CN107974603A - A kind of resistance to high temperature oxidation two-phase composite tungsten material and preparation method thereof - Google Patents

A kind of resistance to high temperature oxidation two-phase composite tungsten material and preparation method thereof Download PDF

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CN107974603A
CN107974603A CN201711170003.XA CN201711170003A CN107974603A CN 107974603 A CN107974603 A CN 107974603A CN 201711170003 A CN201711170003 A CN 201711170003A CN 107974603 A CN107974603 A CN 107974603A
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wsi
preparation
phase
high temperature
resistance
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CN107974603B (en
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罗来马
黄科
刘家琴
昝祥
刘东光
朱晓勇
吴玉程
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Hefei University of Technology
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder

Abstract

The invention discloses a kind of resistance to high temperature oxidation two-phase composite tungsten material and preparation method thereof, and the alloy double phase component of wherein resistance to high temperature oxidation two-phase composite tungsten material doping is WSi2With W0.67Cr0.33, wherein each component is configured to by atomic percent：WSi20.5 1.5%, W0.67Cr0.3398.5 99.5%.By WSi2Alloyed powder with through W made from self- propagating0.67Cr0.33(W 12wt.%Cr) alloyed powder is mixed in proportion, and alloy sample is prepared by discharge plasma sintering.Under the synergistic effect of two-phase, the high-temperature oxidation resistance of tungsten-bast alloy is not only significantly improved, but also significantly improves the mechanical property of tungsten-based composite material at high temperature at the same time.

