alloy of preparation only is limited to strip, filament or Powdered, thereby has limited the application of amorphous alloy, particularly as the application of structural timber.1974, Chen utilized vacuum suction casting technique to prepare Pd-Cu-Si ternary non-crystaline amorphous metal, and size reaches the millimeter level, and critical cooling rate is lower than 103K/s.From then on bulk amorphous alloy (the Bulk Metallic Glass) epoch arrive, and so-called block amorphous alloy is meant the amorphous alloy with higher amorphous formation ability (GFA) and low critical cooling rate Rc, and its three-dimensional space size is all greater than 1mm.Nineteen eighty-two, Turnbull utilizes the boron oxide pack to avoid heterogeneous forming core, successfully prepares the Pd-Ni-P block amorphous alloy that diameter reaches 10mm, and critical cooling rate is in the 10K/s scope, but the block amorphous alloy of preparation only limits to precious metal systems such as Pd.In the latter stage eighties, the Inoue of Japan has broken through the restriction of cooling rate through the method for multicomponent alloyization, prepares the block amorphous alloy of being made up of base metal (as: La-Al-Ni and La-Al-Cu [10]).The Johnson of the U.S. in 1993 successfully prepares the very big Zr-Ti-Cu-Ni-Be block amorphous alloy of glass forming ability, and critical size reaches 14mm.Professor Inoue utilizes water quenching to prepare the Pd-Ni-Cu-P block amorphous alloy of critical diameter for 72mm subsequently, and critical cooling rate reaches 0.1K/s.From then on block amorphous alloy enjoys the concern of field of materials and Condensed Matter Physics area research, and the high undercooling block amorphous alloy of many novel alloys is produced out, as: Ti base, Hf base, Fe base, Pd-Fe base, Co base, Cu base, Zr base etc.The research of aspects such as formation ability, structure, performance, stability and the application of block amorphous alloy has all obtained remarkable progress.
After Inoue etc. summed up three principles obtaining block amorphous alloy, the preparation of block amorphous alloy and performance study thereof had had breakthrough progress.Bulk amorphous alloys is when cooling, and the reason that forming core takes place mainly contains three: the impurity that (1) is brought into from starting material is as the core of heterogeneous body forming core; (2) the alloy oxide inclusion that in melting and casting process, reacts and form with on every side oxidizing atmosphere; (3) speed of cooling causes the formation of nascent nucleus and even crystal grain inadequately greatly.Therefore, in the preparation process of bulk amorphous alloys, key is in process of cooling, to suppress the heterogeneous body forming core of alloy and improve speed of cooling as much as possible to reduce the incubation time of homogeneous nucleus.In order to reduce non-crystaline amorphous metal generation forming core, to carry out strict protection of inert gas to the melting of metal.The impurity in the melt and the internal surface of container can play the effect of heterogeneous body forming core, so purification and slag making during melting are also very important.The principle of the alloy system of the amorphous formation ability that the acquisition that proposes according to Inoue is high, the decision amorphous formation ability will mainly be the composition of alloy.Through selecting suitable alloy system, under low rate of cooling, can obtain amorphous alloy.But, select suitable preparation method will obtain the bigger sample of size for same alloy system.
At present, the preparation method of bulk amorphous alloys can be divided into direct freezing method and powder consolidation moulding method.Directly freezing method mainly comprises: water quenching, copper mold casting method sucks casting, PM technique, argon arc stove smelting process, unidirectional method of fusion etc.
Water quenching is that the batching with bulk amorphous alloys is sealed in the evacuated silica tube, and the shrend cooling of heating back obtains bulk amorphous alloys.If form by HMP in the alloy, be encapsulated in the silica tube again after can batch mixing is processed alloy in the argon arc stove earlier.The advantage of this method is that facility investment is little, and the department of encapsulation silica tube is easy to find, and the larger-size cylindrical large block amorphous rod that is easy to get.Shortcoming be amorphous sample of every preparation must front cover time silica tube, and silica tube will be destroyed when quenching.
Argon arc stove smelting process is to utilize the argon arc stove directly to refine amorphous product after each component is mixed.This method can only be refined the less amorphous sample of size, and the shape of amorphous sample is generally the button shape, is difficult for machine-shaping.This method requires height to the amorphous formation ability of alloy system in addition, otherwise the heart portion of sample or sample can not form amorphous, and the bottom that sample and crucible directly contact is fusing fully sometimes, can become crystallization phases and the core that becomes, and also is prone to crystallization phases.
