CN106676358A

CN106676358A - W-K/W-K-Y alloy with nano potassium bubble distribution and preparing method of alloy

Info

Publication number: CN106676358A
Application number: CN201611222474.6A
Authority: CN
Inventors: 唐军; 石柯; 黄波
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2016-12-27
Filing date: 2016-12-27
Publication date: 2017-05-17

Abstract

The invention discloses a W-K/W-K-Y alloy with nano potassium bubble distribution and a preparing method of the alloy. The blocky W-K/W-K-Y alloy is obtained through sintering of mixed powder with W powder doped with K and Y powder with the weight content of 0 to 0.1%, the potassium bubble size in the W-K/W-K-Y alloy ranges from 20 nm to 130 nm, and the bubbles are distributed in the crystal boundary and crystals of the W-K/W-K-Y alloy; according to the W-K/W-K-Y alloy with nano potassium bubble distribution, the potassium bubble size is in nano scale, the compactness, thermal shock resistance and the like of the W-K alloy or W-K-Y alloy are improved, the potassium bubbles are distributed in the crystal boundary and the crystals, the binding force between the crystalline grains can be enhanced, the tensile performance and thermal shock resistance can be improved, and meanwhile the defect that in the traditional technology, the nano potassium bubble structure is obtained only from the wire W-K alloy is overcome.

Description

W-K/W-K-Y alloys of nanometer potassium bubble distribution and preparation method thereof

Technical field

The invention belongs to field of alloy preparation technology, is related to a kind of W-K alloy preparation techniques, and in particular to a kind of nanometer potassium W-K/W-K-Y alloys of bubble distribution and preparation method thereof.

Background technology

Facing plasma material is mainly limited with the service life of part by transient state thermal shock, PFMs (towards etc. Gas ions plasma facing material) thermal shock resistance research just seem particularly critical, as fusion reactor towards plasma first The candidate material of wall, tungsten-potassium (W-K) alloy is particularly subject to by force because of excellent properties such as its good heat shock resistance, tensile strength height Strong concern.

The preparation of traditional W-K alloys is by AKS tungsten powders compressing (rod type), subsequently in H first₂Atmosphere is in about 2800 DEG C At a temperature of obtain sintered blank after incipient fusion sintering 30min, then improve its consistency through forging；The sintering process temperature of the method Degree is high, time length and potassium bubble can be migrated to crystal boundary upon formation because of unstability, and can also merge length between potassium bubble Greatly, the potassium bubble for ultimately causing business W-K alloy is bigger than normal and be distributed in grain boundary sites；The potassium bubble of W-K alloys is bigger than normal to be concentrated with potassium bubble The reinforcing decreased effectiveness that grain boundary sites steep can potassium is distributed in, so that overall thermal shock resistance properties and intensity of alloy etc. weaken.

Therefore, how to solve the problems, such as that potassium bubble is bigger than normal and potassium steeps integrated distribution in crystal boundary in W-K alloys, there is provided Yi Zhongkang Thermal shock resistance properties it is excellent towards plasma facing materials, be a difficult point of current research.

The content of the invention

The purpose of the present invention aims to business W-K alloy potassium and steeps deficiency bigger than normal and being distributed in grain boundary sites, there is provided one Plant block nanometer potassium and steep W-K/W-K-Y alloys of distribution and preparation method thereof, the potassium bubble that it is included is that nanoscale potassium steeps and divides Cloth is in crystal boundary and transgranular.

