CN105884359B - It is a kind of using composite construction as the B of toughening phase4C composite ceramics and preparation method thereof - Google Patents
It is a kind of using composite construction as the B of toughening phase4C composite ceramics and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of using composite construction as the B of toughening phase4C composite ceramics, with B4C is matrix phase, with (TiB2- SiC) composite construction is as composite toughening phase, by weight percentage, matrix phase B4C70%-95%, toughening phase (TiB2- SiC) compound group 5%-30%, wherein TiB in toughening phase2The mass ratio of the material with SiC is 2:3.The composite ceramics are first with the B of stoichiometric ratio4C, TiC and Si be raw material, after mechanochemistry is handled, then with B4C matrix powder carries out secondary mixing, is finally prepared by high-voltage high-speed sintering technology.The composite ceramics are with lightweight, high hard (TiB2- SiC) compound group as toughening phase, breaches current B4C composite ceramics are independently distributed the limitation as toughening phase using single object phase or multiphase, thus keeping B4Under the premise of C-material lightweight, height are hard, its fracture toughness is increased substantially.
Description
Technical field
The present invention relates to a kind of ceramic composites and preparation method thereof, more particularly to one kind is using composite construction as toughening
The B of phase4C composite ceramics and preparation method thereof.
Background technique
B4C ceramics are a kind of important engineering material, have unique physicochemical properties (high rigidity, high-modulus, low ratio
Weight, excellent heat-resisting quantity), especially integrate ultrahigh hardness and low-density, this be other materials it is incomparable.Cause
This, B4C ceramics have highly important application prospect in modern industry, aerospace and national defense construction field.In recent years, have
Close B4The research of C ceramic material at home and abroad causes great concern.However, B4C high sintering temperature and low fracture are tough
Property to material prepare and application bring extreme difficulties.Develop advanced technology of preparing to reduce sintering temperature, explore novel toughening side
Formula is always B to improve fracture toughness4The important research direction of C-material.
In recent years, B was improved using second-phase dispersion reinforcement technique4The fracture toughness of C ceramics has been obtained extensively
Research, and obtain certain progress.However, the toughening effect of this method is extremely limited, it is various acquired in the technology at present
B4The fracture toughness of C composite ceramics is hovered mostly in 3-6MPam1/2Between, it cannot achieve further breakthrough, correlative study is met
Bottleneck is arrived.Reason is: from microstructure, these current acquired B4C composite ceramics belong to attached drawing 1 mostly
(a) Reinforced structure of single-phase Dispersed precipitate shown in, i.e., a kind of addition are mutually randomly distributed over matrix grain with irregularly spherical
Between.Mutually toughening is used as mutually to prepare B using two kinds of objects on a small quantity although also having at present4The report of C tri compound ceramics, but its institute
The microstructure of the tri compound ceramics of preparation belongs to the Reinforced structure of two-phase independence Dispersed precipitate, as shown in attached drawing 1 (b), two
Kind addition is mutually randomly distributed between matrix phase crystal grain with state independent, and there is no formed again between two kinds of addition phases
It closes, Reinforced structure is substantially similar with two-phase composite ceramics shown in attached drawing 1 (a), and therefore, we can be by both toughening knots
The composite ceramics of structure are referred to as Reinforced structure of the independent object mutually as addition phase.
As reported a kind of B in international magazine Ceramics International (32 (2006) 849-856)4C-SiC-
TiB2Composite ceramics and preparation method thereof, wherein with B4C、Si3N4It is raw material with SiC, and with (Al2O3-Y2O3) it is sintering aid, lead to
It crosses reaction hot-pressing technology and obtains B under conditions of 1880 DEG C4C-SiC-TiB2Tri compound ceramics, acquired sample it is relatively close
Degree is 95.6%, fracture toughness 5.6MPa.m1/2.Although the work has been prepared with SiC and TiB2Two kinds of objects are mutually as addition
The B of phase4C tri compound ceramics, but in the tri compound ceramics prepared by it and have not seen addition phase SiC and TiB2It is formed multiple
Structure is closed, thus its fracture toughness does not realize breakthrough promotion.
