CN102162076B - Method for improving plasticity of bulk metal glass and structural component thereof - Google Patents

Method for improving plasticity of bulk metal glass and structural component thereof Download PDF

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CN102162076B
CN102162076B CN 201110068749 CN201110068749A CN102162076B CN 102162076 B CN102162076 B CN 102162076B CN 201110068749 CN201110068749 CN 201110068749 CN 201110068749 A CN201110068749 A CN 201110068749A CN 102162076 B CN102162076 B CN 102162076B
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metal glass
block metal
plasticity
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glass
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杜宇雷
许宏伟
陈�光
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Nanjing University of Science and Technology
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Abstract

The invention discloses a method for improving plasticity of a bulk metal glass and a structural component thereof. The plasticity of the bulk metal glass and the structural component thereof is improved by using a vapor hydrogenation treatment method. The method comprises the following steps of: 1, selecting components of master alloy matrix, and performing non-consumable arc melting on the components to obtain a master alloy ingot; 2, crushing the master alloy ingot in a container, and performing re-melting and blowing casting to form the bulk metal glass; and 3, performing vapor hydrogenation treatment on the bulk metal glass or the bulk metal glass structural component prepared in the second step. The plasticity of the bulk metal glass and the structural component thereof treated by the method is improved, the bulk metal glass still keeps a glass state structure, and the original thermal stability and the original yield strength of the bulk metal glass are not reduced.