Powder metallurgic method utilizes non-crystalline solids at supercooling liquid phase region Δ T
xThe characteristic that interior virtual viscosity descends significantly applies certain pressure and makes material that even rheology take place, thus compound be block.With the bulk amorphous alloys that powder metallurgy is prepared, not only to satisfy closely knitly, and to avoid crystallization.The block materials of institute's control equipment is very limited at aspects such as purity, density, size and shapings.
Summary of the invention
For solving the problems of the technologies described above, the present invention provides a kind of Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B and preparation method thereof, and its non-crystaline amorphous metal rate of cooling is low; Size is big, and hardness is high, Heat stability is good; Supercooling liquid phase region with broad, amorphous formation ability is good.
Technical scheme of the present invention is: a kind of Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B, and its composition expression formula is ZraCubAlcNidBe, said a, b; C, d, e are the shared per-cent of each element atom in the alloy; A=50% wherein, b=24 ~ 30%, c=10%; D=10%, e=0 ~ 6%, a+b+c+d+e=100%.
The preferred version of the Zr-Cu-Ni-Al non-crystaline amorphous metal of above-mentioned interpolation trace B is: a=50%, and b=28%, and c=10%, and d=10%, e=2%.
The preferred version of the Zr-Cu-Ni-Al non-crystaline amorphous metal of above-mentioned interpolation trace B is: a=50%, and b=26%, and c=10%, and d=10%, e=4%.
The preferred version of the Zr-Cu-Ni-Al non-crystaline amorphous metal of above-mentioned interpolation trace B is: a=50%, and b=24%, and c=10%, and d=10%, e=6%.
A kind of preparation method of Zr-Cu-Ni-Al non-crystaline amorphous metal of above-mentioned interpolation trace B; Its step is following: high purity metal material arc melting under the argon gas atmosphere of process titanium purifying of Zr, Cu, Ni, Al element is become mother alloy; Cut into the required volume weight of copper mold to mother alloy with wire electric discharge then, put into the beaker of containing 97% alcohol behind the well cutting and put into the ultrasonic cleaning instrument and clean, the mother alloy sample after cleaning is placed in the crucible of inhaling casting; Repeat the step of front; To the mother alloy sample melted, it is sucked in the copper mold, charge into air, open the fire door cleaning crucible; At last copper mold is unloaded, promptly get the Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B in the copper mold.
Beneficial effect of the present invention is: the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B provided by the invention has that its non-crystaline amorphous metal rate of cooling is low, and size is big, and hardness is high; Heat stability is good; Supercooling liquid phase region with broad, its preparation method combines arc melting alloy technology and copper mold foundry engieering together, has both utilized the advantage of pollution-free, the good uniformity of arc melting alloy; Utilized again and inhaled the technological melt filling process of casting number; The fast cooling strong point of copper mold, particularly this technology make alloy melting, fill type, process of setting and in vacuum chamber, accomplish through once vacuumizing, belong to a kind of short process making method.
The copper mold casting method that the present invention adopts is provided with a water cooled copper mould below heating unit, get into water cooled copper mould cooling formation amorphous by inhaling casting or additive method after the fusing of non-crystaline amorphous metal component.Though this method requires to have special equipment, because cooling rate prepares the amorphous sample of large-size than high energy, and available different dies prepares difform amorphous sample, also can prepare complex-shaped amorphous sample.Copper mold casting method especially has absorbing and casting device, owing to there being these advantages to be widely used.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of non-crystaline amorphous metal among each embodiment.
Fig. 2 is the shear zone pattern of embodiment 1 said alloy.
Fig. 3 is the shear zone pattern of embodiment 2 said alloys.
Fig. 4 is the shear zone pattern of embodiment 3 said alloys.
Fig. 5 is the stress-strain curves figure in non-crystaline amorphous metal when compression of each embodiment.