Just at present, both at home and abroad for B4The thinking of C composite ceramics Research on Toughening is confined in always mutually to be made with independent object
Acquisition for toughening phase, toughening phase is introduced directly into or with sintering in-situ preparation, without being prepared separately.Reinforced structure is set
Counting thinking is by simply changing toughening phase type or preparing different increasings by using different in situ reaction systems mostly
The B of tough phase (being independently distributed)4Then C composite ceramics verify this toughening with respect to B4C ceramic toughening effect, although different toughening phases
To B4C toughening effect difference, but due to the limitation of independent object phase particulate reinforcement effect, difference is simultaneously little, various
The B for the independent toughening phase of difference that preparation method is prepared4The fracture toughness of C composite ceramics is hovered mostly in 3-6MPa.m1/2It
Between, further breakthrough can not be obtained, and lower fracture toughness seriously drops and reduces B4The use scope of C-material, and reduce
B4The use reliability of C ceramics.
Summary of the invention
The technical problem to be solved by the present invention is to provide one kind in view of the deficiency of the prior art with compound
B of the structure as toughening phase4C composite ceramics and preparation method thereof, with (TiB2- SiC) composite construction group as toughening phase, dashes forward
Break current B4C composite ceramics increase substantially B using independent object mutually as the limitation of toughening phase4The fracture toughness of C ceramics.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
It is a kind of using composite construction as the B of toughening phase4C composite ceramics, with B4C is matrix phase, with (TiB2- SiC) composite junction
Structure is as toughening phase.
According to the above scheme, described using composite construction as the B of toughening phase4C composite ceramics include: base by weight percentage
Body phase B4C70%-95%, toughening phase (TiB2- SiC) composite construction 5%-30%, wherein TiB in toughening phase2With the substance of SiC
Amount ratio be 2:3.
It is above-mentioned using composite construction as the B of toughening phase4C composite ceramics are first according to TiB in toughening phase2With the substance of SiC
Amount ratio be 2:3, weigh B4C, TiC and Si be raw material, after mechanochemistry is handled, then again with matrix phase B4C powder carries out
Secondary mixing is finally prepared by high-voltage high-speed sintering technology.
It is above-mentioned using composite construction as the B of toughening phase4The preparation method of C composite ceramics, includes the following steps:
(1) with B4C powder, TiC powder and Si powder are raw material, according to toughening phase TiB2TiB in-SiC composite construction2With
The mass ratio of the material of SiC is that (raw material is according to reaction equation B for 2:3 progress ingredient4C+2TiC+3Si—2TiB2+ 3SiC is completely anti-
It should be matched, i.e. B4The ratio between amount of substance of C powder, TiC powder and Si powder is 1:2:3), then mixing carries out mechanization
Processing, fabricated in situ have highly disordered (Ti-B-Si-C) composite granule of lattice；
(2) by (Ti-B-Si-C) composite granule obtained by step (1) and B4C powder is mixed, and B is obtained4C-(Ti-B-Si-
C) mixed powder；By weight percentage, (Ti-B-Si-C) composite granule 5%-30%, B4C powder 70%-95%；
(3) by B obtained by step (2)4C- (Ti-B-Si-C) mixed powder carries out high-voltage high-speed sintering processes, obtains with multiple
Close B of the structure as toughening phase4C composite ceramics.
According to the above scheme, the B4C powder granularity is 1-3um, and purity is greater than 96%.
According to the above scheme, the TiC powder granularity is 0.1-3um, and purity is greater than 98%.
According to the above scheme, the Si powder granularity is 1-200um, and purity is greater than 99%.
According to the above scheme, mechanochemical treatment step uses ball-milling technology in the step (1).Specifically, ball-milling technology
Are as follows: ball material mass ratio is 20:1-30:1, and rotational speed of ball-mill 200-500rpm, Ball-milling Time 30-80h, entire mechanical milling process is lazy
It is carried out in property atmosphere.
According to the above scheme, washing and drying are include thed steps that between the step (1) and step (2).Preferably, described
Washing include pickling and washing；The drying is vacuum drying.Specifically, the pickling are as follows: hydrochloric acid is molten at 40 DEG C
Stirring (such as stirring 4-9h) filters afterwards in liquid (hydrochloric acid solution of such as 1-3mol/L)；The washing is molten in deionized water
Solution, stirring, are then filtered.
According to the above scheme, in the step (2) mechanochemical treatment step use wet ball grinding technique, using ethyl alcohol as divide
Dispersion media.