Description

A kind of method that improves block metal glass and structural part plasticity thereof
Technical field
The present invention relates to a kind of method that improves block metal glass and structural part plasticity thereof, particularly a kind of method of utilizing the vapour phase hydrogenation method to improve block metal glass and structural part plasticity thereof.
Background technology
Since the eighties in last century, block metal glass becomes focus and the advanced problems of international research with its excellent mechanical property.Yet the pure amorphous block metallic glass overwhelming majority shows as brittleness at room temperature, has limited greatly the application of block metal glass on engineering.For this solution of problem, mainly adopt in the world at present the method for introducing second-phase at the block metal glass matrix, form bulk metal glass composite material, the plasticity pure amorphous block metallic glass before of block metal glass is improved largely, and two kinds of main technological methods are thought of a way and outer addition in being.Chen Guang etc. have invented the method (patent No.: CN100494437C) of dentrite nodularization in a kind of bulk metallic glass composite, prepare plasticity dentrite/bulk metallic glass composite plate tensile sample by low-pressure casting/water cooled copper mould chilling formation system, again with plasticity dentrite/bulk metallic glass composite plate tensile sample isothermal processes, then shrend, prepare a kind of interior living plasticity spherocrystal phase bulk metal glass composite material, can significantly improve macroscopical plasticity of block metal glass.Jonhson etc. in the block metal glass matrix by adding the continuous fibre wild phase, adopt infiltration casting to prepare continuous fibre Zirconium-based block metal glass matrix material, compression plasticity significantly improves [R. D. Conner, R. B. Dandliker, W. L. Johnson.Acta.Mater.46.6089 (1998)].The method of the raising block metal glass plasticity of above-mentioned report, all be by having changed the internal structure of block metal glass, can't guarantee that the block metal glass of preparing is full non-crystalline state, reduced so to a certain extent the intensity of block metal glass, the performance such as wear resistance and erosion resistance, and in the think of a way interfacial energy of the bulk metal glass composite material wild phase prepared and matrix relatively low, thereby so that its yield strength is lower; The distribution of the bulk metal glass composite material wild phase that the method for adding is prepared is difficult to control, and the interfacial energy of wild phase and matrix is very high, in that surface reaction formation fragility phase occurs at the interface, is unfavorable for the raising of block metal glass mechanical property.In addition, two kinds of above-mentioned methods all are to improve plasticity, the raising of the block metal glass structural part plasticity of moulding of very difficult solution by changing the intrinsic performance of material.Improve the technological method of block metal glass although invented some at present, and the block metal glass of preparing has certain mechanical property, but this can not satisfy people far away to its demand, therefore, the development of novel raising block metal glass plastic method and exploitation have been imperative.
Summary of the invention
The object of the present invention is to provide a kind of method that improves block metal glass and structural part plasticity thereof, a kind of new approaches that improve block metal glass and various size structural part plasticity thereof are provided.
The technical solution that realizes the object of the invention is: a kind of method that improves block metal glass and structural part plasticity thereof, the method for utilizing vapour phase hydrogenation to process improves the plasticity of block metal glass and structural part thereof.
The present invention compared with prior art, its remarkable advantage: the element such as the Zr in the block metal glass, Ti and hydrogen have the elements such as stronger avidity and Ni that the absorption of hydrogen is had katalysis, there are a large amount of tetrahedral interstices that exist energy state different in a large amount of free volumes, the shot-range ordered structure in the block metal glass simultaneously, are conducive to occupying of hydrogen.(1) both can carry out vapour phase hydrogenation to bulk metallic glass materials among the present invention and process, also can carry out to the block metal glass structural part of arbitrary shape vapour phase hydrogenation and process.(2) by being carried out vapour phase hydrogenation, block metal glass processes to improve its plasticity.(3) block metal glass still keeps glassy structure after vapour phase hydrogenation is processed.(4) thermostability of block metal glass does not reduce after vapour phase hydrogenation is processed.(5) yield strength of block metal glass does not reduce after vapour phase hydrogenation is processed.
Description of drawings
Fig. 1 is a kind of techniqueflow chart that improves the method for block metal glass and structural part plasticity thereof of the present invention.
Fig. 2 is the XRD figure sample of the BMG for preparing of hydrogen treatment and hydrogen treatment not.
Fig. 3 is the DSC curve of the BMG for preparing of hydrogen treatment and hydrogen treatment not.
Fig. 4 is the mechanical property contrast of the BMG material prepared of not hydrogenation and hydrogen treatment.Experiment condition is: sample is the column sample of 3 * 6mm, and experimental temperature is room temperature, and compressive strain speed is 5 * 10 -4s -1
Embodiment
The performance that the present invention has broken through by introduce second-phase change material itself in block metal glass improves its plasticity, but by being carried out hydrogen treatment, the block metal glass structural part improves its plasticity, except plasticity was improved, other proper property did not change after the block metal glass structural part process hydrogen treatment.Block metal glass is carried out hydrogen treatment dual mode at present, and a kind of is electrochemistry hydrogenation, and this hydrogenation mode time is long, and block metal glass is had corrosive nature; Another kind is vapour phase hydrogenation, also is hydrogen treatment mode of the present invention, and this invention is conducive to the raising of the plasticity of block metal glass, and main scientific thought is as follows:
Figure DEST_PATH_IMAGE002
The elements such as the Zr in the block metal glass, Ti and hydrogen have stronger avidity.
Figure DEST_PATH_IMAGE004
The elements such as the Ni in the block metal glass have katalysis to the absorption of hydrogen.
There are a large amount of tetrahedral interstices that exist energy state different in a large amount of free volumes, the shot-range ordered structure in the block metal glass, are conducive to occupying of hydrogen.
Below in conjunction with accompanying drawing the present invention is described in further detail.
In conjunction with Fig. 1, the present invention improves the method for block metal glass and structural part plasticity thereof, and the method for utilizing vapour phase hydrogenation to process improves the plasticity of block metal glass and structural part thereof.Concrete steps are:
The first step, the composition of selected mother alloy matrix, the non-consumable arc melting is founded master alloy ingot;
Second step is cast block metal glass with master alloy ingot fragmentation remelting after-blow in container;
The 3rd step, the block metal glass that second step is made or the block metal glass structural part of arbitrary shape carry out vapour phase hydrogenation to be processed, the hydrogen pressure that carries out the vapour phase hydrogenation processing is 1-30MPa, the temperature of carrying out the vapour phase hydrogenation processing is the glass transformation temperature that is lower than block metal glass, and the hydrogen－sucking amount of block metal glass will guarantee that hydrogen does not generate hydride and hydrogen blistering with metal reaction in the vapour phase hydrogenation treating processes.