Description

A kind of resistance to high temperature oxidation two-phase composite tungsten material and preparation method thereof
Technical field
The present invention relates to a kind of metallic composite and preparation method thereof, specifically a kind of resistance to high temperature oxidation two-phase tungsten Composite material and preparation method thereof.
Background technology
Controlled thermonuclear fusion can be the preferable energy in human society future, it is considered to be can effectively solve human future energy One of main outlet of source demand.Tungsten have high-melting-point, highly thermally conductive, minimum to the adsorbance of deuterium and tritium, radioactivity is low, not with H Reaction, the features such as anti-sputtering ability is strong, from the point of view of current research, tungsten is considered as most promising PFMs (Plasma Facing Materials).But when the accident of cooling agent failure occurs in fusion reactor, air will enter in the reactor of vacuum, and PFMs will Bear 1200 DEG C of transient temperature.In practical applications, the synergistic effect of oxygen and vapor causes tungsten material in humid air Rapid oxidation.In order to research and develop the intelligent tungsten alloy of self-passivation, domestic and international researcher employs antioxygen of the doping Cr elements to tungsten Changing performance is improved.W-Cr bianry alloys form compact oxidation layer Cr2O3, but Cr in high-temperature oxidation environment is exposed to for a long time2O3 Oxide layer is difficult to keep stablizing, and is unable to maintain that long-term passivation.Therefore active element is added into W-Cr Binary Alloy Systems, carried The antioxygenic property of high alloy.
At present, the more active element of research report doping W-Cr alloys mainly has Ti, Y, Si element etc., universal both at home and abroad Method be to add W, Cr, third element in the form of simple substance, burnt after long-time mechanical alloying when small (80) Knot.But traditional mechanical alloying technique has disadvantages that, for example, energy consumption is serious；Yield is relatively low to be insufficient for actual life Produce application demand；Mechanical alloying is incomplete；Introduce impurity etc..But use WSi2Doping W-Cr alloys have no report.WSi2 W-Cr two-phase alloys is adulterated, the antioxygenic property and mechanical behavior under high temperature of W alloy can be significantly improved.
The content of the invention
The present invention is intended to provide a kind of resistance to high temperature oxidation two-phase composite tungsten material and preparation method thereof, technology to be solved Problem is to improve the resistance to high temperature oxidation of W-Cr binary alloy materials by the screening of doped chemical and the optimization of preparation process Performance and water resistant mist high temperature oxidation resistance.
Resistance to high temperature oxidation two-phase composite tungsten material of the present invention, its alloy double phase component adulterated is WSi2With W0.67Cr0.33, Wherein each component is configured to by atomic percent：WSi20.5-1.5%, W0.67Cr0.3398.5-99.5%.
The preparation method of resistance to high temperature oxidation two-phase composite tungsten material of the present invention, includes the following steps：
Step 1：Mixed powder
By WSi2Alloyed powder and W0.67Cr0.33Alloyed powder (it is W-12wt.%Cr to be converted into quality than chemical formula) 400 turns/ It is uniformly mixed when stirring 2 is small in the mixed powder machine of minute, obtains two-phase composite powder；Particle Sizes are：WSi2Particle is averaged Size is 4.0 microns, W0.67Cr0.33Particle mean size is 5.2 microns.
The powder of 1/3rd volumes is loaded in step 1 in mixing tank, sets mixed powder machine rotating speed 400r/min, the time is 2h。
Step 2：Sintering
The two-phase composite powder that step 1 is obtained loads graphite jig, then mould is put into discharge plasma sintering stove, At room temperature to sintering stove evacuation, 1450 DEG C are warming up to after 8.5 minutes and keeps the temperature 1 minute, furnace chamber vacuum is kept in sintering process For 2-8Pa, control pressure is no more than 50MPa in sintering, and room temperature is down to after insulation, that is, obtains (WSi2)x(W0.67Cr0.33)y Two-phase tungsten composites.Cr, Si element are present in tungsten-bast alloy in the form of compound, on the one hand, are prevented and made The oxidation of Cr, Si element during standby, on the other hand, avoids and occurs Cr, Si enrichment of element region in block is sintered.
In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
Beneficial effects of the present invention are embodied in：
WSi2It is the metallic compound of tetragonal crystal structure, W0.67Cr0.33It is the unlimited displacement solid solution of body-centered cubic structure Body.Compared with traditional Mechanical Alloying, by WSi2With W0.67Cr0.33Alloy powder is directly mixed with following advantage：It is first First, by way of adding alloyed powder, tradition machinery alloying process is instead of, the energy is saved, yield greatly improved；Its It is secondary, Cr, Si element activity are advantageously weakened, prevents that material preparation process from being aoxidized so that active element Cr, Si sample after sintering Exist in product in the form of solid solution and compound；Finally, in oxidizing process subsurface stratum WSi2With W0.67Cr0.33Aoxidize respectively W-Si-O the and W-Cr-O oxides of formation significantly reduce oxide layer Cr2O3With the thermal stress and growth stress of W matrixes, improve The binding ability of oxide layer and matrix, so as to improve the high temperature oxidation resistance of tungsten-based composite material.It is more with studying at present W-Cr-Si ternary alloy three-partalloys compare, directly adulterate WSi2Effectively steadyization Cr2O3Oxide layer, reduces the generation of rich tungsten phase.It is rich The WO that tungsten is mutually formed in oxidizing process3There is serious harm for the antioxygenic property of material.And work as nuclear fusion reaction When accident occurs for heap, it may appear that 1200 DEG C of high temperature and water mist, oxygen existing extreme case jointly, at this time Cr2O3It can be volatilized into CrO3, protective layer fracture failure.And the glass phase SiO with self-repair function2Can still stable in 1200 DEG C of environment it deposit , and OH in water mist can be reduced-Ion is spread in protective layer.And in WSi2With W0.67Cr0.33The synergistic effect of two-phase Under, significantly improve the high temperature oxidation resistance of tungsten sill, when oxidation 15 is small after, rate of body weight gain is only the 1/8-1/ of pure tungsten material 10。