According to the above scheme, include the steps that evaporating solvent and drying between the step (2) and step (3).Preferably,
The evaporation solvent uses rotary evaporation；The drying is vacuum drying.
According to the above scheme, step (3) the mesohigh Fast Sintering sintering temperature be 1700-1800 DEG C, sintering pressure
For 80-150MPa, soaking time 5-10min.Preferably, high-voltage high-speed sintering uses discharge plasma sintering, sintering schedule
Are as follows: under vacuum or inert atmosphere, 1000 DEG C, pressure 1-5MPa are warming up to 100-200 DEG C/min, then at the same rate
It is warming up to 1700-1800 DEG C of target temperature, pressure 80-150MPa, keeps the temperature natural cooling after 5-10min.
General principles are: B first4C, TiC and Si powder carries out mechanochemistry processing, has its fabricated in situ
Highly disordered (Ti-B-Si-C) the interphase composite granule of lattice, the process, that is, ceramic material powder lead in mechanochemical process
It crosses mechanical induction self- propagating mechanism or atom flooding mechanism occurs reaction in-situ and generates amorphous state micron-nanometer composite granule, this
Kind composite granule is in amorphous unstable state, tends to be sent to crystalline transformation formation (TiB certainly2- SiC) compound；Then will
This composite granule again with matrix B4The secondary mixing of C powder forms B4C- (Ti-B-Si-C) mixed powder；And in mixed powder
Each (Ti-B-Si-C) composite granule particle self-contained unit, with each (Ti-B-Si-C) powder in rapid heating condition
Body particle is the spontaneous, preferential formation (TiB of unit2- SiC) compound group, to guarantee B4TiB inside C matrix2With SiC phase
With (TiB2- SiC) there is (structure as shown in Fig. 2) in compound group form；Heating rate fast simultaneously can promote (Ti-B-
Si- C) powder is to (TiB2- SiC) compound group rapid conversion, and prevent (TiB2- SiC) compound group and its internal grain
The abnormal growth of abnormal growth, matrix grain, to realize B4(TiB in C matrix2- SiC) compound group controllable formation.
(TiB2- SiC) compound group as toughening phase when, there are toughening group inner boundary (TiB in ceramic body2The circle-SiC
Face), the interface (B between toughening group and matrix4C-TiB2Interface and B4The interface C-SiC) and three kinds of objects intersect the three of place
Phase interface (B4C-TiB2- SiC three phase boundary), unlike independent object phase toughening relates only to a kind of interface, therefore, toughening with it is general
Logical independent object phase toughening mechanism has relatively big difference.A variety of interfaces, which exist simultaneously, to generate mutual shadow to interfacial stress to each other
It rings, keeps crack propagation mode complicated and changeable, to consume more crack propagation energy, reach and increase considerably B4C matrix fracture
The purpose of toughness.
Furthermore high pressure (80-150MPa) Fast Sintering technology and the characteristic of mixed powder itself both contribute to reduce B4C
The sintering temperature of composite ceramics.For high-pressure process, particle has extremely close interface cohesion under superelevation pressure condition, this
Atomistic binding is contributed to form, can promote sintering process under the action of sintering temperature；Meanwhile high pressure can also be effective
Particle re-arrangement and the movement for strengthening ceramic particle, quickly exclude stomata, realize quick densifying.It is mechanical for powder characteristics
The powder of chemical method preparation has acceleration of sintering effect, the B of the application preparation4(Ti-B- in C- (Ti-B-Si-C) mixed powder
Si-C) it is to be obtained by mechanochemistry technique, there is high sintering activity；In two sintering processes amorphous (Ti-B-Si-C) to
(TiB2- SiC) it can release energy in transition process, these energy can play the role of assisted sintering.Therefore, it is caused in the above
Under the collective effect of densification mechanism, B can be achieved on4The low temperature densification of C composite ceramics.
Compared with prior art, beneficial effects of the present invention are as follows:
The first, B prepared by the present invention4C composite ceramics are with (TiB2- SiC) composite construction group as composite toughening phase,
Break through current B4Using independent object mutually as the limitation of toughening phase, this special Reinforced structure can be mentioned significantly C composite ceramics
High B4The fracture toughness of C ceramics, it is prepared using composite construction as the B of toughening phase4C composite ceramics have high tenacity.
