CN109943743A - A kind of high-densit, fine brilliant, homogeneous texture self-passivation tungsten alloy preparation method - Google Patents
A kind of high-densit, fine brilliant, homogeneous texture self-passivation tungsten alloy preparation method Download PDFInfo
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- CN109943743A CN109943743A CN201910347937.9A CN201910347937A CN109943743A CN 109943743 A CN109943743 A CN 109943743A CN 201910347937 A CN201910347937 A CN 201910347937A CN 109943743 A CN109943743 A CN 109943743A
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Abstract
The invention discloses a kind of high-densit, fine brilliant, homogeneous texture self-passivation tungsten alloy preparation methods, the self-passivation W alloy powder of homogeneous is obtained using the mechanical alloying technique of optimization first, then pass through control discharge plasma sintering process parameter, it realizes high-densit, fine brilliant, homogeneous texture microscopic structure, and shows prolonged high temperature oxidation resistance.Relative density>95% of self-passivation W alloy of the present invention, crystallite dimension<1 μm (fine crystalline substance), matrix is uniform W-Cr solid solution homogeneous structure, the active element phase particle of addition tiny (nano-scale,<100nm) and disperse is evenly distributed in W-Cr matrix.
Description
Technical field
The invention belongs to the micro-structures controlling fields of infusibility W alloy, and in particular to it is a kind of it is high-densit, fine it is brilliant,
The preparation method of homogeneous texture self-passivation tungsten alloy.
Background technique
W is the highest metal material of fusing point, swollen with high density, Thermal conductivity, excellent elevated temperature strength, low heat
The advantages that swollen coefficient and high Antiradiation, it is widely used in military project national defence, aerospace, electronics industry, radiation shield etc.
Field.W is at high temperature in application, meet the problem of facing high-temperature oxydation.Just such as: W is as the first wall material of the following nuclear fusion device
When material, when in case of cooling failure accident (LOCA) and with vacuum chamber rupture, there is the W of radioactive activity can aoxidize,
Volatilization, to bring the risk of radioactive release.For self-passivation W alloy in high-temperature oxydation, the alloying element of addition can be in material
Expect that surface forms one layer of fine and close protectiveness oxide skin, can to avoid or avoid W from aoxidizing as far as possible, to meet W alloy in high temperature
Use under environment.
Summary of the invention
The present invention is intended to provide a kind of high-densit, fine brilliant, homogeneous texture self-passivation tungsten alloy preparation method, passes through machine
Alloy element Cr, Zr are dissolved into the self-passivation W alloy powder that homogeneous is obtained in W matrix by tool alloying process；Then adopt
It is sintered out high-densit, fine brilliant, homogeneous texture self-passivation W alloy with SPS technology, improves self-passivation W alloy microscopic structure to mention
The long-time high temperature oxidation resistance of high self-passivation W alloy.
High-densit, fine brilliant, homogeneous texture self-passivation tungsten alloy preparation method of the invention, is using mechanical alloying method
It prepares in conjunction with SPS technology, is prepared by control milling parameters and sintering process parameter with long-time resistance to high temperature oxidation
The self-passivation W alloy block of performance.Specifically comprise the following steps:
Step 1: under Ar protective atmosphere, amount weighs W powder, Cr powder and Zr powder that purity is 99.5% according to the ratio, together with
WC abrading-ball is placed in the WC ball grinder of 250ml, and mechanical ball mill is then carried out on planetary ball mill, is turned by regulation ball milling
The techniques such as speed, Ball-milling Time, ratio of grinding media to material, milling atmosphere are to obtain the self-passivation W alloy powder of homogeneous；In order to avoid powder when ball milling
Body aoxidizes, and in powder ball milling early-stage preparations is carried out in Ar atmosphere glove box.
In step 1, in order to obtain the self-passivation W alloy powder of homogeneous, Ball-milling Time is 2~80h, rotational speed of ball-mill 150
~400rad/min, ratio of grinding media to material are 5:1~15:1, milling atmosphere Ar.
