CN110436928A - High-performance nano twin boron carbide ceramics block materials and preparation method thereof - Google Patents
High-performance nano twin boron carbide ceramics block materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-performance nano twin boron carbide ceramics block materials and preparation method thereof, methods are as follows: synthesizes nano twin crystal boron carbide block by discharge plasma sintering method using nano boron carbide powder as raw material (1)；(2) nano twin crystal boron carbide bulk is synthesized by hot-pressing sintering method；(3) nano twin crystal boron carbide bulk is synthesized by high temperature and pressure, the hardness of the nano twin crystal boron carbide block materials synthesized is 30-55GPa, and fracture toughness is 4.0-8.0 MPa m1/2Flexural strength is 500-850MPa, twin width is 1-100nm, size of microcrystal is 10nm-10 μm, consistency 95-100%, has higher consistency, specific strength, the characteristic of high rigidity and high-fracture toughness, as a kind of superhard material, it can be applicable to lightweight armor, bulletproof equipment, cutting element and drill bit, high-temperature-resistant structure component etc. have broad application prospects.
Description
Technical field
The present invention relates to high performance structure ceramic technical fields, in particular to high-performance nano twin boron carbide ceramics block
Material and preparation method thereof.
Background technique
Boron carbide ceramics is a kind of low-density (density is only 2.52g/cm2), and high rigidity (is only second to diamond and cube nitrogen
Change boron), high-melting-point (2450 DEG C), the material of high chemical stability and high neutron absorption section.These excellent performances make carbon
Change boron to be widely applied, as bulletproof armour, cutting element, high-temperature-resistant structure component, wear-resistant parts and neutron-absorbing material etc..However
Due to having very strong covalent bond between of carbonization boron crystal Central Plains, so that its diffusion coefficient during the sintering process is low, plasticity is poor,
Grain Boundary Sliding resistance is big, causes to be difficult to be sintered out fine and close boron carbide bulk to limit its further application.
Under normal conditions, in order to improve the consistency of boron carbide bulk, acceleration of sintering densification can introduce sintering aid
Such as: silicon, aluminium, carbon, carbide and boride etc..Although these sintering aids can reduce sintering temperature and promote densification,
But the introducing of the second phase will lead to theoretical density of the density greater than single-phase boron carbide of product, can also reduce the strong of material sometimes
Degree and hardness and thermal stability, not can guarantee boron carbide ceramics and have both lightweight, high-strength, high hard characteristic.In aerospace, force
The application fields such as device plate armour, the specific strength of boron carbide ceramics material is a most important index, that is to say, the density of material is got over
It is low, strength/hardness is higher, specific strength could be higher, and protective capacities just can be stronger.Therefore, low-density, high-strength, high hard, nothing are prepared
The single-phase boron carbide ceramics of binder is of great significance.It is well known that the pattern of forerunner's boron carbide powder, particle size and
The heterogeneous microstructure of powder by boron carbide bulk product consistency and mechanical property have an important influence on.Usually recognize
For sintering temperature will be reduced by reducing boron carbide precursor powder size to nanoscale, be conducive to sintering densification, obtained high property
It can boron carbide ceramics material.Recently, it is high to have found that nano twin crystal diamond and cubic boron nitride bulk possess by Tian Yongjun et al.
Hardness and fracture toughness, according to the collective effect of Hall Page effect and quantum confined effect, the hardness of covalent material can be with
The reduction (reduction of crystal grain or twin size) of heterogeneous microstructure and continue to increase.Therefore, by introducing high density twin
Carry out thinning microstructure structure to improve the performances such as hardness, the toughness of material as effective way.
Summary of the invention
Use high-purity nano boron carbide powder as predecessor the technical problem to be solved by the invention is to provide a kind of
It is sintered nano twin crystal boron carbide ceramics, obtains high-compactness, low-density, hardness is higher, and intensity is higher, the higher carbon of fracture toughness
Change boron ceramic block material and preparation method thereof.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
High-performance nano twin boron carbide ceramics block materials and preparation method thereof, comprising the following steps:
(1) using nano boron carbide powder as raw material, the pre-molding on powder compressing machine is put into mold；
(2) by raw material after molding using different methods certain pressure, at a temperature of be sintered synthesis.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release.
Further, the partial size of nano boron carbide powder used in the step (1) is 10-1000nm, and purity is greater than
90%。
Further, in the step (2), sintering and synthesizing method is that raw material after molding and graphite jig are put into electric discharge
Pressure is kept to keep the temperature 0-120 minutes under conditions of 30-100MPa, 1600-2100 DEG C of temperature in plasma sintering equipment.