The second, toughening phase (TiB in the present invention2- SiC) composite construction group introducing can guarantee B4C ceramics high rigidity,
Its fracture toughness is increased considerably while Lightness, therefore, the ceramic composite that the present invention obtains can be used as thermal structure
Component is applied to high temperature resistant, corrosion-resistant and in toughness and Lightness demanding harsh environment.
Third, the present invention without add liquid phase sintering can at relatively low temperature (1700-1800 DEG C) low temperature
Prepare the B of closely knit high tenacity4C-(TiB2- SiC) composite ceramics.
4th, preparation process of the present invention remixes two step flouring technologies using mechanochemical reaction-, i.e., first uses mechanochemistry
Compound addition phase is prepared separately in method, then again by addition phase and B4C matrix is mutually secondary to be mixed with the mixing with special construction
Powder, to guarantee prepared B4(TiB in C composite ceramics2- SiC) composite toughening group controllable formation.
Detailed description of the invention
Fig. 1 is the B that independent object is mutually used as toughening phase4The single-phase Dispersed precipitate toughening of C composite ceramics microstructure schematic diagram (a)
Structure；(b) multiphase independence Dispersed precipitate Reinforced structure.
Fig. 2 is B of the two-phase composite construction group as composite toughening phase4C composite ceramics microstructure schematic diagram.
Fig. 3 is B in embodiment 44C-(TiB2- SiC) composite ceramics XRD spectra.
In Fig. 4, a is B in embodiment 54C-(TiB2- SiC) composite ceramics burnishing surface BSE image；B is conventional method
(direct mixing or reaction in-situ) prepares B4C-TiB2The BSE image in the ceramic polished face of-SiC tri compound.
Fig. 5 is B in embodiment 54C-(TiB2- SiC) composite ceramics section SEM image.
Specific embodiment
For a better understanding of the present invention, with reference to the accompanying drawing, the embodiment content that the present invention is furture elucidated, but this hair
Bright content is not limited solely to the following examples.
Embodiment 1
It is a kind of using composite construction as the B of toughening phase4C composite ceramics, with B4C is matrix phase, with (TiB2- SiC) composite junction
Structure includes: matrix phase B as toughening phase by weight percentage4C 95%, toughening phase (TiB2- SiC) composite construction 5%,
TiB in middle toughening phase2The mass ratio of the material with SiC is 2:3.
It by weight percentage, should be using composite construction as the B of toughening phase4C composite ceramics by 1.07% B4(granularity is C
3 um, purity 97%), (granularity is 200 μ for the Si powder of 2.31% TiC (granularity is 3 μm, purity 98%) and 1.62%
M, purity 99%) it is raw material by after mechanized process, then the B of the same race with 95%4C powder carries out secondary mixing, finally leads to
High pressure Fast Sintering technology is crossed to be prepared.
B described in the present embodiment4C-(TiB2- SiC) composite ceramics preparation method, specific steps include:
1. weighing B by weight percentage4C powder 1.07%, TiC powder 2.31% and Si powder 1.62%, by weighed powder
Body is put into stainless steel jar mill, is first vacuumized to ball grinder and is filled with argon gas afterwards, ball: material mass ratio is 300:1, and rotational speed of ball-mill is
500rpm, ball milling 80h, the powder that will acquire stirs 9h in the hydrochloric acid solution of 3mol/L under the conditions of 40 DEG C, through suction filtration-water
After washing 3 times, it is placed in 60 DEG C of vacuum ovens for 24 hours, obtains amorphous high activity (Ti-B-Si-C) composite granule.
2. in percentage by weight, weighing (Ti-B-Si-C) composite granule 5% and B obtained4C matrix powder 95%,
Be then placed in the ball grinder of jar mill and carry out rerolling, using ethyl alcohol as decentralized medium, then rotary evaporation, vacuum drying
After obtain B4C- (Ti-B-Si-C) mixed powder；
3. by B obtained4C- (Ti-B-Si-C) mixed powder is put into graphite jig, and stone is used between powder and mold, pressure head
Black paper separates, and is placed in argon atmosphere sintering, sintering schedule are as follows: be warming up to 1000 with 200 DEG C/min in discharge plasma sintering furnace
DEG C, then pressure 5MPa is warming up to 1800 DEG C of target temperature, pressure 150MPa at the same rate, keep the temperature after 10min from
It is so cooling, B can be obtained4C-(TiB2- SiC) composite ceramics, as using composite construction as the B of toughening phase4C composite ceramics.