Embodiment
Embodiment 1
A kind of Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B, its composition expression formula is: Zr
aCu
bAl
cNi
dB
e, a wherein, b, c; D, e are atomic percent, and a=50%, and b=28%; C=10%, and d=10%, e=2%, a+b+c+d+e=100%; Its x-ray diffraction pattern is shown in the waveform of going up most among Fig. 1, and its shear zone pattern is as shown in Figure 2, and the stress-strain curves during compression is shown in 3 line styles of mark among Fig. 5.Its preparation method is following: bar, block or the frit materials of getting pure metal Zr, Cu, Ni, Al element with above-mentioned atomic percent, and arc melting under through the argon gas atmosphere of titanium purifying at first, alloy needs melt back for several times to guarantee the homogeneity of composition.Cut the demand that mother alloy satisfies the required volume weight of different moulds with wire electric discharge again, put into the beaker of containing 97% alcohol to the material of well cutting, put into the ultrasonic cleaning instrument together and cleaned 1 minute.Mother alloy sample after cleaning is placed in the crucible of inhaling casting, repeats the step of front, after the mother alloy sample melted,, it is sucked in the mould by inhaling the casting button.Charge into air then, open the fire door cleaning crucible, copper mold (mould specification is Φ 5*75mm) is unloaded, take out the Zr-Cu-Ni-Al non-crystaline amorphous metal of the interpolation trace B in the copper mold.Cool off with the rate of cooling greater than 100 ℃/second after the mother alloy sample melted, can form amorphous material, the percent by volume of amorphous phase is no less than 50%.
Embodiment 2
The difference of present embodiment and embodiment 1 only is that a=50%, and b=26%, and c=10%, and d=10%, e=4%.Its x-ray diffraction pattern is shown in Fig. 1 intermediary waveform, and its shear zone pattern is as shown in Figure 3, and the stress-strain curves during compression is shown in 4 line styles of mark among Fig. 5.Its preparation method is identical with embodiment 1.
The difference of present embodiment and embodiment 1 only is that a=50%, and b=24%, and c=10%, and d=10%, e=6%, a+b+c+d+e=100%.Its x-ray diffraction pattern is shown in the waveform of Fig. 1 foot, and its shear zone pattern is as shown in Figure 4, and the stress-strain curves during compression is shown in 2 line styles of mark among Fig. 5.Its preparation method is identical with embodiment 1.
Allow to have small amount of impurities in the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B provided by the invention, like oxygen, nitrogen, phosphorus etc., impurity element mainly comes from atmosphere in starting raw material, the alloy smelting process, foreign matter etc.Some element that occupies than small proportion may exert an influence to the amorphous alloy performance; Like oxygen level the alloy glass forming ability there is considerable influence; It is very active element that the present invention provides the principal element Zr of alloy, has very strong avidity with gaseous impurities elements such as oxygen, therefore; The existence of a spot of oxide compound can guarantee that still alloy has glass forming ability preferably, but oxygen level should not surpass 0.1% (weight ratio) in the alloy.
Claims (6)
1.1 a Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B is characterized in that: its composition expression formula is Zr
aCu
bAl
cNi
dB
e, said a, b, c, d, e are the shared per-cent of each element atom in the alloy, a=50% wherein, b=24 ~ 30%, c=10%, d=10%, e=0 ~ 6%, a+b+c+d+e=100%.
2. the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 1 is characterized in that: a=50%, and b=28%, and c=10%, and d=10%, e=2%.
3. the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 1 is characterized in that: a=50%, and b=26%, and c=10%, and d=10%, e=4%.
4. the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 1 is characterized in that: a=50%, and b=24%, and c=10%, and d=10%, e=6%.
5. the preparation method of the Zr-Cu-Ni-Al non-crystaline amorphous metal of the said interpolation trace B of claim 1; Its step is following: the high purity metal material of Zr, Cu, Ni, Al element arc melting under through the argon gas atmosphere of titanium purifying is become mother alloy, cut into the required volume weight of copper mold to mother alloy with wire electric discharge, put into the beaker of Sheng 97% alcohol behind the well cutting and clean at the ultrasonic cleaning instrument; Mother alloy sample after cleaning is placed in the crucible of inhaling casting; To the mother alloy sample melted, it is sucked in the copper mold, charge into air, open the fire door cleaning crucible; At last copper mold is unloaded, promptly get the Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B in the copper mold.
6. the preparation method of the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 5 is characterized in that: cool off with the rate of cooling greater than 100 ℃/second after the said mother alloy sample melted.
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| CN104498844A (en) * | 2014-11-18 | 2015-04-08 | 北京科技大学 | Heavy size TRIP amorphous composite material and preparation method thereof |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN114438424A (en) * | 2022-02-18 | 2022-05-06 | 山东大学深圳研究院 | In-situ synthesized B2-phase-enhanced TiCuZrPdCo amorphous composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104498844A (en) * | 2014-11-18 | 2015-04-08 | 北京科技大学 | Heavy size TRIP amorphous composite material and preparation method thereof |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN114438424A (en) * | 2022-02-18 | 2022-05-06 | 山东大学深圳研究院 | In-situ synthesized B2-phase-enhanced TiCuZrPdCo amorphous composite material and preparation method thereof |
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Application publication date: 20120418 |