CN105039761A - Method for preparing bulk amorphous alloy by means of spark plasma sintering - Google Patents
Method for preparing bulk amorphous alloy by means of spark plasma sintering Download PDFInfo
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- CN105039761A CN105039761A CN201510411840.1A CN201510411840A CN105039761A CN 105039761 A CN105039761 A CN 105039761A CN 201510411840 A CN201510411840 A CN 201510411840A CN 105039761 A CN105039761 A CN 105039761A
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Abstract
The invention discloses a method for preparing bulk amorphous alloy by means of spark plasma sintering. According to the method, based on the spark plasma sintering technique, amorphous alloy blocks are prepared by reducing the pulse duty ratio. By the adoption of the method, microcell instantaneous energy can be increased, cooling time can be lengthened, glass transition temperature and crystallization temperature depending on heating rate are increased too, and then the bulk amorphous alloy which is high in interface bonding strength and density and maintains good amorphous characteristics is prepared. By the adoption of the method, the technical problem that in the current amorphous alloy powder metallurgy process, high interface bonding performance and an amorphous alloy metastable structure can not be realized at the same time is solved.
Description
Technical field
The present invention relates to the preparing technical field of non-crystaline amorphous metal, particularly relate to a kind of method that discharge plasma sintering prepares bulk amorphous alloys.
Background technology
Non-crystaline amorphous metal is a kind of non-equilibrium metastable metallic substance of longrange disorder short range order.Thus do not have the defects such as the crystal grain in conventional crystal material, crystal boundary, dislocation, its even macroscopic, isotropy, but structure and composition have microinhomogeneity, structure minimal characteristic can reach atom magnitude.Special atom level structure makes it have high hardness, wear resistance, close to the yield strength (being up to 6GPa) of theoretical limit, and low mechanical damping, Young's modulus and high rebound resilience (can 2% be reached).Very little viscous deformation but has high fracture toughness property and impelling strength, because of deformation and the fracture behaviour of its uniqueness, block amorphous alloy be find up to now the most by force, the most firmly, the softest (supercooled liquid phase warm area superplasticity), the most tough, most bullet structural metallic materials.
But, because non-crystaline amorphous metal has obvious weakness: brittleness at room temperature is obvious, be difficult to large size application; Have metastability, hot-work is no more than glass transformation temperature.Although found the strong glass forming ability system that some critical cooling rates are slower, the amorphous formation ability of most system bulk-metallic glass is also more weak.Therefore, the bulk-metallic glass for most system is applicable to considering application with reduced size form, and the small size bottleneck problem of non-crystaline amorphous metal engineer applied is not yet resolved.
Non-crystaline amorphous metal block materials can be prepared by powder metallurgy technology at its supercooled liquid phase warm area, but poor, the narrower supercooled liquid phase warm area of heating uniformity and large pressure limitation the method.Discharge plasma sintering is a kind of pressure sintering method utilizing on and off DC pulse current direct-electrifying to sinter.The Main Function of on and off formula DC pulse current produces discharge plasma, discharge impact pressure, joule heating and electric field diffusion effect.In discharge plasma sintering process, the discharge plasma produced instantaneously when electrode passes into DC pulse current, makes sintered compact each uniform particles ground inner self produce joule heating and particle surface is activated.Discharge plasma sintering process can be regarded as the result of particle electric discharge, conduction heating and pressurization comprehensive action.Except heating with pressurize except the factor of these two accelerations of sintering, in discharge plasma sintering technique, intergranular effective electric discharge can produce localized hyperthermia, makes particle surface local melting, surface mass peels off; The sputtering of high-temperature plasma and discharge impact remove the gas of powder particle surface impurity (as removed surface oxides etc.) and absorption.Therefore, the sintering between granular boundary occurs in very short time range.But, for the non-crystaline amorphous metal system that amorphous formation ability is poor, too small supercooled liquid phase warm area and high viscosity factor make good interface cohesion and avoid Amorphous Crystallization kinetically often occurring contradiction, and in amorphous powdered alloy metallurgical process, good interface combines and is difficult to take into account with non-crystaline amorphous metal metastable structure simultaneously.