Acquired B4C-(TiB2- SiC) composite ceramics performance it is as follows: relative density 98.9%, Vickers hardness 34.2GPa,
Bending strength 562MPa, fracture toughness 6.83MPam1/2。
Embodiment 2
It is a kind of using composite construction as the B of toughening phase4C composite ceramics, with B4C is matrix phase, with (TiB2- SiC) composite junction
Structure includes: matrix phase B as toughening phase by weight percentage4C 95%, toughening phase (TiB2- SiC) composite construction 5%,
TiB in middle toughening phase2The mass ratio of the material with SiC is 2:3.
By weight percentage, the composite ceramics by 1.07% B4C (granularity 2um, purity 97%), 2.31%
The Si powder (granularity is 10 μm, purity 99%) of TiC (granularity is 1 μm, purity 99%) and 1.62% is that raw material passes through machinery
After change process, then the B of the same race with 95%4C powder carries out secondary mixing, is prepared finally by high-voltage high-speed sintering technology.
Using composite construction as the B of toughening phase described in the present embodiment4The preparation method of C composite ceramics, specific steps include:
1. weighing B by weight percentage4C powder 1.07%, TiC powder 2.31% and Si powder 1.62%, by weighed powder
Body is put into stainless steel jar mill, is first vacuumized to ball grinder and is filled with argon gas afterwards, ball: material mass ratio is 25:1, and rotational speed of ball-mill is
300 rpm, ball milling 50h, the powder that will acquire stirs 5h in the hydrochloric acid solution of 2mol/L under the conditions of 40 DEG C, through suction filtration-water
After washing 3 times, it is placed in 60 DEG C of vacuum ovens for 24 hours, obtains amorphous high activity (Ti-B-Si-C) composite granule；
2. in percentage by weight, weighing (Ti-B-Si-C) composite granule 5% and B obtained4C matrix powder 95%,
Be then placed in the ball grinder of jar mill and carry out rerolling, using ethyl alcohol as decentralized medium, then rotary evaporation, vacuum drying
After obtain B4C- (Ti-B-Si-C) mixed powder；
3. by B obtained4C- (Ti-B-Si-C) mixed powder is put into graphite jig, and stone is used between powder and mold, pressure head
Black paper separates, and is placed in vacuum-sintering in discharge plasma sintering furnace, sintering schedule are as follows: is warming up to 1000 DEG C with 200 DEG C/min, pressure
Power is 2MPa, is then warming up to 1750 DEG C of target temperature, pressure 120MPa at the same rate, is kept the temperature naturally cold after 8min
But, B can be obtained4C-(TiB2- SiC) composite ceramics, as using composite construction as the B of toughening phase4C composite ceramics.
Acquired B4C-(TiB2- SiC) composite ceramics performance it is as follows: relative density 99.1%, Vickers hardness 34.9GPa,
Bending strength 554MPa, fracture toughness 7.01MPam1/2。
Embodiment 3
The present embodiment with embodiment 2 the difference is that: B of the be able to composite construction as toughening phase4C composite ceramics
Middle matrix phase B4C 90%, toughening phase (TiB2- SiC) composite construction 10%, wherein TiB in toughening phase2With the amount of the substance of SiC
Than for 2:3.
Embodiment 4
The present embodiment with embodiment 2 the difference is that: B of the be able to composite construction as toughening phase4C composite ceramics
Middle matrix phase B4C 80%, toughening phase (TiB2- SiC) composite construction 20%, wherein TiB in toughening phase2With the amount of the substance of SiC
Than for 2:3.
Embodiment 5
The present embodiment with embodiment 2 the difference is that: B of the be able to composite construction as toughening phase4C composite ceramics
Middle matrix phase B4C 70%, toughening phase (TiB2- SiC) composite construction 30%, wherein TiB in toughening phase2With the amount of the substance of SiC
Than for 2:3.
Embodiment 6
It is a kind of using composite construction as the B of toughening phase4C composite ceramics, with B4C is matrix phase, with (TiB2- SiC) composite junction
Structure includes: matrix phase B as toughening phase by weight percentage4C 70%, toughening phase (TiB2- SiC) composite construction 30%,
Wherein TiB in toughening phase2The mass ratio of the material with SiC is 2:3.