The W-K/W-K-Y alloys of the nanometer potassium bubble distribution that the present invention is provided, it is characterised in that be by the W powder and weight for mixing K Content is that the mixing powder sintering of 0~0.1%Y powder obtains block W-K/W-K-Y alloys, the potassium bubble in the W-K/W-K-Y alloys Size is 20~130nm, is distributed in the crystal boundary of W-K/W-K-Y alloys and transgranular.In W-K/W-K-Y alloys, potassium bubble size is got over The raising of little consistency and thermal shock resistance to alloy etc. is more beneficial；And in the W-K/W-K-Y alloys of the present invention, Potassium bubble is not distributed only over grain boundary sites, and is also distributed transgranular.The potassium bubble of crystal boundary distribution can strengthen intercrystalline combination Power so as to which tensile property is lifted；And the potassium bubble of transgranular distribution can play certain cushioning effect so as to thermal shock resistance Lifted.The W-K/W-K-Y alloys of this nanometer of potassium bubble distribution, mix K contents in the W powder of K and, in 46ppm-144ppm, particularly work as Potassium content is controlled in 68ppm-108ppm, and potassium bubble size in the block W-K/W-K-Y alloys of acquisition can be made to reach about 22- 92nm, it has good compactness and thermal shock resistance etc..The W powder for mixing K that the present invention is adopted is for purchased from Zi Gong hard The AKS-W powder of Alloy Plant Chengdu branch company, the AKS-W powder is mixed with potassium silicate and aluminum nitrate as the object that adulterates, by traditional AKS General labourer's skill is obtained, and the particle diameter of the AKS-W powder is 2~3 μm, purity is higher than 99.9%.Enter again particularly on the basis of the W powder for mixing K The W-K-Y alloys of the nanometer potassium bubble distribution of doping in one step Y powder, while potassium bubble size in improving alloy and forming position, enter One step improves the thermal shock resistance properties of alloy itself, so as to provide a kind of fusion reactor of function admirable towards the wall of plasma first Material.The weight content of Y powder is 0.05~0.1% in W-K-Y alloys.

The W-K/W-K-Y alloy preparation methods of the nanometer potassium bubble distribution that the present invention is provided, comprise the following steps：

Step (1), the W powder that the W powder for mixing K is weighed in inert atmosphere or K is mixed is filled in mould with the mixed powder of Y powder In；

Step (2), the mould of W powder and Y powder mixed powders that will be filled with mixing the W powder of K or mixing K is put in SPS sintering cavities, Be evacuated to no more than 5Pa, be then molded under 40~120Mpa pressure, then be warming up to 1500~2000 DEG C sintering 2~ 6min obtains a nanometer W-K/W-K-Y alloy blocks for potassium bubble distribution.

The preparation method of the present invention, takes and is sintered under higher pressure, only can sinter 2 in 1500~2000 DEG C ~6min, just makes the W powder for mixing K or mixes the W powder of K and the mixed powder molding in the short period of time of Y powder obtains W-K/W-K-Y alloy blocks Body, due to sintering time it is shorter, it is to avoid potassium bubble is migrated to coalescence between crystal boundary and potassium bubble, so as to the block W- for obtaining Potassium steeps size Control in 20~130nm in K/W-K-Y alloys, and while is distributed in alloy crystal boundary and transgranular.

The W-K/W-K-Y alloy preparation methods of above-mentioned nanometer potassium bubble distribution, in the step (1), in order to ensure W-K/W- The purity of K-Y alloys, the W powder for mixing K or the W powder for mixing K and Y powder, need to weigh in inert atmosphere and will mix the W powder of K or mix K's W powder is fitted in mould with Y powder mixed powders.The inert atmosphere refers to that oxygen content is less than 0.1ppm's less than 0.1ppm, water content Argon atmosphere.

The W-K/W-K-Y alloy preparation methods of above-mentioned nanometer potassium bubble distribution, in the step (1), in order to ensure follow-up burning The thermal efficiency in knot, mould preferentially selects graphite jig；For the ease of the later product demoulding, can be with graphite jig inner surface The resistant to elevated temperatures boron nitride releasing agent of even application；For separating releasing agent and W-K/W-K-Y alloys, and further improve insulation effect Really, graphite paper can be put in graphite jig will mix the W powder of K or the W powder of K and wrap up with Y powder mixed powders；Can also with by The graphite insulation sleeve of graphite rope and graphite felt composition, graphite jig is completely encapsulated in graphite felt, in order to not affect SPS to burn Vacuum in knot cavity, needs fully be dried graphite jig, graphite paper, graphite felt etc. using being front put in drying baker.

