CN101668716A - Boron suboxide composite material - Google Patents

Abstract

The invention provides the boron suboxide composite material that comprises boron suboxide and two second phases, wherein said two second phases contain boride.Described boride can be selected from the boride of transition metal of the 4th to the 8th family of periodictable.Especially, described boride can chosen from Fe, the boride of cobalt, nickel, titanium, tungsten, hafnium, tantalum, zirconium, rhenium, molybdenum or chromium.Described boride can also be the platinum metals boride, preferably the boronation palladium.Described two second phases also can contain one or more oxide compounds.

Description

Boron suboxide composite material

Background of invention

The present invention relates to boron suboxide (boron suboxide) matrix material.

Have near or even the exploitation that surpasses the synthesizing superhard material of adamantine hardness value receive material supply section scholar's very big concern always.Diamond with Vickers' hardness of 70-100GPa is known hard material, secondly is that (Hv～60GPa) and boron suboxide (are called B herein to cubic boron nitride ₆O).B ₆The O monocrystalline has the hardness value of 53GPa and 45GPa after measured respectively under 0.49N and 0.98N load, these hardness values are similar to the hardness value [9] of cubic boron nitride.

Known B ₆O can also be non-stoichiometric, promptly presses B ₆O _1-xThere is (wherein x is 0-0.3).Such non-stoichiometric forms is included in term B ₆Among the O.The strong covalent bond of these materials and short interatomic bond length are facilitated uncommon physics and chemical property, for example big hardness, low mass density, high thermal conductivity, high unreactiveness and excellent abrasion resistance [1,2].In the U.S. Patent No. 5,330,937 of Ellison-Hayashi etc., reported and have name and form B ₃O, B ₄O, B ₆O, B ₇O, B ₈O, B ₁₂O, B ₁₅O and B ₁₈The formation of the boron suboxide powder of O.(Japanese Patent No.7 such as Kurisuchiyan, 034,063) and (U.S. Patent No. 5,456 such as Ellison-Hayashi, 735) discussed the potential industrial application, these potential industrial application are included in the use in emery wheel (grinding wheel), abrasive material and the cutter.

Some technology have been used to prepare boron suboxide and have comprised such as make pure boron (B) and boron oxide (B under high aptly pressure and high temperature condition ₂O ₃) the such operation [1] of reaction.In the U.S. Patent No. 3,660,031 of Holcombe Jr. etc., mentioned other method of preparation boron suboxide, for example use magnesium reduction boron oxide (B ₂O ₃), perhaps by using pure boron reduction-oxidation zinc.Yet, there is the defective that hinders the availability of this material in industry in these known procedure each.For example, use magnesium reduction B ₂O ₃In suboxide, produce the sosoloid of magnesium and boronation magnesium pollutent, and only produce relatively little boron suboxide yield and be unusual poor efficiency with boron reduction-oxidation magnesium.(U.S. Patent No. 3,660,031) such as Holcombe Jr. is by preparing B with pure boron reduction-oxidation zinc under 1200 ℃-1500 ℃ temperature ₇O.Having reported the hardness value of this material under 100g load is 38.2GPa, and density is 2.6g.cm ^-3The do not touch upon fracture toughness property of this material.

Petrak etc. [3] have studied hot pressing B ₆The mechanics of O and chemical property, and reported high microhardness value to 34-38GPa.Ellison-Hayashi etc. (United States Patent (USP) 5,330,937) have made the B that is added with magnesium (about 6%) ₆O, this produces the average KHN100 value of 34GPa-36GPa.

Attempted by with other mechanically resistant material for example diamond [4], norbide [5] and cBN[6] form B ₆The O matrix material improves B ₆The mechanical property of O, particularly its fracture toughness property.Under high temperature and pressure condition, make the matrix material that contains diamond and cBN.Intention forms pseudo-binary composite system, at the crystal boundary place than pure B ₆O is stronger.Although (Hv～46GPa), again, the fracture toughness property value is no more than 1.8MPa.m to have write down high hardness value for this matrix material ^0.5Here for B ₆The O-cBN matrix material obtains optimum value.