By weight percentage, the composite ceramics by 6.45% B4C (granularity is 1 um, purity 96%), 13.85%
The Si powder (granularity is 1 μm, purity 99%) of TiC (granularity is 0.1 μm, purity 98%) and 9.70% is that raw material passes through machinery
After change process, then the B of the same race with 70%4C powder carries out secondary mixing, is prepared finally by high-voltage high-speed sintering technology.
Using composite construction as the B of toughening phase described in the present embodiment4The preparation method of C composite ceramics, specific steps include:
1. weighing B by weight percentage4C powder 6.45%, TiC powder 13.85% and Si powder 9.7%, by weighed powder
Body is put into stainless steel jar mill, is first vacuumized to ball grinder and is filled with argon gas afterwards, ball: material mass ratio is 20:1, and rotational speed of ball-mill is
200 rpm, 30 h of ball milling, the powder that will acquire stir 4 h under the conditions of 40 DEG C in the hydrochloric acid solution of 1 mol/L, filtered-
After washing 3 times, it is placed in 60 DEG C of vacuum ovens for 24 hours, obtains amorphous high activity (Ti-B-Si-C) composite granule；
2. in percentage by weight, weighing (Ti-B-Si-C) composite granule 30% and B obtained4C matrix powder
70%, it is then placed in the ball grinder of jar mill and carries out rerolling, using ethyl alcohol as decentralized medium, then rotary evaporation, true
B is obtained after sky is dry4C- (Ti-B-Si-C) mixed powder；
3. by B obtained4C- (Ti-B-Si-C) mixed powder is put into graphite jig, and stone is used between powder and mold, pressure head
Black paper separates, and is placed in argon atmosphere sintering, sintering schedule are as follows: be warming up to 1000 with 100 DEG C/min in discharge plasma sintering furnace
DEG C, pressure is 1 MPa, is then warming up to 1700 DEG C of target temperature at the same rate, pressure is 80 MPa, after keeping the temperature 5 min
B can be obtained in natural cooling4C-(TiB2- SiC) composite ceramics, as using composite construction as the B of toughening phase4C composite ceramics.
Acquired B4C-(TiB2- SiC) composite material performance it is as follows: relative density 98.2%, Vickers hardness 30.6
GPa, 505 MPa of bending strength, 7.56 MPam of fracture toughness1/2。
B obtained by embodiment 2-54C-(TiB2- SiC) composite ceramics performance it is as shown in table 1.
The B of 1 different component content of table4C-(TiB2- SiC) composite ceramics properties
The B of the present invention using composite construction as toughening phase is specifically introduced with reference to the accompanying drawing4The property of C composite ceramics
Matter, including phase composition, compactness, microstructure and mechanical property.
Attached drawing 3 is the B prepared in embodiment 44C-(TiB2- SiC) composite ceramics XRD spectra.From the figure, it can be seen that
Contain in spectrogram and only contains apparent, sharp B4C、TiB2With the diffraction maximum of tri- kinds of substances of SiC, there is no other impurity peaks
Presence, illustrate material powder B4C, TiC and Si can generate object after through mechanochemistry and Fast Sintering technique
Phase, and the object phase crystallinity generated is preferable.To, it was demonstrated that processing route of the present invention be it is feasible, can obtain
Expected product is obtained using composite construction as the B of toughening phase4C composite ceramics.
Attached drawing 4a is B in embodiment 54C-(TiB2- SiC) composite ceramics burnishing surface BSE image, can understand from BSE
Find out sample by 3 object phase compositions.According to energy spectrum analysis, back end color is matrix B4C, bright canescence are TiB2, dark
Canescence is SiC, and sample substantially achieves complete densification, almost without stomata presence.Further, it is also possible to, it is evident that sample
In form by TiB2With (TiB composed by two kinds of object phases of SiC2- SiC) compound group, compound group is by strip TiB2No
Regular SiC is mutually interspersed and forms, and entire group is in irregular shape, and size is about between 5 and 15 mum (as circle in Fig. 4 a
Shown in shape region).It thereby confirms to prepare in lower temperature using the method for the present invention and closely knit there is (TiB2-SiC)
B of the compound group as composite toughening phase4C-(TiB2- SiC) composite ceramics.