The W-K/W-K-Y alloy preparation methods of above-mentioned nanometer potassium bubble distribution, molding pressure size is preferably controlled in the step (2) System is in 80-120Mpa scopes.

The W-K/W-K-Y alloy preparation methods of above-mentioned nanometer potassium bubble distribution, sintering temperature is preferably controlled in the step (2) 1750~1900 DEG C of scopes, sintering time at least 2min；Because the product prepared in embodiment of the present invention is smaller, sintering is warm General control is spent in 2-6min, when product increases, as long as proper extension on this basis.

The W-K/W-K-Y alloy preparation methods of above-mentioned nanometer potassium bubble distribution, find under study for action, when being sintered using two-part During mode, potassium bubble size and distributing position are controllable more preferably in the block W-K/W-K-Y alloys for obtaining, two sections in the present invention Then formula sintering processing is warming up to again first temperature in SPS sintering cavities to be risen to into 1300~1400 DEG C of 6~10min of insulation 1500~2000 DEG C (preferably 1750~1900 DEG C) are sintered at least 2 minutes.Additionally, 1300~1400 DEG C be incubated 6~ 10min, can also make the decomposes before product completely densification of some impurity in product out, improve the pure of final product Degree.

The W-K-Y alloys of the nanometer potassium bubble distribution obtained by above-mentioned preparation method, the potassium bubble size in W-K alloys are improved While with forming position, the thermal shock resistance properties of W-K alloys is further improved.In above-mentioned preparation method, the W powder and Y powder of K is mixed Mixing, can disclosed conventional ball-milling process method be carried out using this area.In order to ensure material purity, the W powder of K is mixed Need to complete charging in inert atmosphere with Y powder, multiple evacuation-logical hydrogen-argon-mixed circulation behaviour is then carried out to ball grinder Make, then carry out being milled to the W powder for mixing K and Y powder mix homogeneously.

As can be seen from the above analysis sintering temperature and sintering time can affect potassium in W-K alloys or W-K-Y alloys The size of bubble and distribution, when sintering temperature is too high, overlong time when, potassium bubble can be made to migrate to crystalline substance because unstable upon formation Can also coalescence between boundary, and potassium bubble；It has been investigated that, reduce high temperature section sintering temperature, shorten sintering time, can be effective Solve the above problems.

Compared with prior art, the invention has the advantages that：

The W-K alloys or W-K-Y alloys of the nanometer potassium bubble distribution that the 1, the present invention is provided, it is to avoid potassium in business W-K alloy Bubble problem bigger than normal and being concentrated mainly on grain boundary sites, its potassium bubble size is nanoscale, can reach 20~130nm, contributes to W-K The raising of the consistency and thermal shock resistance of alloy or W-K-Y alloys etc.；And potassium bubble is distributed in crystal boundary and transgranular, not only may be used To strengthen intercrystalline adhesion so as to which tensile property is lifted, and the potassium bubble of transgranular distribution can play certain buffering Effect so as to which thermal shock resistance is lifted；

2nd, the present invention can realize potassium bubble nano-grade size in block W-K alloys or W-K-Y alloys and be distributed in crystalline substance Boundary and transgranular potassium bubble structure, overcome traditional handicraft and are only capable of the getable nanometer potassium bubble structure of ability in silk material W-K alloy Drawback.

3rd, the present invention is by the W-K-Y alloys that obtain of doping, and potassium bubble size and forming position is same in W-K alloys are improved When, the thermal shock resistance properties of W-K alloys can further be improved by the Y for adulterating.