At present, the report that relevant discharge plasma sintering prepares block amorphous alloy is a lot, but there is not yet the report about low duty ratio technique.
Summary of the invention
The object of the invention is to combine to solve good interface in amorphous powdered alloy metallurgical process the technical problem being difficult to non-crystaline amorphous metal metastable structure simultaneously take into account, providing a kind of method that discharge plasma sintering prepares bulk amorphous alloys.
In discharging plasma sintering equipment, the regulation range of pulse duty factor both on and off ratio of DC pulse is enclosed for 99:1 ~ 1:9.Under certain power, the reduction along with pulse duty factor increases by the height of pulse waveform, and momentary power will increase thereupon.This high instantaneous energy concentrating on granular boundary microcell contributes to the formation of sintered neck.And form the microcosmic heating cooling conditions that is conducive to non-crystaline amorphous metal microstructure and property.Based on discharge plasma sintering technique, by reducing pulse duty factor (reducing the on and off ratio of DC pulse), prepare non-crystaline amorphous metal block materials.Utilize preparation technology of the present invention, can make the raising of microcell instantaneous energy, growth cooling time, the glass transformation temperature and the crystallization temperature that depend on heating rate also increase simultaneously thereupon, thus it is high to prepare interface bond strength, density is high, and amorphous characteristic keeps good agglomerate body non-crystaline amorphous metal.
The present invention includes following steps:
1) selection of pulse duty factor
In discharge plasma sintering, the scope that arranges of pulse duty factor is from 99:1 ~ 1:9.Pulse duty factor little is as far as possible conducive to the generation of local microcell momentary high power, and cooling time is relatively long.This obtains while being conducive to realizing interface cohesion and maintaining the metastable characteristic of amorphous.Described pulse duty factor is the on and off ratio of DC pulse.
2) measurement of pulse waveform
By sample upper and lower end face voltage real-time online accurate monitoring device, obtain the change of assembly real-time voltage and the relation sintering assembling process.In order to better measure the pulse signal at powder two ends, except the part contacted with powder, the place of other and contacting dies has all covered the boron nitride of insulating effect.
3) discharge plasma sintering densification
Adopt discharge plasma sintering method, under suitable little duty cycle condition, carry out the cold pressing densification sintering of base of powder be shaped, sintering process realize high-strength sintered while reach densification and crystallization do not occur.
Beneficial effect of the present invention
The present invention is based on discharge plasma sintering technique, by reducing pulse duty factor (reducing the on and off ratio of DC pulse), preparing non-crystaline amorphous metal block.Utilize preparation technology of the present invention, the raising of microcell instantaneous energy, growth cooling time can be made, simultaneously due to kinetic reasons, the glass transformation temperature and the crystallization temperature that depend on heating rate also increase thereupon, thus it is high to prepare interface bond strength, density is high, and amorphous characteristic keeps good agglomerate body non-crystaline amorphous metal.
Accompanying drawing explanation
Fig. 1 is discharge plasma sintering pulsed test signal principle schematic.
Fig. 2 is that [(Fe is prepared in aerosolization
0.8co
0.2)
0.75b
0.2si
0.05]
96nb
4amorphous powder particle surface SEM schemes.
Fig. 3 is the oscillogram of different pulse duty factor in discharge plasma sintering process.
Fig. 4 is the XRD figure preparing style under amorphous powdered alloy and different pulse mode.
Fig. 5 is the SEM figure preparing sample under 2:9 (on:off) pattern and 12:2 (on:off) pattern.
Embodiment
The present invention includes following steps:
1) selection of pulse duty factor
In discharge plasma sintering, the scope that arranges of pulse duty factor is from 99:1 ~ 1:9.Pulse duty factor little is as far as possible conducive to the generation of local microcell momentary high power, and cooling time is relatively long.This obtains while being conducive to realizing interface cohesion and maintaining the metastable characteristic of amorphous.Described pulse duty factor is the on and off ratio of DC pulse.