If preparing B using conventional method (direct mixing or reaction in-situ)4C-TiB2- SiC tri compound ceramics, although
Product, which also has mutually to be used as there are two types of object, adds phase, but major part TiB in its internal structure2It is mutually with respectively independent with SiC object
There is (as shown in Figure 4 b) in the form of distribution, for Reinforced structure with independent object phase toughening without essential distinction, this is also to lead to B4C
The main reason for composite ceramics fracture toughness cannot achieve further breakthrough.Therefore, the B that the present invention prepares4C-(TiB2-SiC)
Composite ceramics are almost with TiB entirely2With the mutually interspersed and composed (TiB of SiC2- SiC) composite construction as composite toughening phase,
Its Reinforced structure has larger difference with independent object phase toughening.Wherein, (TiB2- SiC) compound group as toughening phase when, ceramic body
Inside there is toughening group inner boundary (TiB2The interface-SiC), the interface (B between toughening group and matrix4C-TiB2Interface and B4C-
The interface SiC) and three kinds of objects intersect the three phase boundary (B at place4C-TiB2- SiC three phase boundary), only unlike independent object phase toughening
It is related to a kind of interface；And a variety of interfaces exist simultaneously and can influence each other to interfacial stress generation to each other, make crack propagation
Mode is complicated and changeable, to consume more crack propagation energy, reaches and increases considerably B4The purpose of C matrix fracture toughness.
Fig. 5 is B in embodiment 54C-(TiB2- SiC) composite ceramics section SEM image.It can be seen that from Fig. 5 (a)
B4The plane of disruption of C matrix is smooth, and fracture mode is transgranular fracture, and (TiB2- SiC) fracture mode inside compound group is edge
Crystalline substance fracture；The agglomeration unit is amplified, it is just shown as shown in Fig. 5 (b), it can be clearly seen that, (TiB2- SiC) compound group is practical
On be by partial size about in 2-5 μm of SiC and TiB2Crystal grain is mutually compound and forms, and the break surface inside agglomeration unit is concave-convex
Injustice shows apparent grain boundary fracture mode, microscopic appearance and fracture mode and TiB2- SiC composite ceramics are identical.Cause
This, can be interpreted as TiB for these compound groups2- SiC composite ceramics, i.e. TiB2- SiC composite ceramics integrally mutually disperse as addition
In B4In C matrix, it is this using composite construction unit integrally as it is compound addition mutually be promoted B4C composite ceramics fracture toughness
Major reason, and this special Reinforced structure is structure specific to the composite ceramics of the method for the present invention preparation.
Using the method for the present invention it can be seen from embodiment 1-6, can in the case where not adding any sintering aid in
It is prepared under the lower temperature that 1800 DEG C of 1700- with novel toughening structure (with (TiB2- SiC) conduct of composite construction group is again
Close toughening phase) B4C-(TiB2- SiC) composite ceramics, obtained B4C-(TiB2- SiC) relative densities of composite ceramics is all larger than
98%.
The performance of embodiment 2-5 sample is compared, analyzed and summarized, it can be deduced that rule: in same process condition
Under, with (TiB2- SiC) compound group content increase, gained B4C-(TiB2- SiC) composite ceramics relative density increased
Add；Vickers hardness is in a slight decrease, but its minimum value is also greater than 32GPa；Bending strength slightly reduces, but its minimum value also greater than
515MPa；Especially note that its fracture toughness is in the trend increased, and maximum may be up to 7.82MPam1/2, minimum is also greater than 7
MPa·m1/2, illustrate that B can be increased substantially using the composite ceramics prepared by the present invention with novel toughening structure4C-material
Fracture toughness.As it can be seen that the present invention can quickly prepare the B with novel toughening structure at a lower temperature4C-(TiB2- SiC) it is multiple
Ceramics are closed, which can keep B4C high rigidity, it is Lightness under the premise of, significantly promote its fracture toughness.
The above is only a preferred embodiment of the present invention, cited each raw material can realize the present invention, each raw material
Bound value and its interval value can realize the present invention, present invention process parameter (such as proportion, temperature, time) it is upper
Lower limit value and its interval value can realize the present invention, embodiment numerous to list herein.It should be pointed out that for this field
For those of ordinary skill, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these
Belong to protection scope of the present invention.