4th, the W-K alloys or W-K-Y alloy preparation methods of nanometer potassium of the invention bubble distribution, in higher molding pressure (40~120Mpa), can complete to sinter preparation process in 1500~2000 DEG C of 2~6min of sintering, relative to traditional preparation side Method, not only reduces high temperature sintering temperature, and shortens sintering time, can so avoid potassium from steeping upon formation because of shakiness Surely migrate to crystal boundary and potassium bubble between coalescence, so as to ensure the block W-K alloys for make acquisition in potassium bubble size Control exist 20~130nm, and while it is distributed in alloy crystal boundary and transgranular.

5th, the present invention is only sintered by SPS one-part forms or two-part sintering just can make acquisition with AKS-W powder as raw material Nanometer potassium bubble distribution W-K alloys, preparation process is simple, short preparation period, it is adaptable to be widely popularized in this area.

Description of the drawings

Fig. 1 is potassium bubble distribution in the W-K alloys that the embodiment of the present invention 1 is obtained to embodiment 3 under different sintering temperatures SEM schemes, wherein (a) be embodiment 1 in 1600 DEG C of sintered samples, be (b) embodiment 2 in 1750 DEG C of sintered samples, (C) to implement Example 3 is in 1900 DEG C of sintered samples.

Fig. 2 is transgranular and grain boundaries nanometer potassium bubble in the W-K alloys obtained when K contents are 82ppm in the embodiment of the present invention 8 The TEM figures of distribution, wherein (a) is in the sample for amplifying observation under conditions of 100,000 times, (b) it is to amplify under conditions of 500,000 times The sample of observation, is (c) in the sample for amplifying observation under conditions of 200,000 times.

Specific embodiment

Clear, complete description is carried out to the technical scheme of various embodiments of the present invention below with reference to accompanying drawing, it is clear that retouched State a part of embodiment that embodiment is only the present invention, rather than the embodiment of whole.Based on the embodiment in the present invention, this The resulting all other embodiment on the premise of creative work is not made of field those of ordinary skill, belongs to this Bright protected scope.

In order to ensure the sintering temperature of raw material to be sintered, the mould adopted in following examples is being used for graphite jig Before graphite jig, high temperature resistant boron nitride releasing agent is first uniformly sprayed at the inner surface of graphite jig by needs, is then put Toast more than 2 hours in electric drying oven with forced convection, to remove the organic solvent for being used for disperseing boron nitride.In following examples also Graphite paper is placed in graphite jig, for wrapping up sample to be sintered, specific implementation is to cut out in advance and graphite jig Graphite paper and the graphite paper disk consistent with graphite jig internal diameter that inner surface is fitted completely, and using graphite rope and by graphite The graphite felt that mould is coated completely makes a graphite and is incubated sleeve.The graphite such as above-mentioned graphite jig, graphite paper, graphite paper disk Product be fully dried in electric drying oven with forced convection using front being needed to be put into, and prevents from affecting the vacuum of vacuum chamber during high temperature sintering Degree.

The W powder for mixing K adopted in following examples for purchased from the AKS-W powder of the long Chengdu branch company of Zi Gong hard alloy, its Particle diameter is 2~3 μm, and purity is higher than 99.9%.

Embodiment 1 is to embodiment 3

Embodiment 1

The content of K is 68ppm in AKS-W powder in the present embodiment.

The present embodiment nanometer potassium steeps the W-K alloy preparation process of distribution：

(1) by graphite pressure head in the glove box of the argon atmosphere in oxygen content less than 0.1ppm, water content less than 0.1ppm Load one end of graphite jig sleeve, and be put into a ready graphite for graphite paper and graphite pressure head to be separated in advance Paper disk, by graphite paper the inner surface of graphite jig is fitted in；After graphite jig is ready to complete, the AKS-W powder 10g of weighing are filled out Fill in graphite jig, cover another piece of graphite paper disk and beyond the Great Wall graphite pressure head, at graphite jig two ends Graphite pad is added, Then graphite jig is forced into into 2MPa with powder compressing machine, make push-down head be higher by graphite jig sleeve length it is consistent；