Further, in the step (2), sintering and synthesizing method is that raw material after molding and graphite jig are put into hot pressing
In sintering furnace, 1-600 minutes are kept the temperature under conditions of 1800-2300 DEG C of temperature, pressure 20-100MPa.
Further, in the step (2), sintering and synthesizing method is that the raw material after pre-molding is put into high temperature and pressure conjunction
At in mold, pressure 1-25GPa, heat preservation 0-120 minutes of 1400-2000 DEG C of temperature are kept.
Further, high-performance nano twin boron carbide ceramics block materials have been prepared by the above method.
Further, the high-performance nano twin boron carbide ceramics block materials of above method preparation, intra-die contain
There is high density feather organization, twin width is 1-100nm, and size of microcrystal is 10nm-10 μm.
Further, the high-performance nano twin boron carbide ceramics block materials of above method preparation, crystal structure is water chestnut
The B of square structure4C, hardness 30GPa-55GPa, fracture toughness are 4.0-8.0 MPa m1/2, flexural strength 500-
850Mpa。
By adopting the above-described technical solution, the technological progress achieved by the present invention is:
1. the advantages that the present invention is based on nano boron carbide powders to have partial size small, and surface can be big, and sintering activity is high, uses nanometer
Boron carbide powder effectively improves the problem of boron carbide is difficult to densified sintering product as predecessor, makes to prepare high-compactness, high-performance
Boron carbide bulk be possibly realized.
2. the present invention is according to Hall Page effect and quantum confined effect, by reducing heterogeneous microstructure: reducing crystal grain
Or tiny twin substructure is introduced, significantly improve the hardness of boron carbide ceramics, the performances such as fracture toughness.On this basis, make
It uses nano boron carbide powder as predecessor, obtains high-compactness, high rigidity, high-fracture toughness and high-intensitive boron carbide pottery
Porcelain bulk.
3. in the present invention, using nano boron carbide powder as raw material, the large specific surface area of nano-powder, surface energy
Height facilitates the sintering and densification of boron carbide ceramics, and to prepare high-compactness, high performance boron carbide bulk provides new way
Diameter.
4. preparation method of the present invention is easy to implement, equipment used is all common apparatus, is to buy in face in the market
Equipment, device model is not unique, can be substituted by same kind.For example, discharge plasma equipment of the present invention is Japan
The 3.20MK-IV type of Sinter Land company production；Hot-press equipment is by the limited public affairs of Jinzhou City's boda high-temperature material device fabrication
Take charge of the ZRY-15 type multifunctional high-temperature hot-pressed sintering furnace of manufacture；The CS-1B type six of high temperature and pressure agglomerating plant osmanthus smelting heavy industry production
Push up the T25 type high temperature and pressure synthesis device of hydraulic press and the production of Rockland Research company, the U.S. in face.
5. obtained high-performance nano twin boron carbide ceramics block materials contain largely in intra-die in the present invention
Twin structure, the twin boundary present in boron carbide bulk can inhibit the movement and sliding of dislocation, improve its mechanicalness
Energy.
6. the high-performance nano twin boron carbide that the present invention compared with the boron carbide block materials of prior art preparation, obtains
Consistency, hardness, fracture toughness and the intensity of ceramic block material are higher than commercial boron carbide bulk, and hardness is up to
55GPa, fracture toughness are up to 8.0 MPa m1/2, flexural strength is up to 850MPa.Nano twin crystal boron carbide bulk
In bulletproof armour, cutting element, wear-resistant parts and grinding materials and grinding tool etc. have broad application prospects.
7. preparation method of the present invention is simple, parameter is easily controllable, is suitble to industrialized production.
Detailed description of the invention
The picture of Fig. 1 nano boron carbide powder scanning electron microscope；
The X-ray diffractogram of Fig. 2 nano boron carbide powder and nano twin crystal boron carbide ceramics block materials；
Transmission electron microscope (a) shape appearance figure and (b) High-Resolution Map of Fig. 3 nano twin crystal boron carbide ceramics block materials；
The Vickers indentation figure of Fig. 4 nano twin crystal boron carbide ceramics block materials.
Specific embodiment
The present invention is described in further details combined with specific embodiments below:
The present invention provides high-performance nano twin boron carbide ceramics block materials and preparation method thereof, comprising the following steps:
(1) using nano boron carbide powder as raw material, the pre-molding on powder compressing machine is put into mold；Nano silicon carbide used
The partial size of boron powder is 10-1000nm, it is highly preferred that being 10-500nm.As reaction raw materials, it is desirable that its purity 90% or more,
Preferably material purity is 95% or more.