Shabalala etc. (WO 2007/029102 and [7]) have made the B with aluminum compound ₆O matrix material, described aluminum compound produce the aluminum borate phase at the crystal boundary place.Obtained to have about 3.5MPa.m of the corresponding hardness of 29.3GPa ^0.5Fracture toughness property.The aluminium that is present in this matrix material is soft mutually, though and they can improve the fracture toughness property of gained matrix material, they are helpless to the overall hardness of this matrix material.In addition, except that crystalline aluminium borate, also form be rich in boron oxide, chemically unstable non-crystalline state mutually and microvoid structure, thereby further cause the hardness [10,11] that reduces.The preparation method of this matrix material comprises that this has applied metallic particle with washing boron suboxide particles and sintering.Unique embodiment in this specification sheets is about aluminum borate two second phases (secondary phase) or tackiness agent phase.

Summary of the invention

According to the present invention, the boron suboxide composite material that comprises boron suboxide and two second phases is provided, wherein said two second phases contain boride.

For this specification sheets, the various materials in " two second phases " expression matrix material except that boron suboxide, and can all or part ofly be crystalline state or amorphous, can comprise more than a kind of thermodynamics phase.

In addition, any citation of " boride " comprises the boride of a boride, diboride and any other form.

Boride can be selected from the boride of the 4th to the 8th group 4 transition metal of periodictable.Especially, boride can chosen from Fe, the boride of cobalt, nickel, titanium, tungsten, hafnium, tantalum, zirconium, rhenium, molybdenum or chromium.

Boride can also be the platinum metals boride, preferred boronation palladium.

The amount of the boride that exists in the matrix material can change according to the character and the required performance of composites of this boride.Usually, for hard borides ZrB for example ₂, HfB ₂, W ₂B ₅(this boride has the WB of comprising ₂Homogenous area), Mo ₂B ₅, CrB ₂, TiB ₂, ReB ₂, TaB ₂And NbB ₂, the amount of this boride can be the 50 volume % at the most of matrix material.For the softer boride boride of nickel, cobalt, iron, manganese, palladium and platinum for example, the amount of this boride is preferably the 10 volume % at the most of matrix material.

Two second phases can also contain one or more oxide compounds.This oxide compound can be the rare-earth oxide in rare-earth oxide and the oxide compound that preferably is selected from scandium, yttrium (it is for preferred) and lanthanon.This oxide compound can also be the oxide compound of IA, IIA, IIIA or the IVA family metal of periodictable.The example of such preferred oxides is Al ₂O ₃, SiO ₂, MgO, CaO, BaO or SrO.Two second phases can contain these hopcalites.

Boron suboxide can be the boron suboxide of particulate state (particulate) or grains (granular).The mean particle size of boron suboxide particles or crystal grain itself is preferably thin and can is 100nm-100 μ m, preferred 100nm-10 μ m.

Can for example, the boron suboxide source prepare the fine particulate boron suboxide by being milled.If mill containing in the presence of the medium of milling of iron or cobalt, some iron and/or cobalt will be introduced in the agglomerating material.In order to obtain the material of iron-free, the powder that the acceptable salts acid elution is milled perhaps can use the oxidation aluminium pot and the ball of milling is milled.Found that advantageously the powder of milling with warm water or alcohol washing is to remove any excessive B ₂O ₃Or H ₃BO ₃

Matrix material of the present invention comprises two second phases of the boron suboxide that is generally particle or crystal grain form and bonded adhesion form.Two second phases preferably exist with the percent by volume littler than boron suboxide and are evenly dispersed in the boron suboxide.Two second phases can be non-crystalline state or part crystalline state.