(2) SPS sintering systems are opened, the graphite jig that step (1) prepares is put into graphite insulation sleeve, be put into SPS burnings In knot cavity, no more than 5Pa is evacuated to, then graphite jig is forced into into 80MPa, while with the intensification speed of 100 DEG C/min Rate is warming up to 1600 DEG C, and under the conditions of 80MPa pressure, 1600 DEG C 6min is incubated, using monochromatic infrared radiation thermometer in experimentation Carry out temperature survey and feedback；After the completion of sintering, about 30min is cooled down under vacuum conditions, then will sinter sample using tablet machine Product demoulding from graphite jig is taken out, and obtains W-K block alloys.

Embodiment 2

The AKS-W powder that the present embodiment is adopted is same as Example 1.

The preparation process of the W-K alloys of the present embodiment nanometer potassium bubble distribution is substantially the same manner as Example 1, and difference is The sintering temperature of the present embodiment is 1750 DEG C.

Embodiment 3

The AKS-W powder that the present embodiment is adopted is same as Example 1.

The preparation process of the W-K alloys of the present embodiment nanometer potassium bubble distribution is substantially the same manner as Example 1, and difference is The sintering temperature of the present embodiment is 1900 DEG C.

Embodiment 1 to sample prepared by embodiment 3 is processed by shot blasting, and observes potassium in each sample using SEM and TEM Bubble, as shown in figure 1, can only observe minimal amount of potassium bubble in the sample of the preparation of embodiment 1, and is smaller in size than 50nm, sample Consistency is 93.1%；The potassium bubble quantity observed in sample prepared by embodiment 2 is compared embodiment 1 and is increased considerably, and chi Very little about 50~100nm, sample consistency is 98.2%；The potassium bubble quantity observed in sample prepared by embodiment 3 compares reality Apply example 2 to have reduced, and its potassium bubble size is about 100~200nm, sample consistency is 99.1%.Can from above-mentioned analysis Go out, when sintering temperature is relatively low, it is difficult to form more potassium bubble, and sample consistency is relatively low；And when sintering temperature is higher, though So sample consistency is higher, but the potassium bubble for being formed is easily because potassium bubble merges and overgrowth, therefore, in preparation process preferably Sintering temperature is 1750~1900 DEG C, in the temperature range, not only can form more nanoscale potassium bubble, and sample is fine and close Degree is also relatively high.

Embodiment 4 is to embodiment 6

Embodiment 4

The content of K is 54ppm in AKS-W powder in the present embodiment.

The present embodiment nanometer potassium steeps the preparation process of the W-K alloys of distribution：

Step (1) is same as Example 1；

(2) SPS sintering systems are opened, the graphite jig that step (1) prepares is put into graphite insulation sleeve, be put into SPS burnings In knot cavity, no more than 5Pa is evacuated to, then graphite jig is forced into into 40MPa, while with the intensification speed of 100 DEG C/min Rate is warming up to 1750 DEG C, and under the conditions of 40MPa pressure, 1750 DEG C 2min is incubated, using monochromatic infrared radiation thermometer in experimentation Carry out temperature survey and feedback；After the completion of sintering, about 30min is cooled down under vacuum conditions, then will sinter sample using tablet machine Product demoulding from graphite jig is taken out, and obtains W-K block alloys.

Embodiment 5

The AKS-W powder that the present embodiment is adopted is same as Example 4.

The preparation process of the W-K alloys of the present embodiment nanometer potassium bubble distribution is substantially the same manner as Example 4, and difference is Graphite jig is forced into 80MPa by the present embodiment, and under the conditions of 80MPa pressure, 1750 DEG C 2min is incubated.

Embodiment 6

The AKS-W powder that the present embodiment is adopted is same as Example 4.

The preparation process of the W-K alloys of the present embodiment nanometer potassium bubble distribution is substantially the same manner as Example 4, and difference is Graphite jig is forced into 120MPa by the present embodiment, and under the conditions of 120MPa pressure, 1750 DEG C 2min is incubated.

