CN107099717A - The technology of preparing of crystal boundary auto purification tungsten magnesium alloy - Google Patents
The technology of preparing of crystal boundary auto purification tungsten magnesium alloy Download PDFInfo
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- CN107099717A CN107099717A CN201710342132.6A CN201710342132A CN107099717A CN 107099717 A CN107099717 A CN 107099717A CN 201710342132 A CN201710342132 A CN 201710342132A CN 107099717 A CN107099717 A CN 107099717A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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Abstract
The invention provides a kind of technology of preparing of crystal boundary auto purification tungsten magnesium alloy, mixed using metal magnesium powder with tungsten powder, by adding appropriate particle diameter and mass percent magnesium powder into tungsten powder, under vacuum, segmentation pressure sintering is carried out, the first stage is warming up to 400 DEG C of 800 DEG C of 1 30min of sintering first, second segment heating is then carried out, in 1200 DEG C of 1600 DEG C of 1 60min of sintering, then the 3rd section of heating is carried out, in 1600 DEG C of 1900 DEG C of 1 30min of sintering, tungsten magnesium alloy is made.The present invention utilizes the mobility and the more hole of mixed powder original state of magnesium, micro flow of the magnesium in tungsten basal body can be realized, absorb the oxygen element touched, harmful oxygen element of part is purified, and the enhancing phase of dispersion stability is combined to form with oxygen element intrinsic in matrix, attenuation of the oxygen element to tungsten crystal boundary is eliminated, tough tungsten magnesium alloy is stablized in formation, the mechanical property of tungsten magnesium alloy block is significantly improved, hot industry field is can be widely used for.
Description
Technical field
The invention belongs to tungsten field of magnesium alloy material, and in particular to a kind of technology of preparing of crystal boundary auto purification tungsten magnesium alloy.
Background technology
Tungsten is a kind of metal material extensively using each industrial circle, with high density, high-melting-point, high heat conductance, low-heat
The features such as coefficient of expansion.In war industry, nuclear industry, Aero-Space aspect has the application of uniqueness.Under these application conditions, tungsten
Need often to bear coupling outer field action, such as high temperature, irradiation and thermal shock, tungsten material is easy to failure under these operating modes,
It is mainly shown as that the recrystallization by the brittle fracture in the case of external force and under fuel factor is brittle.It is body-centered cubic for crystal structure
Tungsten for, its grain-boundary strength is poor, is the easy place that is broken, under plus load is acted on, mostly occur grain boundary fracture.Therefore
For tungsten material, purification crystal boundary and the effective means that reinforcing crystal boundary is toughness reinforcing tungsten material.Second-phase dispersion reinforcing be tungsten most
Effective toughening technology.Dispersion-strengtherning particle mainly has two major classes：Metal carbides (such as titanium carbide, zirconium carbide, hafnium carbide
Deng) and rare earth oxide (yittrium oxide, lanthana, thorium oxide etc.).Such as document《Add trace Ti C to the performance of tungsten with it is micro-
The influence of tissue》(China YouSe Acta Metallurgica Sinica, 2015 (1):80-85), added with Mechanical Alloying into tungsten 1% carbon
Change titanium valve body, its sintered state intensity brings up to 401MPa by 260MPa, and fracture mode is changed into " edge from the grain boundary fracture of pure tungsten
Brilliant fracture+transgranular fracture ".Similarly, document《La_2O_3 is to ultra-fine tungsten composite powder sintering character and tungsten alloy microscopic structure
Influence》(Materials Science and Engineering of Powder Metallurgy, 2014 (3):By adding 0.7% lanthana into tungsten in 439-445),
The bending strength of sintered state brings up to 548MPa by 213MPa.Research shows that the addition of superfine ceramic granular powder makes tungsten above
The crystal grain of matrix is refined, so that obdurability is improved.But carbide and oxide may be formed as disperse phase causes tungsten
Middle carbon oxygen element content rise.As document《Impurity is on the brittle influence of tungsten crystal boundary》(Rare Metals Materials and engineering, (1986)
Pointed out in 41-45), these segregations are in the performance of the element influences tungsten basal body of crystal boundary, and these Element segregations can cause to show in crystal boundary
Write reduction grain-boundary strength；Meanwhile, rare earth oxide fusing point is relatively low, can occur to melt and Evaporation Phenomenon under high temperature, leave pit-hole, make
Into a series of microfissures, it is unfavorable for the holding of elevated temperature strength.