Concrete techniqueflow is as follows
Figure DEST_PATH_IMAGE008
, mother alloy melting: calculate each constituent mass according to Composition Design and carry out proportioning.Under the high-purity argon gas protection; Utilize melting Ti pure metal to remove oxygen in the chamber, utilize water jacketed copper crucible non-consumable arc melting mother alloy.Mother alloy at least melting 5 times and carry out induction stirring guarantee composition evenly.
, the BMG moulding: mother alloy is put into the quartz crucible remelting after the fragmentation again, the insulation regular hour after the fusing evenly, utilize pressure difference that high-purity argon gas produces that the mother alloy of fusing is blown into preparation moulding BMG in the copper mold fast, the block metal glass structural part of the arbitrary shape that perhaps prepares by other approach.
Figure DEST_PATH_IMAGE010
, hydrogen treatment: with BMG gas phase hydrogen treatment regular hour under certain temperature and hydrogen pressure of preparing.
Figure DEST_PATH_IMAGE012
, structure and mechanical property characterize: utilize XRD, DSC and opticmicroscope triplicity that the matrix material of preparation is carried out Microstructure characterization, guarantee that the material of preparing is the block metal glass of full amorphous.Hydrogen treatment and not hydrotreated block metal glass are carried out Mechanics Performance Testing, relatively its mechanical property difference.Behind the technical maturity, this step can be omitted.
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
The selection of matrix composition: it is 99.9% Cu, 99.99% Zr, 99.5% Al and 99.99% Ni that the preparation master alloy ingot is selected raw-material purity, and the alloy nominal composition is Cu 45Zr 46Al 7Ni 2(atomic percent).
Figure DEST_PATH_IMAGE014
The preparation of mother alloy: air-breathing at Ti, under the high-purity argon gas protective condition, adopt the non-consumable arc melting to found mother alloy.
Figure 374920DEST_PATH_IMAGE002
The surperficial mechanical grinding of raw metal is removed surperficial oxide skin, according to the composition proportion batching that designs; Weighing is smart
Really in 0.001g, the material that will prepare according to the weight about every ingot 60-80g is put into the water jacketed copper crucible of smelting furnace
In, cover bell and be evacuated down to 5 * 10 -3Below the Pa; Charged pressure is the high-purity argon gas of 0.06MPa in the stove.
Before founding master alloy ingot, will for the Ti ingot melting of degasification 3 times, remove the remnant oxygen in the furnace chamber.
With Cu, Zr, Al, Ni melting 2 times, use mechanical manipulator that alloy pig is turned to another side after the melting the 2nd time, spindle melts the again melting at least 3 times of rear use induction stirring fully, guarantees the mother alloy homogeneous chemical composition.
Figure DEST_PATH_IMAGE016
The preparation of sample: mother alloy is broken, take by weighing about 10 grams and put into quartz crucible, be 5 * 10 in vacuum -3The following fusing of Pa, use is blown casting mother alloy is expelled to moulding in the copper mold.
Figure DEST_PATH_IMAGE018
Hydrogen treatment: with sample hydrogenation 1 hour under the hydrogen pressure of room temperature 7.5MPa of preparation.
Figure DEST_PATH_IMAGE020
Performance Detection: in conjunction with Fig. 2, Fig. 3, Fig. 4, the sample after the hydrogen treatment and not hydrotreated sample are carried out respectively XRD and DSC detect, found that the structure of the BMG sample after the hydrogen treatment does not change, thermostability does not change yet.Room temperature quasistatic Compressive Mechanical Properties test result shows that the BMG after the hydrogen treatment has 3% amount of plastic deformation, and not hydrotreated BMG non-plastic.
Embodiment 2
Matrix composition is chosen as Zr 41.2Ti 13.8Cu 12.5Ni 10Be 22.5(atomic percent).The preparation of mother alloy is with embodiment 1 step 2, and sample prepares with embodiment 1 step 3, and difference is that hydrotreated temperature is 100 ℃, and hydrogen pressure is 5MPa, and hydrogenation time is 1.5 hours.Performance Detection is with embodiment 1 step 5, and structure and the thermostability of hydrotreated BMG do not change, and the BMG after the hydrogen treatment has 3.5% amount of plastic deformation, not hydrotreated BMG non-plastic.
Embodiment 3
Matrix composition is chosen as La 62Al 14(Cu, Ni) 24(atomic percent).The preparation of mother alloy is with embodiment 1 step 2, and sample prepares with embodiment 1 step 3, and difference is that hydrotreated temperature is 80 ℃, and hydrogen pressure is 10MPa, and hydrogenation time is 0.5 hour.Performance Detection is with embodiment 1 step 5, and structure and the thermostability of hydrotreated BMG do not change, and the BMG after the hydrogen treatment has 2.5% amount of plastic deformation, not hydrotreated BMG non-plastic.
Embodiment 4
Matrix composition is chosen as Zr 56.2Ti 13.8Nb 5.0Cu 6.9Ni 5.6Be 12.5(atomic percent).The preparation of mother alloy is with embodiment 1 step 2, and sample prepares with embodiment 1 step 3, and difference is that hydrotreated temperature is 90 ℃, and hydrogen pressure is 10MPa, and hydrogenation time is 1.5 hours.Performance Detection is with embodiment 1 step 5, and structure and the thermostability of hydrotreated BMG do not change, and the BMG after the hydrogen treatment has 5% amount of plastic deformation, not hydrotreated BMG non-plastic.
Embodiment 5
Matrix composition is chosen as Cu 47Zr 45Al 8(atomic percent).The preparation of mother alloy is with embodiment 1 step 2, and sample prepares with embodiment 1 step 3, and difference is that hydrotreated temperature is 120 ℃, and hydrogen pressure is 30MPa, and hydrogenation time is 3 hours.Performance Detection is with embodiment 1 step 5, and structure and the thermostability of hydrotreated BMG do not change, and the BMG after the hydrogen treatment has 3% amount of plastic deformation, not hydrotreated BMG non-plastic.
Embodiment 6
Matrix composition is chosen as Cu 47Zr 45Al 4Ag 4(atomic percent).The preparation of mother alloy is with embodiment 1 step 2, and sample prepares with embodiment 1 step 3, and difference is that hydrotreated temperature is 50 ℃, and hydrogen pressure is 25MPa, and hydrogenation time is 2 hours.Performance Detection is with embodiment 1 step 5, and structure and the thermostability of hydrotreated BMG do not change, and the BMG after the hydrogen treatment has 7% amount of plastic deformation, not hydrotreated BMG non-plastic.
Embodiment 7
Matrix composition is chosen as Zr 62Cu 15.5Ni 12.5Al 10(atomic percent).The preparation of mother alloy is with embodiment 1 step 2, and sample prepares with embodiment 1 step 3, and difference is that hydrotreated temperature is 200 ℃, and hydrogen pressure is 20MPa, and hydrogenation time is 0.5 hour.Performance Detection is with embodiment 1 step 5, and structure and the thermostability of hydrotreated BMG do not change, and the BMG after the hydrogen treatment has 4.5% amount of plastic deformation, not hydrotreated BMG non-plastic.
Embodiment 8
Matrix composition is chosen as Fe 73C 7.0Si 3.3B 5.0P 8.7Mo 3.0(atomic percent).The preparation of mother alloy is with embodiment 1 step 2, and sample prepares with embodiment 1 step 3, and difference is that hydrotreated temperature is room temperature, and hydrogen pressure is 30MPa, and hydrogenation time is 1 hour.Performance Detection is with embodiment 1 step 5, and structure and the thermostability of hydrotreated BMG do not change, and the BMG after the hydrogen treatment has 3% amount of plastic deformation, not hydrotreated BMG non-plastic.