Embodiment 4 to sample prepared by embodiment 6 is processed by shot blasting, and observes potassium in each sample using SEM and TEM Bubble, potassium bubble size is about 50~100nm in sample prepared by embodiment 4, and sample consistency is 94.79%；Prepared by embodiment 5 Potassium bubble size is about 50~100nm in sample, and its consistency is 97.25%；Potassium bubble size is about in sample prepared by embodiment 6 50~100nm, sample consistency is 98.26%.As can be seen from the above analysis, when applying pressure and being less, the densification of sample Property can be affected, although apply pressure it is larger when sample compactness preferably, it is contemplated that mould itself to be held during sintering The pressure received is not higher than 120MPa；Therefore, it is 80~120MPa that the preferable scope of pressure is applied in preparation process.

Embodiment 7 is to embodiment 11

Embodiment 7

The content of K is 46ppm in AKS-W powder in the present embodiment.

Step (1) is same as Example 1；

(2) SPS sintering systems are opened, the graphite jig that step (1) prepares is put into graphite insulation sleeve, be put into SPS burnings In knot cavity, no more than 5Pa is evacuated to, then graphite jig is forced into into 80MPa, while with the intensification speed of 100 DEG C/min Rate is warming up to 1400 DEG C, and under the conditions of 80MPa pressure, 1400 DEG C 6min is incubated；Then 1750 DEG C are warming up to again, in 80MPa pressures By force, 2min is incubated under the conditions of 1750 DEG C, temperature survey and feedback are carried out using monochromatic infrared radiation thermometer in experimentation；Sinter Cheng Hou, cools down under vacuum conditions about 30min, and then using tablet machine, by sintered sample, the demoulding from graphite jig is taken out, and is obtained To W-K block alloys.

Embodiment 8

The content of K is 82ppm in AKS-W powder in the present embodiment.

The preparation process of the W-K alloys of the present embodiment nanometer potassium bubble distribution is same as Example 7.

Embodiment 9

The content of K is 108ppm in AKS-W powder in the present embodiment.

Embodiment 10

The content of K is 122ppm in AKS-W powder in the present embodiment.

Embodiment 11

The content of K is 144ppm in AKS-W powder in the present embodiment.

Embodiment 7 to sample prepared by embodiment 11 is processed by shot blasting, and observes potassium in each sample using SEM and TEM Bubble, potassium bubble size is about 14~48nm in sample prepared by embodiment 7, and sample consistency is 98.3%；Sample prepared by embodiment 8 Potassium bubble size is about 24~70nm in product, and its consistency is 98.0%；In sample prepared by embodiment 9 potassium bubble size be about 22~ 92nm, sample consistency is 97.8%；Potassium bubble size is about 40~100nm, sample consistency in sample prepared by embodiment 10 For 97.3%；Potassium bubble size is about 35~123nm in sample prepared by embodiment 14, and sample consistency is 97.2%.From above-mentioned As can be seen that when K contents are on the low side, the potassium bubble quantity of formation is few and grain refining effect is not good enough for analysis；When K contents it is on the high side When, cavity can be caused to increase, consistency declines；Therefore, in preparation process when potassium content is in 68ppm-108ppm scopes, with it Potassium bubble size is about 22-92nm in the W-K alloys obtained for raw material；Potassium content tungsten potassium-sodium alloy within the range has excellent Thermal shock resistance and mechanical strength.

Additionally, from figure 2 it can be seen that nanoscale potassium bubble be not distributed only near W-K alloy crystal boundaries, be also distributed in W-K Alloy is transgranular.

Embodiment 12 is to embodiment 13

Embodiment 12

The content of K is 82ppm in AKS-W powder in the present embodiment, and Y powder is Aladdin reagent, and purity is 99.9%, and size is 325 mesh.