Mechanical alloying, such as document being used the method for preparing dispersion-strengtherning tungsten powder more《A kind of nano yttrium oxide dispersion-strengtherning
The preparation method of tungsten alloy》The report of (Chinese .CN201310123415.3 [P] .2015-04-08), i.e., by diffusing particle and tungsten
Powder mixing is put into ball mill, carries out the ball milling of long-time high-energy, and second phase particles are passed through into the physics such as mechanical collision and grinding
Effect reaches compound effect with tungsten powder.Equally also have using precipitation cladding process, such as document《A kind of sub-micron sphere-like tungsten powder
Preparation method》The report of (Chinese .CN201010581902.0 [P] .2012-06-06), soluble tungsten salt and diffusing particle are matched somebody with somebody
Well mixed disperse solution is set to, by adjusting solution pH value, generation wolframic acid precipitation, these precipitations are by suspended in solution the
Two-phase particle carries out coating reaction, obtains core shell structure, by calcining reduction, obtains the tungsten powder of dispersion-strengtherning.For machinery conjunction
For aurification, it needs to consume the strenuous exercise due to tank body and abrading-ball in substantial amounts of energy, mixed process, is readily incorporated miscellaneous
Matter, and this method preparation disperse tungsten powder cycle is long, it is less economical.Precipitation cladding process can obtain that disperse homogeneous quality is good to be mixed
Miscellaneous tungsten powder, but precipitation coating reaction is carried out because this method needs the soda acid of more amount to allocate control solution pH value, it is a kind of
To the disagreeableness method of environment.In summary, it will be seen that traditional dispersion-strengtherning is all from original state to tungsten basal body
The second phase of middle introducing, this introducing process is readily incorporated impurity element, and the second of addition is typically mutually the stable ceramics of property
Grain or oxide, can not react with the oxygen element contained in powder preparing processes.And adding means and technological process
It is complicated so that the production procedure of tungsten material is elongated, cost rise.
Magnesium is a kind of active metal element, easily with the element reaction such as oxygen.In ripe steel and iron industry, magnesium has as one
The addition element of benefit demonstrates it and purifies matrix already, reduces the effect of steel oxygen content.The fusing point of magnesium, than relatively low, is 648
DEG C, the fusing point of magnesia is then 2852 degree.Magnesia is a kind of high-temperature refractory of good performance, in addition, in high temperature
Under, magnesia can react with tungsten, generate magnesium tungstate, and the generation of magnesium tungstate can increase between Second Phase Particle and matrix
Adhesion, solidifies oxygen element, strengthens matrix.
The content of the invention
The present invention be directed to above-mentioned deficiency, propose to mix with tungsten powder using metal magnesium powder, by adding appropriate into tungsten powder
Particle diameter and mass percent magnesium powder, using multi-steps sintering technique, promote magnesium to be flowed in tungsten basal body, and with oxygen intrinsic in matrix
Element combines to form the enhancing phase of dispersion stability, eliminates attenuation of the oxygen element to tungsten crystal boundary, and tough tungsten magnesium is stablized in formation
Alloy.Preparation method is simple and effective, and there is the tungsten magnesium alloy block prepared significant mechanical property to improve, and can be widely used for height
Temperature industrial field.
The present invention implementation be：Choose the magnesium powder and tungsten powder for being adapted to granularity --- machinery is carried out under protective atmosphere mixed
Close --- mixed powder carries out multi-steps sintering technique --- and obtain tungsten magnesium alloy block.Specific step of preparation process is as follows：
Magnesium powder and tungsten powder are prepared, mechanical mixture is carried out under protective atmosphere, then mixed powder is subjected to loading mould, true
Under empty condition, segmentation pressure sintering is carried out, the first stage first is warming up to 400 DEG C of -800 DEG C of sintering 1-30min, then carries out the
Two sections of heatings, in 1200 DEG C of -1600 DEG C of sintering 1-60min, then carry out the 3rd section of heating, in 1600 DEG C of -1900 DEG C of sintering 1-
30min, is made tungsten magnesium alloy.
The preparation magnesium powder and tungsten powder, are that the magnesium powder that mass percent is 0.1%-2%, magnesium powder granularity are added in tungsten powder
Less than 1 micron.
The tungsten powder selects business pure tungsten powder.
The process for preparation is carried out under argon atmospher protection.
It is described that mechanical mixture is carried out under protective atmosphere, it is that the powder of preparation is added into batch mixing tank body, in argon atmospher protection
Lower carry out mechanical mixture, incorporation time is according to the difference of addition, between 0.5h to 2h.
The sintering pressure selection 1-100MPa of the segmentation pressure sintering, and keep each section of sintering pressure constant.
The beneficial effects of the invention are as follows, first paragraph low-temperature sintering, using magnesium mobility and mixed powder original state compared with
Many holes, it is possible to achieve micro flow of the magnesium in tungsten basal body, absorb the oxygen element touched, and react a generation part
Stable magnesia, has purified harmful oxygen element of part；Second segment intermediate sintering temperature, is densified to matrix, secures more
Scattered seed, while contact is grown up between crystal grain, a part of oxide particle that will be present on crystal boundary is wrapped up into intra-die, shape
Into dispersoid particle；3rd section of high temperature sintering, under the comprehensive function of high temperature, vacuum and sintering pressure so that be present in matrix
In partial oxidation magnesium reacted with tungsten basal body, generate a certain amount of magnesium tungstate, the knot between increase diffusing particle and matrix
With joint efforts.