The invention provides the matrix material that contains boron suboxide and boride, this matrix material has high fracture toughness property and high hardness.Especially, this matrix material has usually greater than 3.5MPa.m ^0.5Fracture toughness property and with Vickers' hardness (H greater than 25GPa _V).Preferably, the fracture toughness property of this matrix material is greater than 3.5MPa.m ^0.5And 4.0MPa.m at least more preferably ^0.5And be more preferably 5.0MPa.m at least ^0.5Fracture toughness property (K used herein _IC) be that common load with 5kg records at the impression place.Use the mean value of 5 measuring results to determine the B that is hereinafter discussed ₆The performance of O sample.Use following Anstis equation [8] to measure K by the DCM method _IC:

$\left(1\right),K_C=\mathrm{\δ}{\left(\frac{E}{H}\right)}^{\frac{1}{2}}\frac{P}{c^{\frac{3}{2}}}$

Wherein E is a Young's modulus, and H is a hardness, and δ is the constant that only depends on the pressure head geometrical shape.For the Young's modulus value in this equation, use the value of 470GPa.For standard Vickers diamond pyramid indenter, people such as Anstis have set up the value of δ=0.016 ± 0.004 as calibration constants, measure for these and also use this constant.

The hardness of this matrix material is preferably greater than 25GPa and is preferably 30GPa at least.Use the loading of pressing in of 5kg to measure Vickers' hardness.Use the mean value of measuring hardness value for 5 times to determine B ₆The performance of O composite sample.

Fig. 1 has shown that matrix material of the present invention is with respect to the hardness of prior art boron suboxide material and the preferred lower threshold in fracture toughness property interval.It is believed that the tough property improvement of these type matrix materials is attributable to a plurality of factors, for example the crack deflection that causes by the generation of internal stress, occur in crack arrest mechanism and B in two second phases that produced ₆The change of properties of the performance of crystal boundary and composition between the O particle.In addition, find by use contain independent or with two second phases of the rare-earth oxide of another kind of oxide compound or boride combination, strengthened effective densification of matrix material during the preparation.95% the density that surpasses theoretical density is possible.Especially, obtained the density of 98%-99%.When having oxide compound in two second phases, can under relatively mild temperature and pressure condition, realize densification.

Being added in of oxide compound chemically makes amorphous grain boundary stable, and matrix material is resistance to worn more.This amorphous grain boundary produces oxide compound and B during liquid phase of densification ₂O ₃Between reaction.They form oxide compound liquid together, and this oxide compound liquid during cooling becomes glassy phase (being amorphous oxide attitude crystal boundary).For abrasion resistance, chemical stability and the high-temperature stability that improves material, B in the preferred crystal boundary ₂O ₃Content low.Preferably less than 60 B ₂O ₃/ (B ₂O ₃+ other oxide compound) mol ratio is more preferably less than 30 mol ratio, and is more preferably the mol ratio less than 20.

Matrix material of the present invention can make by following: boron suboxide particles or crystal grain source are provided; Thereby the compound that makes this boron suboxide source and boride maybe can produce boride contacts and produces reaction mass; Thereby produce boron suboxide composite material with this reaction mass of sintering.This method forms another aspect of the present invention.

Sintering preferably carries out under low relatively temperature and pressure, promptly less than the pressure of 200MPa be no more than 1950 ℃ temperature.For example hot pressing of preferred lower pressure power sintering method (HP), gas pressure sintering, hot isostatic pressing (HIP) or discharge plasma sintering (SPS).The SPS method is characterised in that heating rate and 5 minutes or the isothermal hold-time still less of the isothermal hold-time, particularly 50-400K/ of heating very fast and lacking minute.Hot-press method is characterised in that 10-20K/ minute heating rate and about 15-25 minute, 20 minutes isothermal hold-time of typical case.

Before sintering step, boron suboxide can be mixed with the necessary component of generation two second phases.As an alternative, can before sintering, apply boron suboxide with two minor phase constituents.

The component that is used for two second phases is contacting with boron suboxide and can be the boron oxide form during sintering then.Scheme as an alternative, this component can be oxide compound or other suitable form that can change boride during sintering processes into.

Be used for that the boron suboxide of reaction mass can be particle or crystal grain form usually before the sintering, and preferably have 100nm to 20 micron mean particle size and more preferably 100nm to 10 micron mean particle size.