Step 2: the self-passivation W alloy powder filling that step 1 is obtained is in graphite jig, using discharge plasma sintering
Technology (SPS) densifies the homogeneous self-passivation W alloy powder of acquisition, passes through heating rate, isothermal in control sintering process
The technological parameters such as time, sintering temperature, to obtain high-compactness, fine brilliant, homogeneous texture self-passivation W alloy.
In step 2, in order to obtain high-densit, fine brilliant, homogeneous texture self-passivation W alloy, SPS technological parameter regulates and controls model
Enclose: heating rate is 50~300 DEG C/min, sintering temperature is 1360~1600 DEG C, soaking time is 0~5min.
Sintering method of the present invention is able to suppress crystal grain and grows up, and can fast implement densification.
The basic component of self-passivation W alloy of the present invention includes: W matrix, is passivated element Cr and active element Y and/or Zr；
Wherein, 10wt%≤passivation element Cr≤13wt%, 0wt% < active element Y and/or Zr≤2wt%.
Self-passivation W alloy produced by the present invention, relative density>95%, crystallite dimension<1 μm (fine crystalline substance), matrix is
Uniform W-Cr solid solution homogeneous structure, the active element phase particle of addition tiny (nano-scale, < 100nm) and disperse is uniform
It is distributed in W-Cr matrix.
The key of self-passivation tungsten alloy preparation method of the present invention is selected mechanical alloying method technological parameter and SPS skill
Art process parameter control.In order to obtain the self-passivation W alloy of homogeneous texture, the present invention is first with regard to proposing to pass through mechanical alloying
The alloy powder of method acquisition homogeneous.In order to obtain the self-passivation W alloy of high-densit, fine crystalline substance, the present invention proposes can be in low temperature reality
The SPS technology now densified densifies the alloy powder of homogeneous.However, according to the phasor of self-passivation W alloy it is found that
When low temperature (being lower than its liquidoid) densification, since Solid solution precipitation can generate cenotype, to cannot get the self-passivation W of homogeneous texture
Alloy.Therefore, one aspect of the present invention is kept away as far as possible by regulating and controlling heating rate, soaking time and the sintering temperature of SPS technique
Exempt from that Solid solution precipitation phenomenon occurs；On the other hand fully consider that SPS technical characteristic reduces self-passivation W alloy and sends out in densification process
The tendency of raw Solid solution precipitation.
Detailed description of the invention
Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c) are respectively the SEM using mechanical alloying method preparation self-passivation W alloy powder
Figure, the section SEM-FIB of large-size particle powder and XRD spectrum.By Fig. 1 it can be found that bulky grain powder section is without obvious different
Matter structure and XRD presentation phase structure.This is absolutely proved, under current preparation process and test condition, the self-passivation W of preparation is closed
Bronze body is the alloy powder of homogeneous texture being dissolved completely.
Fig. 2 (a) and Fig. 2 (b) is respectively the microscopic structure and XRD spectrum of self-passivation W alloy after SPS densification.By Fig. 2
(a) it can be found that the self-passivation W alloy dense structure of preparation, matrix grain are less than 300nm, active element phase particle is less than
100nm.Bcc structure peak is presented in XRD spectrum, is W-Cr single phase solid solution peak.
Fig. 3 is the self-passivation W alloy of the preparation of embodiment 1 in Ar-20vol.%O2Under atmosphere, 1000 DEG C are aoxidized 44 hours
Mass-change curve.