Brief description of the drawings
Fig. 1 is (WSi2)0.01(W0.67Cr0.33)0.99Alloy sintering state microstructure image, Fig. 1 a are surface topography, Fig. 1 b For fracture apperance.
Fig. 2 is to aoxidize after ten minutes, W0.67Cr0.33(WSi2)0.01(W0.67Cr0.33)0.99Tin oxide layers Cross Section Morphology Image, Fig. 2 a are W0.67Cr0.33Oxide layer Cross Section Morphology, Fig. 2 b (WSi2)0.01(W0.67Cr0.33)0.99Alloy oxidation layer cross section shape Looks.
Fig. 3 is oxidizing dynamics curve when oxidation 15 is small.
Fig. 4 be oxidation 15 it is small when after alloy feature image, Fig. 4 a pure tungstens, Fig. 4 b W0.67Cr0.33, Fig. 4 c (WSi2)0.01 (W0.67Cr0.33)0.99。
Embodiment
Technical scheme is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
Resistance to high temperature oxidation (WSi in the present embodiment2)0.005(W0.67Cr0.33)0.995Two-phase tungsten composites, it is adulterated Alloy double phase component be WSi2With W0.67Cr0.33, wherein each component is configured to by atomic percent：WSi20.5%, W0.67Cr0.3399.5%.
Resistance to high temperature oxidation (WSi in the present embodiment2)0.005(W0.67Cr0.33)0.995The preparation side of two-phase tungsten composites Method is as follows：
1st, powder processed：By the WSi of proportional quantity2With W0.67Cr0.33For alloyed powder in 400 revs/min of mixed powder machine, stirring 2 is small When, obtain two-phase composite powder；Particle Sizes are：WSi2Particle mean size is 4.0 microns, W0.67Cr0.33Particle is averaged Size is 5.2 microns.
2nd, sinter：Two-phase composite powder is loaded into graphite jig, then mould is put into discharge plasma sintering stove, room temperature Under to sinter stove evacuation, be warming up to after 8.5 minute minute 1450 DEG C keep the temperature 1 minute, in sintering process keep furnace chamber vacuum 2Pa, control pressure is no more than 50MPa in sintering, and room temperature is down to after insulation, that is, obtains (WSi2)0.005 (W0.67Cr0.33)0.995Two-phase tungsten composites.
In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
The second distributed mutually of composite material after sintering is uniform, and oxide layer is relatively compact in oxidizing process, has higher resist High temperature oxidation resistance, oxidation 15 it is small when after, rate of body weight gain is only the 1/10 of pure tungsten material.
Embodiment 2：
Resistance to high temperature oxidation (WSi in the present embodiment2)0.015(W0.67Cr0.33)0.985Two-phase tungsten composites, it is adulterated Alloy double phase component be WSi2With W0.67Cr0.33, wherein each component is configured to by atomic percent：WSi21.5%, W0.67Cr0.3398.5%.
Resistance to high temperature oxidation (WSi in the present embodiment2)0.015(W0.67Cr0.33)0.985The preparation side of two-phase tungsten composites Method is as follows：
1st, powder processed：By WSi2With a certain proportion of W0.67Cr0.33For alloyed powder in 400 revs/min of mixed powder machine, stirring 2 is small When, obtain two-phase composite powder；Particle Sizes are：WSi2Particle mean size is 4.0 microns, W0.67Cr0.33Particle is averaged Size is 5.2 microns.
2nd, sinter：Two-phase composite powder is loaded into graphite jig, then mould is put into discharge plasma sintering stove, room temperature Under to sinter stove evacuation, be warming up to after 8.5 minutes 1450 DEG C keep the temperature 1 minute, in sintering process keep furnace chamber vacuum be 5Pa, control pressure is no more than 50MPa in sintering, and room temperature is down to after insulation, that is, obtains (WSi2)0.015 (W0.67Cr0.33)0.985Two-phase tungsten composites.
In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
The second distributed mutually of composite material after sintering is uniform, and oxide layer is relatively compact in oxidizing process, has higher resist High temperature oxidation resistance, oxidation 15 it is small when after, rate of body weight gain is only the 1/8 of pure tungsten material.
Embodiment 3：
Resistance to high temperature oxidation (WSi in the present embodiment2)0.01(W0.67Cr0.33)0.99Two-phase tungsten composites, what it was adulterated Alloy double phase component is WSi2With W0.67Cr0.33, wherein each component is configured to by atomic percent：WSi21%, W0.67Cr0.33 99%.
Resistance to high temperature oxidation (WSi in the present embodiment2)0.01(W0.67Cr0.33)0.99The preparation method of two-phase tungsten composites It is as follows：
1st, powder processed：By WSi2With a certain proportion of W0.67Cr0.33For alloyed powder in 400 revs/min of mixed powder machine, stirring 2 is small When, obtain two-phase composite powder；Particle Sizes are：WSi2Particle mean size is 4.0 microns, W0.67Cr0.33Particle is averaged Size is 5.2 microns.
2nd, sinter：Two-phase composite powder is loaded into graphite jig, then mould is put into discharge plasma sintering stove, room temperature Under to sinter stove evacuation, be warming up to after 8.5 minute minute 1450 DEG C keep the temperature 1 minute, in sintering process keep furnace chamber vacuum For 8Pa, control pressure is no more than 50MPa in sintering, and room temperature is down to after insulation, that is, obtains (WSi2)0.01 (W0.67Cr0.33)0.99Two-phase tungsten composites.
In sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
Composite material pattern after sintering is as shown in Figure 1, the second distributed mutually is uniform, the sky of material from microstructure Gap is less, relatively compact.To business tungsten, W0.67Cr0.33(self- propagating) alloy, (WSi2)0.01(W0.67Cr0.33)0.99Two-phase tungsten closes Epoxidation experiments when gold carries out 1000 degree Celsius 15 small.Oxidizing atmosphere：20vol.%O2, 80vol.%N2.In order to analyze oxidation Mechanism, after ten minutes, observation sample oxidation bed boundary is as shown in Fig. 2, W for oxidation0.67Cr0.33The oxidation thickness of (self- propagating) alloy About 2.6 μm of degree, and (WSi2)0.01(W0.67Cr0.33)0.99The oxidated layer thickness of two-phase tungsten alloy is about 1.8 μm, and oxide layer It is relatively compact.Oxidation 15 as a child oxidizing dynamics curve as shown in figure 3, (WSi2)0.01(W0.67Cr0.33)0.99Two-phase tungsten alloy With excellent oxidation-resistance property, 15 it is small when oxidation weight gain be less than W0.67Cr0.33Alloy, far below business pure tungsten.Fig. 4 is Aoxidize 15 it is small when after alloy feature image, pure tungsten complete oxidation is yellow tungsten (WO3),(WSi2)0.01(W0.67Cr0.33)0.99Two-phase tungsten Alloy oxidation skin is compared with W0.67Cr0.33Alloy it is more fine and close.The second distributed mutually of composite material after sintering is uniform, in oxidizing process Oxide layer is relatively compact, has a higher high temperature oxidation resistance, when oxidation 15 is small after, rate of body weight gain is only the 1/9 of pure tungsten material.