The tungsten magnesium conjunction alloy of preparation is analyzed, shows, there is the dispersion of amorphous state, intra-die on crystal boundary
There is tiny diffusing particle.Mechanics Performance Testing is carried out to it, it is shown that bending strength and hardness are significantly improved.It is simultaneously this
The performance difference that production technology need not be carried out between the hybrid technique of long-time high energy consumption, powder batch is small, it is possible to achieve economical
Efficient production.
Brief description of the drawings
Fig. 1 is the sintered state macrograph of 0.1% tungsten magnesium alloy.
Fig. 2 is the sintered state macrograph of 0.5% tungsten magnesium alloy.
Fig. 3 is the sintered state macrograph of 1% tungsten magnesium alloy.
Fig. 4 a are transgranular dispersion energy spectrum analysis in tungsten magnesium alloy.
Fig. 4 b are crystal boundary dispersion energy spectrum analysis in tungsten magnesium alloy.
Embodiment
The present invention is further described with example below in conjunction with the accompanying drawings.
Embodiment 1：
Method described above is prepared for the tungsten magnesium alloy that content is 0.1% magnesium, and to its morphology microstructure, sintered state pattern is carried out
Observe and carry out Mechanics Performance Testing and observed with fracture apperance, as shown in Figure 1.
1st, a diameter of 3 μm of a diameter of 50nm of 0.02g magnesium powder and 19.98g pure tungsten powder is taken to be mixed in glove box.It is put into
Batch mixer, 0.5h mechanical mixtures are carried out under argon gas protection.
2nd, the powder mixed is put into diameter 20mm, height 40mm graphite jig carries out multi-steps sintering.Sintering pressure
For 50MPa.First paragraph：700 DEG C of insulation 3min, second segment：1400 DEG C are warming up to, 5min, the 3rd section is incubated：It is warming up to 1600
DEG C, 1min is incubated, tungsten magnesium alloy is made.
Embodiment 2：
Method described above is prepared for the tungsten magnesium alloy that content is 0.5% magnesium, and to its morphology microstructure, sintered state pattern is carried out
Observe and carry out Mechanics Performance Testing and observed with fracture apperance, as shown in Figure 2.
1st, a diameter of 3 μm of a diameter of 50nm of 0.1g magnesium powder and 19.9g pure tungsten powder is taken to be mixed in glove box.It is put into mixed
Material machine, 0.6h mechanical mixtures are carried out under argon gas protection.
2nd, the powder mixed is put into diameter 20mm, height 40mm graphite jig carries out multi-steps sintering.Sintering pressure
For 55MPa.First paragraph：750 DEG C of insulation 3min, second segment：1450 DEG C are warming up to, 5min, the 3rd section is incubated：It is warming up to 1650
DEG C, 1min is incubated, tungsten magnesium alloy is made.
Embodiment 3：
Method described above is prepared for the tungsten magnesium alloy that content is 1% magnesium, and to its morphology microstructure, sintered state pattern is seen
Examine and carry out Mechanics Performance Testing and observed with fracture apperance, as shown in Figure 3.
1st, a diameter of 3 μm of a diameter of 50nm of 0.2g magnesium powder and 19.8g pure tungsten powder is taken to be mixed in glove box.It is put into mixed
Material machine, 0.7h mechanical mixtures are carried out under argon gas protection.
2nd, the powder mixed is put into diameter 20mm, height 40mm graphite jig carries out multi-steps sintering.Sintering pressure
For 60MPa.First paragraph：800 DEG C of insulation 3min, second segment：1500 DEG C are warming up to, 5min, the 3rd section is incubated：It is warming up to 1700
DEG C, 1min is incubated, tungsten magnesium alloy is made.
The small bar that 2mm*3mm*18mm is cut into the sample prepared carries out micro-hardness measurement and three-point bending resistance respectively
Experiment, it is as a result as follows.