Specific embodiment
Embodiment 1:
Under Ar protective atmosphere, successively weighing purity is 99.5%W powder 95.59g, Cr powder 12.54g and Zr powder 1.87g,
It is fitted into the WC ball grinder of 250ml together according to ratio of grinding media to material 5:1 and WC ball.Then on planetary ball mill, with rotational speed of ball-mill
The ball-milling technology for being 60h for 250rad/min, Ball-milling Time carries out ball milling.The alloyed powder that this ball-milling technology obtains according to Fig. 1
Body.This illustrate addition powder after this Parameter Conditions ball milling, the alloy powder of available homogeneous.Alloy powder is loaded
In graphite jig, densified using SPS technology.Sintering process: heating rate is 200 DEG C/min, sintering temperature is
1460 DEG C, soaking time 1min.Fig. 2 is the tissue of the self-passivation W alloy obtained under the process conditions.Homogeneous knot can be obtained
The self-passivation W alloy of structure, matrix grain is less than 300nm, active element phase particle is less than 100nm.Higher heating rate, meaning
Taste the action time short in high temperature, this tissue for being beneficial to obtain fine crystalline substance and the powder characteristics for keeping original homogeneous.Pass through
Archimedes's drainage, measuring its relative density is 98.5%.Since atom will be promoted under SPS technology under to a certain degree
Migration, to be easier to realize densification.
Embodiment 2:
Under Ar protective atmosphere, successively weighing purity is 99.5%W powder 96.36g, Cr powder 12.54g and Zr powder 1.1g,
It is fitted into the WC ball grinder of 250ml together according to ratio of grinding media to material 5:1 and WC ball.Then on planetary ball mill, with rotational speed of ball-mill
The ball-milling technology for being 60h for 250rad/min, Ball-milling Time carries out ball milling, obtains corresponding alloy powder.Alloy powder is filled
It fills out in graphite jig, is densified using SPS technology.Sintering process: heating rate is 50 DEG C/min, sintering temperature is
1500 DEG C, soaking time 0min.The self-passivation W alloy of homogeneous texture can be obtained, matrix grain is less than 800nm, activation
Element phase particle is less than 100nm.By Archimedes's drainage, measuring its relative density is 97.2%.Obtain matrix grain ruler
Very little relatively previous case is big, on the other hand it is due to phase that this aspect, which is because higher sintering temperature facilitates crystal grain and grows up,
To lower heating rate, causing material, the duration is long at relatively high temperatures, grows up to also result in crystal grain.
Embodiment 3:
Under Ar protective atmosphere, successively weighing purity is 99.5%W powder 96.36g, Cr powder 12.54g and Zr powder 1.1g,
It is fitted into the WC ball grinder of 250ml together according to ratio of grinding media to material 5:1 and WC ball.Then on planetary ball mill, with rotational speed of ball-mill
The ball-milling technology for being 60h for 250rad/min, Ball-milling Time carries out ball milling, obtains corresponding alloy powder.Alloy powder is filled
It fills out in graphite jig, is densified using SPS technology.Sintering process: heating rate is 200 DEG C/min, sintering temperature is
1380 DEG C, soaking time 5min.It was found that preparation self-passivation W alloy Solid solution precipitation cenotype, matrix grain be less than 400nm,
Active element phase particle is less than 100nm.By Archimedes's drainage, measuring its relative density is 96.5%.When due to heat preservation
Between be 5min, last crystallite dimension is more bigger than embodiment 1.In addition, sintering temperature is lower, thus its consistency relatively preceding two is real
It is more slightly lower to apply regular meeting.
Claims (5)
1. a kind of high-densit, fine brilliant, homogeneous texture self-passivation tungsten alloy preparation method, it is characterised in that:
It is prepared using mechanical alloying method combination SPS technology, is prepared by control milling parameters and sintering process parameter
Self-passivation W alloy block with long-time high temperature oxidation resistance；Include the following steps:
Step 1: under Ar protective atmosphere, amount weighs W powder, Cr powder and Zr powder that purity is 99.5% according to the ratio, grinds together with WC
Ball is placed in the WC ball grinder of 250ml, and mechanical ball mill is then carried out on planetary ball mill, by regulating and controlling rotational speed of ball-mill, ball
The techniques such as time consuming, ratio of grinding media to material, milling atmosphere are to obtain the self-passivation W alloy powder of homogeneous；
Step 2: the self-passivation W alloy powder filling that step 1 is obtained is in graphite jig, using discharge plasma sintering technique
The homogeneous self-passivation W alloy powder of acquisition is densified, heating rate, isothermal time, sintering in control sintering process are passed through
The technological parameters such as temperature, to obtain high-compactness, fine brilliant, homogeneous texture self-passivation W alloy.
