阅读说明：本技术 一种高韧性高耐磨性的高熵陶瓷及其制备方法和应用 (A kind of high entropy ceramics of high-ductility high wear-resistant and its preparation method and application ) 是由 郭伟明 张岩 张威 吴利翔 林华泰 于 2019-08-05 设计创作，主要内容包括：本发明属于陶瓷加工技术领域,公开了一种高韧性高耐磨性的高熵陶瓷及其制备方法和应用。高熵陶瓷的分子式为(Me1<Sub>a</Sub>Me2<Sub>b</Sub>Me3<Sub>c</Sub>Me4<Sub>d</Sub>Me5<Sub>e</Sub>)B<Sub>2</Sub>,其中,0.1≤a,b,c,d和e≤0.9；Me1和Me5为Hf、Zr或Ti；Me2为Nb或Ta；Me3为Cr、Me4为Mo；高熵陶瓷是将Me1的氧化物、Me2的氧化物、Me3的氧化物、Me4的氧化物、Me5的氧化物和无定型硼粉球磨混合,压成坯体升温至800～1200℃煅烧,经洗涤,抽滤和干燥,采用放电等离子烧结将所得高熵硼化物粉体升温至1600～1700℃时保护气氛加压,升温至1700～1900℃烧结制得。高熵陶瓷的相对密度95～100％,断裂韧性8～20MPa·m<Sup>1/2</Sup>,晶粒尺寸为1～3μm。(The invention belongs to ceramic processing technique fields, disclose a kind of high entropy ceramics and its preparation method and application of high-ductility high wear-resistant.The molecular formula of high entropy ceramics is (Me1 a Me2 b Me3 c Me4 d Me5 e )B 2 , wherein 0.1≤a, b, c, d and e≤0.9；Me1 and Me5 is Hf, Zr or Ti；Me2 is Nb or Ta；Me3 is Cr, Me4 Mo；High entropy ceramics are by the oxide of Me1, the oxide of Me2, the oxide of Me3, the oxide of Me4, the oxide of Me5 and unformed boron powder ball milling mixing; it is pressed into green body and is warming up to 800~1200 DEG C of calcinings; it is washed; it filters and dry; protective atmosphere pressurizes when the high entropy boride powder of gained being warming up to 1600~1700 DEG C using discharge plasma sintering, is warming up to 1700~1900 DEG C of sintering and is made.The relative density 95~100% of high entropy ceramics, 8~20MPam of fracture toughness 1/2 , crystallite dimension is 1~3 μm.)

1. a kind of high entropy ceramics of high-ductility high wear-resistant, which is characterized in that the molecular formula of the high entropy ceramics is (Me1_aMe2_bMe3_cMe4_dMe5_e)B₂, wherein 0.1≤a≤0.9,0.1≤b≤0.9,0.1≤c≤0.9,0.1≤d≤0.9, 0.1≤e≤0.9；The Me1 and Me5 is Hf, Zr or Ti；Me2 is Nb or Ta；Me3 is Cr, Me4 Mo；The high entropy ceramics It is to be with the oxide of Me1, the oxide of Me2, the oxide of Me3, the oxide of Me4, the oxide of Me5 and unformed boron powder Raw material is added solvent A and through ball milling obtains mixed powder, gained green body is put into graphite crucible after being molded, it is warming up to 800~ 1200 DEG C of calcinings, obtain high entropy boride powder, wash through solvent B, will be high using discharge plasma sintering after filtering and drying Entropy boride powder is filled with protective atmosphere and pressurizes when being warming up to 1600~1700 DEG C, then heats to 1700~1900 DEG C of sintering It is made.

2. the high entropy ceramics of high-ductility high wear-resistant according to claim 1, which is characterized in that the a=0.2, b= 0.2, c=0.2, d=0.2, e=0.2.

3. the high entropy ceramics of high-ductility high wear-resistant according to claim 1, which is characterized in that the phase of the high entropy ceramics It is 95~100% to density, fracture toughness is 8~20MPam^1/2, crystallite dimension is 1~3 μm, and the high entropy ceramics are in B₄C For wear medium, wear 1~10min, machine 500~720r/min of revolving speed under the load of 10~100N, abrasion Mass lost 0.1 ~2g；The partial size of the high entropy boride powder is 0.01~0.45 μm.