Nano boron carbide powder used in the present invention, boron carbide powder particle are irregular chondritic, and partial size is equal
It is even average in 100nm or so, as shown in Figure 1.
(2) by raw material after molding using different methods certain pressure, at a temperature of be sintered conjunction
At.There are three types of methods altogether:
A. first method is to be put into raw material after molding and graphite jig in discharging plasma sintering equipment that pressure is kept to exist
30-100MPa keeps the temperature 0-120 minutes under conditions of 1600-2100 DEG C of temperature.The pressure limit 30-100MPa used, such as:
30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa or 100Mpa；The temperature range used is 1600-2100
DEG C, such as: from 1600 DEG C, 1700 DEG C, 1800 DEG C, 1900 DEG C, 2000 DEG C, 2100 DEG C or 1800-2100 DEG C；Sintering time is 0-
120 minutes, such as: 0,10,15,20,30,40,50,60,100,120 minutes.It can not keep the temperature, temperature reaches preset value i.e.
It can.
B. second method is that raw material after molding and graphite jig are put into hot-pressed sintering furnace, in temperature 1800-
2300 DEG C, 1-600 minutes are kept the temperature under conditions of pressure 20-100MPa.1800-2300 DEG C of the temperature used, such as: from 1800,
1900,2000 to 2150,2200,2250,2300 DEG C；Pressure 20-100MPa, such as: 20,30,40,50,60 to 80,
100Mpa；Soaking time 1-600 minutes, such as: 1,30,50,70,90,100 minutes or 100-200,200-300,400-600
Minute.
C. the third method is that the raw material of pre-molding is put into high temperature and pressure synthetic mould, keeps pressure 1-
25GPa, heat preservation 0-120 minutes of 1400-2000 DEG C of temperature.The pressure used is 1GPa-25GPa, such as: 1,5,10,15,20,
25 or 1-10,10-20,20-25Gpa；1400-2000 DEG C of temperature, such as: 1400,1500,1600,1650,1750,1800,
1850,1900,1950,2000℃；Soaking time 0-120 minutes, such as: 0,5,10,20,30,40,50,60 minutes or 60-
120 minutes.It can not keep the temperature, temperature reaches preset value.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release.
During step (1) and step (2) are by preparing powder to before being packed into sintering mold, raw material is preferably put
In vacuum environment or inert atmosphere, such as in argon gas glove box.
The high-performance nano twin boron carbide ceramics block materials of above method preparation, intra-die contain high density twin
Tissue, twin width are 1-100nm, and size of microcrystal is 10nm-10 μm, and crystal structure is the B of water chestnut square structure4C, consistency are up to
95% or more, hardness 30GPa-55GPa, fracture toughness are 4.0-8.0 MPa m1/2, flexural strength 500-
850Mpa.Size of microcrystal is 10nm-10 μm, such as: from 10,20,30,40,50,60,70,80,90,100 or 110nm to 1 μm,
2-10μm；Its hardness be 30GPa-55GPa, such as: from 30,31,32,33,34,35GPa or 35-45Gpa, 46,47,48,49,
55Gpa；Fracture toughness is 4.0-8.0 MPa m1/2, such as: 4.0,4.5 or 5.0 MPa m1/2To 5-8 MPa m1/2；Bending resistance
Qu Qiangdu is 500-850Mpa, such as: 500,550,600,650,700 or 800 MPa to 850 MPa.
Contain a large amount of twin structure in the intra-die of high-performance nano twin boron carbide ceramics block materials, is being carbonized
Twin boundary present in boron bulk can inhibit the movement and sliding of dislocation, to improve its mechanical performance；With high-compactness,
The high-performance boron carbide ceramic block material of high specific strength, high rigidity and high-fracture toughness.
Specific embodiment is as follows:
Embodiment 1:
The embodiment prepares high-performance nano twin boron carbide ceramics block materials using discharge plasma sintering.
(1) discharge plasma is sintered (SPS) raw material preparation: weighing the graphite that 2g nano boron carbide powder is put into Φ 15mm
In mold, pressurize 2MPa pre-molding on powder compressing machine.
(2) SPS synthesized high-performance nano twin crystal boron carbide ceramics block materials: by the raw material and graphite of above-mentioned pre-molding
Mold is put into SPS equipment, is evacuated to vacuum degree lower than 1e-2Pa, pressurize 50MPa, is warming up to 1850 DEG C and heats 3 minutes.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release is cooling.