2. preparation method according to claim 1, it is characterised in that:
In step 1, in order to obtain the self-passivation W alloy powder of homogeneous, Ball-milling Time is 2~80h, rotational speed of ball-mill is 150~
400rad/min, ratio of grinding media to material are 5:1~15:1, milling atmosphere Ar.
3. preparation method according to claim 1, it is characterised in that:
In step 2, in order to obtain high-densit, fine brilliant, homogeneous texture self-passivation W alloy, SPS technological parameter modification scope: rise
Warm rate is 50~300 DEG C/min, sintering temperature is 1360~1600 DEG C, soaking time is 0~5min.
4. preparation method according to claim 1, it is characterised in that:
The basic component of the self-passivation W alloy includes: W matrix, is passivated element Cr and active element Y and/or Zr；Wherein,
10wt%≤passivation element Cr≤13wt%, 0wt% < active element Y and/or Zr≤2wt%.
5. preparation method according to claim 1, it is characterised in that:
Crystallite dimension < 1 μm of the self-passivation W alloy, matrix are uniform W-Cr solid solution homogeneous structure, active element
Phase particle < 100nm and disperse is evenly distributed in W-Cr matrix.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110438357A (en) * | 2019-09-17 | 2019-11-12 | 合肥工业大学 | A method of quickly preparing homogeneous texture tungsten alloy |
| CN111139388A (en) * | 2020-03-09 | 2020-05-12 | 合肥工业大学 | Low-alloy-element-reinforced high-temperature oxidation-resistant self-passivated tungsten alloy and preparation method thereof |
| CN111334695A (en) * | 2020-03-09 | 2020-06-26 | 合肥工业大学 | High-density nano W alloy with good self-passivation behavior and preparation method thereof |
| CN111334678A (en) * | 2020-03-09 | 2020-06-26 | 合肥工业大学 | Method for inhibiting Cr precipitation behavior in W-Cr alloy and improving oxidation resistance of W-Cr alloy |
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| CN103602868A (en) * | 2013-12-07 | 2014-02-26 | 西北有色金属研究院 | Preparation method of high-density fine-grain W-TiC alloy material |
| US10016839B1 (en) * | 2017-03-09 | 2018-07-10 | King Fahd University Of Petroleum And Minerals | Friction stir welding tool and a method of fabricating the same |
| CN108866498A (en) * | 2018-08-10 | 2018-11-23 | 合肥工业大学 | A kind of W self-passivation alloy and preparation method thereof with long-time high temperature oxidation resistance |
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| CN103602868A (en) * | 2013-12-07 | 2014-02-26 | 西北有色金属研究院 | Preparation method of high-density fine-grain W-TiC alloy material |
| US10016839B1 (en) * | 2017-03-09 | 2018-07-10 | King Fahd University Of Petroleum And Minerals | Friction stir welding tool and a method of fabricating the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110438357A (en) * | 2019-09-17 | 2019-11-12 | 合肥工业大学 | A method of quickly preparing homogeneous texture tungsten alloy |
| CN111139388A (en) * | 2020-03-09 | 2020-05-12 | 合肥工业大学 | Low-alloy-element-reinforced high-temperature oxidation-resistant self-passivated tungsten alloy and preparation method thereof |
| CN111334695A (en) * | 2020-03-09 | 2020-06-26 | 合肥工业大学 | High-density nano W alloy with good self-passivation behavior and preparation method thereof |
| CN111334678A (en) * | 2020-03-09 | 2020-06-26 | 合肥工业大学 | Method for inhibiting Cr precipitation behavior in W-Cr alloy and improving oxidation resistance of W-Cr alloy |
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Application publication date: 20190628 |