Table 1 0.1%Mg, 0.5%Mg, 1%Mg tungsten block and pure tungsten mechanical property contrast table
| Material category | Microhardness (HV) | Three-point bending resistance intensity (MPa) |
| Pure tungsten | 412 | 356.7 |
| 0.1%Mg tungsten | 509 | 724 |
| 0.5%Mg tungsten | 562 | 807.4 |
| 1%Mg tungsten | 584 | 1105.2 |
From the point of view of test result, adding the bending strength and hardness of the tungsten magnesium alloy that magnesium is prepared has obvious increase,
And the trend of increase is presented with the increase of addition, this with magnesium to the crystal boundary catharsis of tungsten and generation second mutually more
Scattered invigoration effect is inseparable.Observe in the microstructure of tungsten magnesium alloy, such as Fig. 1, it can be seen that, in tungsten crystal boundary and crystal grain
Portion, is dispersed with the second phase of two kinds of forms, and the first is the bar that distortion is elongated along crystal boundary, and also one kind is wrapped around crystalline substance
The pointing object in intragranular portion, with the increase of content of magnesium, such as Fig. 2 and Fig. 3, the second phase amount in tungsten basal body is dramatically increased, but still
Old holding is evenly distributed on transgranular and crystal boundary.Energy spectrum analysis is carried out to the disperse phase on transgranular and crystal boundary, as shown in figure 4,
Dispersion on transgranular and crystal boundary contains a certain amount of magnesia and magnesium tungstate respectively, it was confirmed that tungsten magnesium alloy is in preparation process
Generate containing the second phase for having magnesia and magnesium tungstate.Solidification of the magnesium elements to oxygen element in tungsten basal body is proved, and
The adhesion that the formation of magnesium tungstate is enhanced between diffusing particle and matrix reaches purification tungsten crystal boundary and to form dispersion-strengtherning effective
Improve the effect of material bending strength and hardness.
Claims (6)
1. a kind of technology of preparing of crystal boundary auto purification tungsten magnesium alloy, it is characterised in that magnesium powder and tungsten powder are prepared, under protective atmosphere
Mechanical mixture is carried out, then mixed powder is subjected to loading mould, under vacuum, segmentation pressure sintering, first first is carried out
Stage is warming up to 400 DEG C of -800 DEG C of sintering 1-30min, then carries out second segment heating, in 1200 DEG C of -1600 DEG C of sintering 1-
60min, then the 3rd section of heating is carried out, in 1600 DEG C of -1900 DEG C of sintering 1-30min, tungsten magnesium alloy is made.
2. the technology of preparing of crystal boundary auto purification tungsten magnesium alloy according to claim 1, it is characterised in that the preparation magnesium powder
It is that the magnesium powder that mass percent is 0.1%-2% is added in tungsten powder, magnesium powder granularity is less than 1 micron with tungsten powder.
3. the technology of preparing of crystal boundary auto purification tungsten magnesium alloy according to claim 1, it is characterised in that the tungsten powder selection
Business pure tungsten powder.
4. the technology of preparing of crystal boundary auto purification tungsten magnesium alloy according to claim 1, it is characterised in that the process for preparation
It is to be carried out under argon atmospher protection.
5. the technology of preparing of crystal boundary auto purification tungsten magnesium alloy according to claim 1, it is characterised in that described in protection gas
Mechanical mixture is carried out under atmosphere, is that the powder of preparation is added into batch mixing tank body, mechanical mixture is carried out under argon atmospher protection, during mixing
Between between 0.5h to 2h.
6. the technology of preparing of crystal boundary auto purification tungsten magnesium alloy according to claim 1, it is characterised in that the segmentation pressurization
The sintering pressure selection 1-100MPa of sintering, and keep each section of sintering pressure constant.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020235A (en) * | 2019-12-27 | 2020-04-17 | 厦门钨业股份有限公司 | Method for recovering tungsten from tungsten-containing waste material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080230964A1 (en) * | 2005-09-21 | 2008-09-25 | Basf Se | Tungsten Shot |
| JP2016518516A (en) * | 2013-03-05 | 2016-06-23 | ローレンス リバモア ナショナル セキュリティー， エルエルシー | System and method for additive manufacturing based on high power diodes |
| CN105986159A (en) * | 2015-03-04 | 2016-10-05 | 海南大学 | Fast preparation method for novel W-Ni-Mn alloy |
| CN106591662A (en) * | 2016-12-29 | 2017-04-26 | 河南时代云通信技术有限公司 | High-strength alloy material and preparation method thereof |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080230964A1 (en) * | 2005-09-21 | 2008-09-25 | Basf Se | Tungsten Shot |
| JP2016518516A (en) * | 2013-03-05 | 2016-06-23 | ローレンス リバモア ナショナル セキュリティー， エルエルシー | System and method for additive manufacturing based on high power diodes |
| CN105986159A (en) * | 2015-03-04 | 2016-10-05 | 海南大学 | Fast preparation method for novel W-Ni-Mn alloy |
| CN106591662A (en) * | 2016-12-29 | 2017-04-26 | 河南时代云通信技术有限公司 | High-strength alloy material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020235A (en) * | 2019-12-27 | 2020-04-17 | 厦门钨业股份有限公司 | Method for recovering tungsten from tungsten-containing waste material |
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