4. high-ductility high wear-resistant according to claim 1 high entropy ceramics, which is characterized in that the unformed boron powder with The oxide of Me1 and the oxide mol ratio of Me5 are (2~4): 1, the oxide mol ratio of unformed the boron powder and Me2 For (7~9): 1, the oxide mol ratio of the unformed boron powder and Me3 are (8~9): 1, the unformed boron powder and Me4's Oxide mol ratio is (4~5): 1.

5. the high entropy ceramics of high-ductility high wear-resistant according to claim 1, which is characterized in that the oxidation with Me1 Object, the oxide of Me2, the oxide of Me3, the oxide of Me4, Me5 the purity of oxide be 99.0~99.9wt%, institute Stating with the partial size of oxide of the oxide of Me1, the oxide of Me2, the oxide of Me3, the oxide of Me4, Me5 is 0.1 ~10 μm, the purity of the unformed boron powder is 95~99wt%, and the partial size of the unformed boron powder is 0.1~10 μm.

6. high-ductility high wear-resistant according to claim 1 high entropy ceramics, which is characterized in that the solvent A be ethyl alcohol, Propyl alcohol, methanol or acetone；The solvent B is water, dehydrated alcohol or acetone.

7. the high entropy ceramics of high-ductility high wear-resistant according to claim 1, which is characterized in that the protective atmosphere is N₂ Or Ar.

8. the high entropy ceramics of high-ductility high wear-resistant according to claim 1, which is characterized in that it is described be warming up to 800~ 1200 DEG C are 5~20 DEG C/min with rate when being warming up to, and the time of the calcining is 1~3h；It is warming up to 1700~1900 DEG C the rate of heating be 100~400 DEG C/min, time of the sintering is 5~20min, the pressure of the pressurization is 10~ 50MPa。

9. the method for the high entropy ceramics of high-ductility high wear-resistant according to claim 1-8, which is characterized in that packet Include following specific steps:

S1. with the oxide of Me1, the oxide of Me2, the oxide of Me3, the oxide of Me4, the oxide of Me5 and unformed Boron powder is raw material, and solvent A and ball-milling medium is added, and 10~48h is mixed on ball mill, after dry, obtains mixed powder；

S2. the green body after mixed powder being molded is put into graphite crucible, 800 are warming up to the rate of 5~20 DEG C/min~ 1200 DEG C of 1~3h of heat preservation after filtering drying, obtain high entropy boride powder after washing 0~4 time；

S3. high entropy boride powder is washed through solvent B, after filtering and drying, is put into graphite jig, using plasma discharging Protective atmosphere is filled in sintering when being warming up to 1600~1700 DEG C with 100~400 DEG C/min rate, pressurize 10~50MPa, then with 100 ~400 DEG C/min rate is warming up to 1700~1900 DEG C of sintering, keeps the temperature 5~20min, and (Me1 is made_aMe2_bMe3_cMe4_dMe5_e)B₂ High entropy ceramics.

10. the high entropy ceramics of the described in any item high-ductility high wear-resistants of claim 1-8 are in the application processed in wear-resisting field.

Technical field

The invention belongs to ceramic processing technique fields, more particularly, to a kind of high entropy ceramics of high-ductility high wear-resistant And its preparation method and application.

Background technique

There are ceramic material the metal materials such as excellent high temperature resistant, wear-resistant, corrosion resistance to be difficult to the property being equal to. It is also widely used as component of machine and ceramic powder processing mill Jie etc. other than being applied to high temperature resistant, corrosion resistant components It is required that in the product used under many adverse circumstances such as wear-resisting crushing, ball milling, cutting element, deforming moulds.It is required that material has There is high-wearing feature, therefore the wearability of ceramic material starts to cause watching attentively for people.High entropy ceramics tool there are five types of or five kinds or more Constituent element, if its solid solution becomes single-phase solid solution ceramics, because of entropy with higher, easily obtain the high solid solution phase of thermal stability and Nanostructure, different high entropy ceramics have different characteristics, and performance is better than traditional ceramics material.And for its wearability The also non-someone's report of research.