Prepared by the present embodiment is a nanometer W-K-Y alloys for potassium bubble distribution, and its preparation process is：

(1) will first weigh in the glove box of the argon atmosphere in oxygen content less than 0.1ppm, water content less than 0.1ppm AKS-W powder, then according to Y powder accounts for the ratio of the 0.05wt.% of AKS-W powder and Y powder gross weights to weigh Y powder, and will weigh AKS-W powder and Y powder pour ball grinder into, and (ball milling top tank structure adopts the WC-8wt.%Co of high hardness wear-resisting, and outer wall is stainless using 304 Steel matter) in, then according to weight compares 1：2 add two kinds of abrading-balls that diameter Distribution is 10mm and 6mm, and (wherein abrading-ball is using high hard The wear-resisting WC-8wt.%Co of degree, abrading-ball is 5 with the mass ratio of powder:1, then ball grinder is accessed into vacuum system and hydrogen argon is mixed Close gas bottle (hydrogen volume ratio accounts for 7%), first ball grinder is evacuated to into 10Pa, be then charged with it is hydrogen-argon-mixed to atmospheric pressure, Above operation is repeated, keeps for five times air pressure in spherical tank to be 0.9 atmospheric pressure afterwards repeatedly, ball milling tank valve is closed, subsequently by ball Grinding jar is fitted in ball mill, the ball milling 40h under the conditions of rotating speed 250rmp, after ball milling terminates, by mixed AKS-W powder and Y powder It is fitted into stand-by in bag；

(2) in the glove box of the argon atmosphere in oxygen content less than 0.1ppm, water content less than 0.1ppm, by graphite pressure head Load one end of graphite jig sleeve, and be put into a ready graphite for graphite paper and graphite pressure head to be separated in advance Paper disk, by graphite paper the inner surface of graphite jig is fitted in；After graphite jig is ready to complete, the mixed AKS- that will be weighed W powder and the common 10g of Y powder are filled in graphite jig, another piece of graphite paper disk and beyond the Great Wall graphite pressure head are covered, in graphite jig two End adds Graphite pad, then graphite jig is forced into into 2MPa with powder compressing machine, makes push-down head be higher by graphite jig set The length of cylinder is consistent；

(3) SPS sintering systems are opened, the graphite jig that step (1) prepares is put into graphite insulation sleeve, be put into SPS burnings In knot cavity, no more than 5Pa is evacuated to, then graphite jig is forced into into 80MPa, while with the intensification speed of 100 DEG C/min Rate is warming up to 1400 DEG C, and under the conditions of 80MPa pressure, 1300 DEG C 10min is incubated；Then 1750 DEG C are warming up to again, in 80MPa pressures By force, 2min is incubated under the conditions of 1750 DEG C, temperature survey and feedback are carried out using monochromatic infrared radiation thermometer in experimentation；Sinter Cheng Hou, cools down under vacuum conditions about 30min, and then using tablet machine, by sintered sample, the demoulding from graphite jig is taken out, and is obtained To W-K-0.05wt.%Y block alloys.

Embodiment 13

The AKS-W powder and Y powder that the present embodiment is adopted is identical with embodiment 12.

The preparation process of the W-K-Y alloys of the present embodiment nanometer potassium bubble distribution is substantially the same manner as Example 12, difference It is 0.1wt.% that the Y powder adopted in the present embodiment accounts for AKS-W powder and Y powder gross weights.