2) measurement of pulse waveform
By sample upper and lower end face voltage real-time online accurate monitoring device, obtain the change of assembly real-time voltage and the relation (as shown in Figure 1) sintering assembling process.In order to better measure the pulse signal at powder two ends, except the part contacted with powder, the place of other and contacting dies has all covered the boron nitride of insulating effect.
3) discharge plasma sintering densification
Adopt discharge plasma sintering method, under suitable little duty cycle condition, carry out the cold pressing densification sintering of base of powder be shaped, sintering process realize high-strength sintered while reach densification and crystallization do not occur.
Specific examples:
Adopt commercially available aerosolization [(Fe
0.8co
0.2)
0.75b
0.2si
0.05]
96nb
4powder is raw materials for sintering, raw materials for sintering surface topography as shown in Figure 2, use the sintered-carbide die of former internal diameter diameter 15mm, graphite paper is placed with between former and formpiston and between formpiston and sample, and test copper coin is positioned over the position shown in Fig. 1, make galvanic couple thermometer hole and sample be centrally located at sustained height after pretension, ensure that thermometric is true and reliable, after powder cold compaction embryo, carry out discharge plasma sintering.Discharge plasma sintering test is carried out on DR.SINTERSPS-625 type discharge plasma sintering machine, and temperature rise rate is 100 DEG C/min, rises to 500 DEG C.Longitudinal uniaxial tension of formpiston is 600MPa, is held in whole sintering process.Under the prerequisite that above-mentioned experiment condition is identical, adopt different pulse duty factors, 12:2,2:2,2:9, carry out [(Fe
0.8co
0.2)
0.75b
0.2si
0.05]
96nb
4the preparation of non-crystaline amorphous metal.Fig. 3 is the oscillogram of different pulse duty factor in discharge plasma sintering process, and under certain heating power, the height of peak value increases along with the reduction of pulse duty factor.This high momentary power creates higher transient energy at microcell just.Fig. 4 is the XRD figure preparing sample under amorphous powdered alloy and different pulse mode, as seen from the figure, little pulse duty factor has less crystallization, and the amorphous block prepared under 12:2 and 2:2 pattern shows crystallization trend, and under 2:2 pulse mode, crystallization is larger.This is because little pulse duty factor makes interface create high instantaneous energy, and heat high in identical turn-off time can not fully spread, and pulse persistance carries out, and impels local temperature too high, makes amorphous easily crystallization occur.Comparatively speaking, amorphous block is prepared under 2:9 pulse mode, after the high instantaneous energy promotion interface sintering at interface, there is the longer heat radiation time, be conducive to the appearance avoiding crystallization, further, this instantaneous heating makes the glass transformation temperature of non-crystaline amorphous metal and purifies transition temperature to high temperature future development, and this more alleviates the contradictory relation of non-crystaline amorphous metal non-crystaline amorphous metal interface and amorphous powder crystallization in preparation process.Fig. 5 is the SEM image of different pulse electric current sintering densification sample, comparison diagram a and figure b, and can clearly be seen that the sintered neck of interface under the condition of little dutycycle is formed more more obvious, interface cohesion is better.Finer and close as can be seen from the sintering of figure a1 and figure b1, figure b1, interface cohesion is tightr.This is the fusion that the high momentary power provided due to little pulse duty factor facilitates interface, and then has prepared the good Fe base noncrystal alloy of interface cohesion.