Claims (7)

  1. A kind of 1. resistance to high temperature oxidation two-phase composite tungsten material, it is characterised in that：Its alloy double phase component adulterated is WSi2With W0.67Cr0.33, wherein each component is configured to by atomic percent：WSi20.5-1.5%, W0.67Cr0.3398.5-99.5%.
  2. 2. the preparation method of the resistance to high temperature oxidation two-phase composite tungsten material described in a kind of claim 1, it is characterised in that including such as Lower step：
    Step 1：Mixed powder
    By WSi2Alloyed powder and W0.67Cr0.33Alloyed powder is added in mixing tank and is uniformly mixed, and obtains two-phase composite powder；
    Step 2：Sintering
    The two-phase composite powder that step 1 is obtained loads graphite jig, then mould is put into discharge plasma sintering stove, room temperature Under to sinter stove evacuation, be warming up to 1450 DEG C keep the temperature 1 minute, in sintering process keep furnace chamber vacuum, carry out vacuum-sintering, Room temperature is down to after insulation, that is, obtains (WSi2)x(W0.67Cr0.33)yTwo-phase tungsten composites.
  3. 3. preparation method according to claim 2, it is characterised in that：
    In step 1, Particle Sizes are：WSi2Particle mean size is 4.0 microns, W0.67Cr0.33Particle mean size is 5.2 micron.
  4. 4. preparation method according to claim 2, it is characterised in that：
    In step 1, the powder of 1/3rd volumes, mixing tank rotating speed 400r/min, mixing time 2h are loaded in mixing tank.
  5. 5. preparation method according to claim 2, it is characterised in that：
    In step 2, pressure is controlled to be no more than 50MPa in sintering process.
  6. 6. preparation method according to claim 2, it is characterised in that：
    In step 2, in sintering process, heating rate is 100 DEG C/min, and rate of temperature fall is 100 DEG C/min.
  7. 7. preparation method according to claim 2, it is characterised in that：
    It is 2-8Pa that furnace chamber vacuum is kept in step 2, in sintering process.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108817387A (en) * 2018-07-09 2018-11-16 合肥工业大学 A kind of preparation method of the tungsten-based composite material with high rigidity and high temperature oxidation resistance

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1123908A1 (en) * 1998-07-07 2001-08-16 Institut Fiziki Tverdogo Tela Akademii Nauk Sssr High-temperature strength and heat-resistant composite material "refsic"
US20130096217A1 (en) * 2011-10-12 2013-04-18 Wayde R. Schmidt Method for fabricating a ceramic material
CN104451320A (en) * 2014-11-20 2015-03-25 中原工学院 Method of preparing Mo(Si,Al)-2-SiC metal ceramic composite material through reaction method
CN106834777A (en) * 2016-12-30 2017-06-13 梅庆波 A kind of preparation method of low-expansion coefficient composition metal base ceramic die material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1123908A1 (en) * 1998-07-07 2001-08-16 Institut Fiziki Tverdogo Tela Akademii Nauk Sssr High-temperature strength and heat-resistant composite material "refsic"
US20130096217A1 (en) * 2011-10-12 2013-04-18 Wayde R. Schmidt Method for fabricating a ceramic material
CN104451320A (en) * 2014-11-20 2015-03-25 中原工学院 Method of preparing Mo(Si,Al)-2-SiC metal ceramic composite material through reaction method
CN106834777A (en) * 2016-12-30 2017-06-13 梅庆波 A kind of preparation method of low-expansion coefficient composition metal base ceramic die material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108817387A (en) * 2018-07-09 2018-11-16 合肥工业大学 A kind of preparation method of the tungsten-based composite material with high rigidity and high temperature oxidation resistance
CN108817387B (en) * 2018-07-09 2020-02-14 合肥工业大学 Preparation method of tungsten-based composite material with high hardness and high-temperature oxidation resistance

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