Claims (6)
1. a kind of using composite construction as the B of toughening phase4The preparation method of C composite ceramics, it is characterised in that include the following steps:
It (1) is that 1:2:3 weighs B according to the ratio between amount of substance4C powder, TiC powder and Si powder are raw material, then mix carry out machine
Tool chemical treatment, fabricated in situ have highly disordered (Ti-B-Si-C) composite granule of lattice；Wherein, the mechanochemistry processing
Step uses planetary ball mill technique, and ball material mass ratio is 20:1-30:1, rotational speed of ball-mill 200-500rpm, Ball-milling Time 30-80
H, entire mechanical milling process carry out in an inert atmosphere；
(2) by (Ti-B-Si-C) composite granule obtained by step (1) and B4C powder is mixed, and B is obtained4C- (Ti-B-Si-C) is mixed
Close powder；By weight percentage, (Ti-B-Si-C) composite granule 5%-30%, B4C powder 70%-95%；
(3) by B obtained by step (2)4C- (Ti-B-Si-C) mixed powder carries out high-voltage high-speed sintering processes, obtains with composite construction
B as toughening phase4C composite ceramics.
2. according to claim 1 a kind of using composite construction as the B of toughening phase4The preparation method of C composite ceramics, it is special
Sign is the B4C powder granularity is 1-3 μm, and purity is greater than 96%；The TiC powder granularity is 0.1-3 μm, and purity is big
In 98%；The Si powder granularity is 1-200 μm, and purity is greater than 99%.
3. according to claim 1 a kind of using composite construction as the B of toughening phase4The preparation method of C composite ceramics, it is special
Sign is to include the steps that washing and drying between the step (1) and step (2)；Between the step (2) and step (3)
Include the steps that evaporating solvent and drying.
4. according to claim 1 a kind of using composite construction as the B of toughening phase4The preparation method of C composite ceramics, it is special
Sign is in the step (2) that mixing step uses wet ball grinding technique, using ethyl alcohol as decentralized medium.
5. according to claim 1 a kind of using composite construction as the B of toughening phase4The preparation method of C composite ceramics, it is special
Sign is that the sintering temperature of the step (3) mesohigh Fast Sintering is 1700-1800 DEG C, sintering pressure 100-200MPa,
Soaking time is 5-10min.
6. according to claim 1 a kind of using composite construction as the B of toughening phase4The preparation method of C composite ceramics, it is special
Sign be high-voltage high-speed sintering using discharge plasma sintering, sintering schedule are as follows: under vacuum or inert atmosphere, with 100-200 DEG C/
Min is warming up to 1000 DEG C, pressure 1-5MPa, is then warming up to 1700-1800 DEG C of target temperature at the same rate, and pressure is
80-150 MPa keeps the temperature natural cooling after 5-10min.
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| CN108794013B (en) * | 2018-07-26 | 2021-05-04 | 北京理工大学 | B4C ceramic block and rapid preparation method thereof |
| CN108751997B (en) * | 2018-07-26 | 2021-04-27 | 北京理工大学 | B4C-TiB2-SiC composite ceramic block and rapid preparation method thereof |
| CN108997015A (en) * | 2018-08-20 | 2018-12-14 | 宁夏昌杨科技有限公司 | A kind of boron carbide-based bulletproof ceramic composite material and preparation method |
| CN109748589A (en) * | 2019-03-06 | 2019-05-14 | 东北大学 | A kind of high-performance boron carbide ceramic composite and preparation method |
| CN110256081A (en) * | 2019-06-25 | 2019-09-20 | 合肥工业大学 | A kind of boron carbide base composite ceramic material and its preparation process |
| CN110282983B (en) * | 2019-07-05 | 2022-07-29 | 河南理工大学 | High-hardness TiB without intermediate phase 2 -B 4 Preparation method and application of C ceramic composite material |
| CN115991606B (en) * | 2023-02-22 | 2023-05-26 | 中南大学 | TiB2-SiC-B4C ternary superhard ceramic material and preparation method thereof |
| CN116751060A (en) * | 2023-05-31 | 2023-09-15 | 郑州大学 | High-strength high-toughness B 4 C composite bulletproof ceramic material and preparation method thereof |
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