Sample prepared by embodiment 12 and embodiment 13 is processed by shot blasting, and observes potassium in each sample using SEM and TEM Bubble, potassium bubble size is about 24-70nm in sample prepared by embodiment 12, and sample consistency is 98.12%；Prepared by embodiment 13 Potassium bubble size is about 24-70nm in sample, and its consistency is 97.88%.For the tensile property and heat shock resistance of study sample Performance, stretching is further carried out to embodiment 12 and the gained sample of embodiment 13 and rushes level experiment with heat, and experiment draws, embodiment 12 The W-K-0.05wt.%Y Alloy At Room Temperatures fracture strength of acquisition is 312.5MPa, and the W-K-0.1wt.%Y that embodiment 13 is obtained is closed Golden room temperature fracture strength is 323MPa, and 0.62GW/m is used at room temperature²Power density carry out the single thermal shock experiment of 5ms, There is not crackle in embodiment 12 and the gained sample surfaces of embodiment 13.As can be seen from the above analysis, mix in W-Y alloys During at least 0.05wt.Y, not only have in gained block alloy and be distributed in crystal boundary and transgranular nanoscale potassium bubble, and with excellent Good tensile property and thermal shock resistance.

One of ordinary skill in the art will be appreciated that embodiment here is to aid in the reader understanding present invention's Principle, it should be understood that protection scope of the present invention is not limited to such especially statement and embodiment.This area it is common Technical staff can make various other various tools without departing from essence of the invention according to these technology enlightenments disclosed by the invention Body deforms and combines, and these deformations and combination are still within the scope of the present invention.

Claims

1. W-K/W-K-Y alloys of a kind of nanometer of potassium bubble distribution, it is characterised in that be by the W powder and weight content of mixing K be 0~ The mixing powder sintering of 0.1%Y powder obtains block W-K/W-K-Y alloys, and potassium in W-K/W-K-Y alloys bubble size is 20~ 130nm, is distributed in the crystal boundary of W-K/W-K-Y alloys and transgranular.

2. the W-K/W-K-Y alloys that according to claim 1 nanometer potassium bubble is distributed, it is characterised in that mix K contents in the W powder of K For 46ppm-144ppm.

3. the W-K/W-K-Y alloys that according to claim 2 nanometer potassium bubble is distributed, it is characterised in that mix K contents in the W powder of K For 68ppm-108ppm.

4. described in claim 1 or 2 or 3 nanometer potassium bubble distribution W-K/W-K-Y alloy preparation methods, it is characterised in that include with Lower step：

Step (1), the W powder that the W powder for mixing K is weighed in inert atmosphere or K is mixed is filled in mould with the mixed powder of Y powder；

Step (2), the mould of W powder and Y powder mixed powders that will be filled with mixing the W powder of K or mixing K is put in SPS sintering cavities, takes out true Then sky is molded to no more than 5Pa under 40~120Mpa pressure, then is warming up to 1500~2000 DEG C of 2~6min of sintering Obtain a nanometer W-K/W-K-Y alloy blocks for potassium bubble distribution.

5. the W-K/W-K-Y alloy preparation methods that according to claim 4 nanometer potassium bubble is distributed, it is characterised in that step (1) Described in inert atmosphere be oxygen content less than 0.1ppm, water content less than 0.1ppm argon atmosphere.

6. the W-K/W-K-Y alloy preparation methods that according to claim 4 nanometer potassium bubble is distributed, it is characterised in that step (1) Described in mould be graphite jig.

7. according to the W-K/W-K-Y alloy preparation methods of one of claim 4 to 6 nanometer potassium bubble distribution, it is characterised in that Molding pressure described in step (2) is 80-120Mpa.

8. according to the W-K/W-K-Y alloy preparation methods of one of claim 4 to 6 nanometer potassium bubble distribution, it is characterised in that Sintering temperature described in step (2) is 1750~1900 DEG C.

9. the W-K/W-K-Y alloy preparation methods that according to claim 7 nanometer potassium bubble is distributed, it is characterised in that sintered Journey is first warming up to 1300~1400 DEG C of 6~10min of insulation, then is warming up to 1750~1900 DEG C of 2~6min of sintering.

10. the W-K/W-K-Y alloy preparation methods that according to claim 8 nanometer potassium bubble is distributed, it is characterised in that sintered Journey is first warming up to 1300~1400 DEG C of 6~10min of insulation, then is warming up to 1750~1900 DEG C of 2~6min of sintering.