For the boride ZrB of refractory metal₂、HfB₂、NbB₂、TaB₂、CrB₂、TiB₂And MoB₂Because its excellent physics, Chemistry and mechanical performance and be concerned.But just because of haveing excellent performance, cause its sintering temperature high.Its high entropy boride pottery Although porcelain also have high intensity, hardness, excellent wearability, excellent high temperature strength, good structural stability and well Corrosion resistance and the excellent property such as inoxidizability, but the sintering temperature of reported high entropy boride ceramics is above 2000 DEG C, it also needs further to probe into for improving its sintering character method.

Summary of the invention

In order to solve above-mentioned the shortcomings of the prior art and disadvantage, primary and foremost purpose of the present invention is to provide a kind of high tenacity The high entropy ceramics of high-wearing feature.The ceramics have uniform solid solution phase, constituent element is stable, fracture toughness and wear-resisting property are excellent Low-temperature sintering the characteristics of.

Another object of the present invention is to provide a kind of preparation method of the high entropy ceramics of above-mentioned high-ductility high wear-resistant.

Still a further object of the present invention is to provide a kind of application of the high entropy ceramics of above-mentioned high-ductility high wear-resistant.

The purpose of the present invention is realized by following technical proposals:

A kind of high entropy ceramics of high-ductility high wear-resistant, the molecular formula of the high entropy ceramics are (Me1_aMe2_bMe3_cMe4_dMe5_e)B₂, wherein 0.1≤a≤0.9,0.1≤b≤0.9,0.1≤c≤0.9,0.1≤d≤0.9, 0.1≤e≤0.9；The Me1 and Me5 is Hf, Zr or Ti；Me2 is Nb or Ta；Me3 is Cr, Me4 Mo；The high entropy ceramics It is to be with the oxide of Me1, the oxide of Me2, the oxide of Me3, the oxide of Me4, the oxide of Me5 and unformed boron powder Raw material is added solvent A and through ball milling mixing obtains mixed powder, and gained green body is put into graphite crucible after being molded, it is warming up to 800~ After 1200 DEG C of calcinings, high entropy boride powder is obtained, is washed through solvent B, it, will using discharge plasma sintering after filtering and drying High entropy boride powder is filled with protective atmosphere and pressurizes when being warming up to 1600~1700 DEG C, then heats to 1700~1900 DEG C of burnings High entropy ceramics are made in knot.

Preferably, the a=0.2, b=0.2, c=0.2, d=0.2, e=0.2.

Preferably, the relative density of the high entropy ceramics is 95~100%, and fracture toughness is 8~20MPam^1/2, crystal grain Having a size of 1~3 μm, the high entropy ceramics are in B₄C is wear medium, wears 1~10min, machine revolving speed under the load of 10~100N 500~720r/min wears 0.1~2g of Mass lost.

Preferably, the partial size of the high entropy boride powder is 0.01~0.45 μm.

Preferably, the unformed boron powder and the oxide of Me1 and the oxide mol ratio of Me5 are (2~4): 1, institute The oxide mol ratio for stating unformed boron powder and Me2 is (7~9): 1, the oxide mol ratio of the unformed boron powder and Me3 is (8~9): 1, the oxide mol ratio of the unformed boron powder and Me4 are (4~5): 1.

Preferably, it is described with the oxide of Me1, the oxide of Me2, the oxide of Me3, the oxide of Me4, Me5 oxygen The purity of compound is 99.0~99.9wt%, described with the oxide of Me1, the oxide of Me2, the oxide of Me3, Me4 Oxide, Me5 the partial size of oxide be 0.1~10 μm, the purity of the unformed boron powder is 95~99wt%, the nothing The partial size of sizing boron powder is 0.1~10 μm.

Preferably, the solvent A is ethyl alcohol, propyl alcohol, methanol or acetone；The solvent B is water, dehydrated alcohol or acetone.

Preferably, the protective atmosphere is N₂Or Ar.

It is preferably, described that be warming up to 800~1200 DEG C and rate when being warming up to be 5~20 DEG C/min, the calcining Time be 1~3h；The rate for being warming up to 1700~1900 DEG C of heating is 100~400 DEG C/min, and the time of the sintering is 5~20min, the pressure of the pressurization are 10~50MPa.