The performance for the high-performance nano twin boron carbide ceramics block materials that the embodiment is prepared: its density is
2.46g/cm3, relative density is up to 98%, and X ray diffracting spectrum is as shown in Fig. 2, its phase composition is pure phase B4C, by hardometer
It is 38GPa that KB-5 BVZ microscope, which tests hardness, and for relative density up to 98%, fracture toughness is 6 MPa m1/2, flexural strength is
780MPa。
As shown in Figure 3, the transmission electron microscope picture of high-performance nano twin boron carbide ceramics block materials can be seen that in crystalline substance
Highdensity twin structure is contained in intragranular portion, and twin width is about 5-15nm.
Embodiment 2:
The embodiment prepares high-performance nano twin boron carbide ceramics block materials using discharge plasma sintering.
(1) discharge plasma raw materials for sintering prepares: weighing the graphite mo(u)ld that 2.5g nano boron carbide powder is put into Φ 15mm
In tool, pressurize 2MPa pre-molding on powder compressing machine.
(2) SPS synthesized high-performance nano twin crystal boron carbide ceramics block materials: by the sample and graphite of above-mentioned pre-molding
Mold is put into SPS equipment, is evacuated to vacuum degree lower than 1e-2Pa, pressurize 100MPa, is warming up to 1600 DEG C, heat preservation
120min。
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release is cooling.
The performance for the high-performance nano twin boron carbide ceramics block materials that the embodiment is prepared: its density is
2.51g/cm3, relative density is up to 100%, consisting of pure phase B4C, crystallite dimension 100nm, hardness 37GPa are broken tough
Property be 5.0 MPa m1/2, flexural strength 750MPa.
Embodiment 3:
The embodiment prepares high-performance nano twin boron carbide ceramics block materials using hot pressed sintering.
(1) it hot pressed sintering raw material preparation: weighs 2g nano boron carbide powder and is put into the graphite jig of Φ 15mm, in powder
Pressurize 2MPa pre-molding on tablet press machine.
(2) by after precompressed raw material and graphite jig be put into hot press, be evacuated to vacuum degree lower than 10Pa, be warming up to
2100 DEG C, heating rate is 5 DEG C/min, and pressurize 50Mpa, keeps the temperature 30 minutes at 2100 DEG C.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release is cooling.
The performance for the high-performance nano twin boron carbide ceramics block materials that the embodiment is prepared: according to Archimedes
It is 97.5% that drainage measurement, which obtains its relative density, hardness 36GPa, and fracture toughness is 5.4 MPa m1/2, flexural strength
For 700MPa.
Embodiment 4:
The embodiment prepares high-performance nano twin boron carbide ceramics block materials using hot pressed sintering.
(1) it hot pressed sintering raw material preparation: weighs 2g nano boron carbide powder and is put into the graphite jig of Φ 15mm, in powder
Pressurize 2MPa pre-molding on tablet press machine.
(2) by after precompressed raw material and graphite jig be put into hot press, be evacuated to vacuum degree lower than 10Pa, be warming up to
2300 DEG C, it is forced into 100Mpa, keeps the temperature 100 minutes, obtains high-performance nano twin boron carbide ceramics block after release cooling down
Body material.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release is cooling.
The performance for the high-performance nano twin boron carbide ceramics block materials that the embodiment is prepared: consisting of pure phase
B4C, average grain size are 10 μm, and test shows that its hardness is 38GPa, and fracture toughness is 4.5 MPa m1/2, flexural strength
For 850MPa.
Embodiment 5:
The embodiment uses cubic hinge press high temperature and pressure sintering high-performance nano twin crystal boron carbide ceramics block materials.
(1) nano boron carbide powder high temperature and pressure raw material preparation: is pressed into diameter of phi 5mm, the cylinder block of height 8mm.
(2) high temperature and pressure synthesizes: the above-mentioned raw material pressed is put into diameter of phi 5mm, the hexagonal boron nitride crucible of height 8mm
It is interior, it is then charged into the device of high temperature and pressure synthetic sample, 6GPa is first forced into and is warming up to 1700 again with the rate of 100 DEG C/min
DEG C, 15min is kept the temperature, obtains high-performance nano twin boron carbide ceramics block materials after release cooling down.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release is cooling.
The performance for the high-performance nano twin boron carbide ceramics block materials that the embodiment is prepared: its X-ray diffraction
As shown in Fig. 2, its phase composition is pure phase B4C, hardness 38GPa, fracture toughness are 6.2 MPa m1/2, relative density 99%.
Embodiment 6:
The embodiment uses cubic hinge press high temperature and pressure sintering high-performance nano twin crystal boron carbide ceramics block materials.
(1) nano boron carbide powder high temperature and pressure raw material preparation: is pressed into diameter of phi 5mm, the cylinder block of height 8mm.