Claims (1)

1. method that improves block metal glass plasticity is characterized in that: the method for utilizing vapour phase hydrogenation to process improves the plasticity of block metal glass; Step is:
The first step, the composition of selected mother alloy matrix, the non-consumable arc melting is founded master alloy ingot;
Second step is cast block metal glass with master alloy ingot fragmentation remelting after-blow in container;
In the 3rd step, the block metal glass that second step is made carries out the vapour phase hydrogenation processing; The hydrogen pressure that carries out the vapour phase hydrogenation processing is 1-30MPa; The temperature of carrying out the vapour phase hydrogenation processing is the glass transformation temperature that is lower than block metal glass; The hydrogen－sucking amount of block metal glass does not generate hydride and hydrogen blistering with metal reaction for guaranteeing hydrogen in the vapour phase hydrogenation treating processes.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906598A (en) * 2009-06-08 2010-12-08 比亚迪股份有限公司 Zirconium-base amorphous alloy and preparation method thereof

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JP4850526B2 (en) * 2006-02-01 2012-01-11 国立大学法人東北大学 Method for producing metal glass alloy and method for producing metal glass alloy product

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906598A (en) * 2009-06-08 2010-12-08 比亚迪股份有限公司 Zirconium-base amorphous alloy and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JP特开2007-204812A 2007.08.16
刘鹏等.氢化处理铸造镁锂系合金.《铸造》.2006,第55卷(第5期),第505-508页. *
张兴超等.大块非晶合金的复合韧化研究进展.《稀有金属材料与工程》.2006,第35卷(第4期),第510-515页. *

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