The method of the high entropy ceramics of the high-ductility high wear-resistant, comprises the following specific steps that:

S1. with the oxide of Me1, the oxide of Me2, the oxide of Me3, the oxide of Me4, the oxide of Me5 and nothing Sizing boron powder is raw material, and solvent A and ball-milling medium is added, and 10~48h is mixed on ball mill, obtains mixed powder after dry；

S2. the green body after mixed powder being molded is put into graphite crucible, is warming up to 800 with the rate of 5~20 DEG C/min ~1200 DEG C of 1~3h of heat preservation after filtering drying, obtain high entropy boride powder after washing 0~4 time；

S3. high entropy boride powder is washed through solvent B, after filtering and drying, is put into graphite jig, using electric discharge etc. Ion sintering fills protective atmosphere when being warming up to 1600~1700 DEG C with 100~400 DEG C/min rate, and pressurize 10~50MPa, then with 100~400 DEG C/min rate is warming up to 1700~1900 DEG C of sintering, keeps the temperature 5~20min, is made (Me1_aMe2_bMe3_cMe4_dMe5_e)B₂High entropy ceramics.

The high entropy ceramics of the high-ductility high wear-resistant are in the application processed in wear-resisting field.

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

1. low-temperature sintering of the invention prepares the high entropy ceramics of high-ductility high wear-resistant, the ceramics are the oxidations with Me1 Object, the oxide of Me2, the oxide of Me3, the oxide of Me4, the oxide of Me5 and unformed boron powder are raw material, are forged through low temperature Washing obtains ultra-fine high entropy boride powder after burning, after through discharge plasma sintering (Me1 is made_aMe2_bMe3_cMe4_dMe5_e)B₂ High entropy ceramics, low-temperature sintering which has uniform solid solution phase, that constituent element is stable, fracture toughness and wear-resisting property are excellent The characteristics of.

2. the present invention is by being after raw material mixes, after (< 1200 DEG C) of low temperature calcinings by metal oxide and unformed boron powder Washing, remove boron thermal response in meeting so that particle growth B₂O₃By-product, prepares ultra-fine high entropy boride powder, which is Nanometer grade powder can realize densified sintering product at low temperature, improve sintering character, improve material property.

3. method of the invention realizes the quick preparation of high entropy ceramic material using SPS, when greatly shortening crystal grain and growing up Between, can get the tiny ceramics of crystal grain, in wear test compared with little crystal grain be plastic deformation and part transgranular fracture based on, It wears less；Then occur in such a way that material internal grain boundary fracture or even big crystal grain are extracted from material internal compared with big crystal grain larger Abrasion, therefore high entropy ceramic material of the invention have better wear-resisting property.

4. the crystallite dimension that the present invention is sintered out ceramics is small, when material is broken, ceramic material fracture will increase Path increases crack deflection, and the high entropy ceramics for comparing coarse grain size improve toughness of material and are greater than 50%.

5. sintering temperature of the invention is lower than 1900 DEG C, low-temperature sintering further promotes the preparation of superfine ceramics, and temperature Degree is significantly lower than temperature reported in the literature, and the ceramic material haveing excellent performance is prepared while energy saving.

Illustrate attached drawing

Fig. 1 is the XRD diagram of high entropy boride powder made from 5 in embodiment.

Fig. 2 is the SEM photograph of high entropy boride powder made from 5 in embodiment.

Fig. 3 is that embodiment 5 is made through the sintered (Hf of SPS_0.2Ta_0.2Cr_0.2Ti_0.2Zr_0.2)B₂The XRD diagram of high entropy ceramics.

Fig. 4 is that embodiment 5 is made through the sintered (Hf of SPS_0.2Ta_0.2Cr_0.2Ti_0.2Zr_0.2)B₂The high ceramic polished surface of entropy Corrosion SEM photograph.

Fig. 5 is the SEM photograph of high entropy boride powder made from comparative example 1.

Fig. 6 is that comparative example 1 is made through the sintered (Hf of SPS_0.2Ta_0.2Cr_0.2Ti_0.2Zr_0.2)B₂The high ceramic polished surface of entropy Corrosion SEM photograph.

Specific embodiment

The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention. Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.