(2) high temperature and pressure synthesized high-performance nano twin crystal boron carbide ceramics block materials: the above-mentioned raw material pressed is put into
In the hexagonal boron nitride crucible of diameter of phi 5mm, height 8mm, it is then charged into the device of high temperature and pressure synthetic sample, is first forced into
1Gpa, then 2000 DEG C are warming up to the rate of 100 DEG C/min, keep the temperature 0min.It is twin that high-performance nano is obtained after release cooling down
Brilliant boron carbide ceramics block materials.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release is cooling.
The performance for the high-performance nano twin boron carbide ceramics block materials that the embodiment is prepared: its phase composition is pure
Phase B4C, hardness 38GPa, fracture toughness are 8.0 MPa m1/2, relative density 99%.
Embodiment 7:
The embodiment uses T25 high temperature and pressure synthesized high-performance nano twin crystal boron carbide ceramics block materials.
(1) nano boron carbide powder high temperature and pressure raw material preparation: is pressed into diameter of phi 1.5-3mm, the block of high 3-5mm in advance
Body.
(2) high temperature and pressure prepares high-performance nano twin boron carbide ceramics block materials: by the block material of above-mentioned precompressed
It is put into high temperature and pressure synthesizer, is then charged into T25 pressurizing device, be slowly forced into 25GPa, heat up 1100-1600 DEG C,
Heating and thermal insulation 10 minutes, high-performance nano twin boron carbide ceramics block materials were obtained after release cooling down.
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release is cooling.
The performance for the high-performance nano twin boron carbide ceramics block materials that the embodiment is prepared: it is arranged by Archimedes
Water law measures its relative density greater than 99%, is illustrated in figure 4 its Vickers hardness impression figure, and hardness 42-55Gpa is broken tough
Property be 7-8 MPa m1/2。
Analysis of experimental results shows the synthetic method using high temperature and pressure, can synthesize high property at relatively low temperature
Energy nano twin crystal boron carbide ceramics block materials, and crystal grain does not occur abnormal growth, obtains high-compactness, high rigidity, height fracture
The boron carbide ceramics block materials of toughness.
It is in summary a specific embodiment of the invention, but protection scope of the present invention is not limited to this, it is any to be familiar with
Those skilled in the art in the technical scope disclosed by the present invention, all cover by the replacement or variation that can be readily occurred in
Within protection scope of the present invention.
Claims (7)
1. the preparation method of high-performance nano twin boron carbide ceramics block materials, it is characterised in that: the following steps are included:
(1) using nano boron carbide powder as raw material, the pre-molding on powder compressing machine is put into mold；
(2) by raw material after molding using different methods certain pressure, at a temperature of be sintered synthesis；
(3) high-performance nano twin boron carbide ceramics block materials are obtained after cooling release.
2. the preparation method of high-performance nano twin boron carbide ceramics block materials according to claim 1, feature exist
In: the partial size of nano boron carbide powder used in the step (1) is 10-1000nm, and purity is greater than 90%.
3. the preparation method of high-performance nano twin boron carbide ceramics block materials according to claim 1, feature exist
In: in the step (2), sintering and synthesizing method is that raw material after molding and graphite jig are put into discharging plasma sintering equipment
Middle holding pressure keeps the temperature 0-120 minutes under conditions of 30-100MPa, 1600-2100 DEG C of temperature.
4. the preparation method of high-performance nano twin boron carbide ceramics block materials according to claim 1, feature exist
In: in the step (2), sintering and synthesizing method is that raw material after molding and graphite jig are put into hot-pressed sintering furnace, in temperature
1800-2300 DEG C is spent, keeps the temperature 1-600 minutes under conditions of pressure 20-100MPa.
5. the preparation method of high-performance nano twin boron carbide ceramics block materials according to claim 1, feature exist
In: in the step (2), sintering and synthesizing method is that the raw material after pre-molding is put into high temperature and pressure synthetic mould, is kept
Pressure 1-25GPa, keeps the temperature 0-120 minutes by 1400-2000 DEG C of temperature.
6. high-performance nano twin boron carbide ceramics block materials, it is characterised in that: block materials internal grain contains high density
Feather organization, twin width are 1-100nm, and size of microcrystal is 10nm-10 μm.
7. high-performance nano twin boron carbide ceramics block materials according to claim 6, it is characterised in that: block materials
Crystal structure is the B of water chestnut square structure4C, hardness 30GPa-55GPa, fracture toughness are 4.0-8.0 MPa m1/2, counter-bending
Intensity is 500-850MPa.
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