Claims (1)
1. discharge plasma sintering prepares a method for bulk amorphous alloys, and the method comprises the following steps:
1) selection of pulse duty factor
In discharge plasma sintering, the scope that arranges of pulse duty factor is from 99:1 ~ 1:9; Pulse duty factor little is as far as possible conducive to the generation of local microcell momentary high power, and cooling time is relatively long; This obtains while being conducive to realizing interface cohesion and maintaining the metastable characteristic of amorphous;
2) measurement of pulse waveform
By sample upper and lower end face voltage real-time online accurate monitoring device, obtain the change of assembly real-time voltage and the relation sintering assembling process; In order to better measure the pulse signal at powder two ends, except the part contacted with powder, the place of other and contacting dies has all covered the boron nitride of insulating effect;
3) discharge plasma sintering densification
Adopt discharge plasma sintering method, under suitable little duty cycle condition, carry out the cold pressing densification sintering of base of powder be shaped, sintering process realize high-strength sintered while reach densification and crystallization do not occur.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018121314A1 (en) * | 2016-12-30 | 2018-07-05 | 常州世竟液态金属有限公司 | Method for shaping amorphous alloy |
| WO2022160465A1 (en) * | 2021-01-31 | 2022-08-04 | 华中科技大学 | Method for calibrating internal temperature field when preparing amorphous alloy by using spark plasma sintering |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062972A (en) * | 1990-12-30 | 1992-07-22 | 中国科学院金属研究所 | High-temperature thermocouple insulating tube and manufacturing method thereof |
| CN101492781A (en) * | 2008-11-18 | 2009-07-29 | 华南理工大学 | High-ductility titanium based ultra-fine crystal composite material and method for producing the same |
| CN101935777A (en) * | 2010-09-14 | 2011-01-05 | 华南理工大学 | Titanium-based ultrafine grain or fine grain composite material with high compression ratio strength and preparation method thereof |
| CN102142309A (en) * | 2010-12-30 | 2011-08-03 | 长春工业大学 | Block amorphous/ferrite soft magnetic composite material and preparation method thereof |
| CN102534301A (en) * | 2012-03-02 | 2012-07-04 | 华南理工大学 | High-strength low-modulus medical ultra-fine grain titanium matrix composite and preparation method thereof |
| CN103305722A (en) * | 2013-06-04 | 2013-09-18 | 华南理工大学 | Ti-based high temperature alloy with high toughness in bi-state structure and preparation method and application thereof |
-
2015
- 2015-07-14 CN CN201510411840.1A patent/CN105039761A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062972A (en) * | 1990-12-30 | 1992-07-22 | 中国科学院金属研究所 | High-temperature thermocouple insulating tube and manufacturing method thereof |
| CN101492781A (en) * | 2008-11-18 | 2009-07-29 | 华南理工大学 | High-ductility titanium based ultra-fine crystal composite material and method for producing the same |
| CN101935777A (en) * | 2010-09-14 | 2011-01-05 | 华南理工大学 | Titanium-based ultrafine grain or fine grain composite material with high compression ratio strength and preparation method thereof |
| CN102142309A (en) * | 2010-12-30 | 2011-08-03 | 长春工业大学 | Block amorphous/ferrite soft magnetic composite material and preparation method thereof |
| CN102534301A (en) * | 2012-03-02 | 2012-07-04 | 华南理工大学 | High-strength low-modulus medical ultra-fine grain titanium matrix composite and preparation method thereof |
| CN103305722A (en) * | 2013-06-04 | 2013-09-18 | 华南理工大学 | Ti-based high temperature alloy with high toughness in bi-state structure and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李少龙，郭薇等: "放电等离子烧结参数对Fe76Si9B10P5非晶合金致密化及晶化的影响", 《长春工业大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018121314A1 (en) * | 2016-12-30 | 2018-07-05 | 常州世竟液态金属有限公司 | Method for shaping amorphous alloy |
| WO2022160465A1 (en) * | 2021-01-31 | 2022-08-04 | 华中科技大学 | Method for calibrating internal temperature field when preparing amorphous alloy by using spark plasma sintering |
| US11673192B2 (en) | 2021-01-31 | 2023-06-13 | Huazhong University Of Science And Technology | Method for calibrating internal temperature field of amorphous alloy prepared by spark plasma sintering |
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