Matrix material according to the present invention can be used for cutting and uses and wear part.Also it can be crushed to the sand grains form and be used for abrasive application.In addition, this matrix material can be used for armoring application examples such as bulletproof armour, particularly watch box plate armour.

The accompanying drawing summary

Fig. 1 shows B of the present invention ₆O matrix material and from the relative hardness of the similar type material of prior art and the coordinate diagram of fracture toughness property value.

Fig. 2 is by being mixed with 10 weight %TiB ₂, 2.0 weight %Al ₂O ₃With 2.0 weight %Y ₂O ₃B ₆The SEM image (embodiment 5) of the sintered composite materials of O preparation.

Fig. 3 is by being mixed with 4 weight %WO ₃, 2.0 weight %Al ₂O ₃B ₆The SEM image of the sintered composite materials of O preparation has shown the W of submicron ₂B ₅The oxide compound crystal boundary (embodiment 4) that precipitate (white phase) and part are wiped.

Fig. 4 comprises pure B ₆O and doping B ₆(white is Pd to 5 SEM images of the hot pressed samples of O mutually ₂B, grey form and aspect are B ₆O; Dim spot is residual hole).

The description of embodiment of the present invention

To the present invention be described by the following example now.Table 1 has gathered these materials and their measured hardness and toughness properties so that compare.In these embodiments, term " two second phases " all obtained using with " crystal boundary mutually ".Described term uses and is meant identical phase interchangeably.

For this specification sheets, every kind of material in " two second phases " expression matrix material except that boron suboxide, and can be crystalline state or non-crystalline state whole or in part, and can comprise more than a kind of thermodynamics phase.

Embodiment 1

Use the jet mill B that mills ₆The O initial powder.Average particle size particle size after milling is 2.3 μ m.With the B that mills ₆O powder and 2 weight %Al ₂O ₃(comprising wearing and tearing), 2 weight %Y from alumina balls ₂O ₃, 2 weight %ZrO ₂(promptly using the stable in addition TZP of 3 moles of yttrium oxide) and 0.53 weight %MgO mix in Virahol and utilize masher Al ₂O ₃Ball was milled 6 hours.At no Y ₂O ₃Second kind of sample of preparation under the situation of adding.The mixture that uses the rotatory evaporator drying to mill also is placed in the graphite mo(u)ld that scribbles six side BN then, uses the SPS method to carry out sintering with 50K/ minute heating rate and 5 minutes hold-time under argon atmospher.

Make the matrix material of the abundant densification that comprises boron suboxide particles, two second phases are evenly dispersed in this matrix material.Containing Y ₂O ₃Sample in, formed ZrB ₂And ZrB ₁₂, and amorphous crystal boundary.There is not Y ₂O ₃In the sample that adds, detect by XRD and to contain Al ₁₈B ₄O ₃₃Other crystalline state phase.MgO and residue B ₂O ₃With some Al ₂O ₃Form amorphous crystal boundary phase together.This amorphous grain boundary is compared and is only used Al ₂O ₃The sort of (Shabalala) that forms is more stable.Do not observe the characteristic feature that micropore forms, thereby produce higher hardness value.ZrO ₂Change ZrB into ₂And part changes ZrB into ₁₂That must mention is ZrB ₁₂The peak skew a little takes place than standard value, show to exist some to be dissolved in yttrium or aluminium in the lattice.

The cross section of polishing sample also tries hardness and fracture toughness property with Vickers impression instrumentation then.Discovery hardness under 0.4kg load is about 36.9GPa, and fracture toughness property is about 4MPa.m ^0.5

Embodiment 2-4

Use with condition identical described in the embodiment 7 to prepare boron suboxide composite material, difference is to use respectively HfO ₂, WO ₃And TiB ₂Substitute ZrO in the ratio that provides in the table 1 ₂Under 1850 ℃ and 1900 ℃, carry out densification.Under 1850 ℃, the density that observes is 96-98%.Under 1900 ℃, the density that observes is greater than 98%.In embodiment 8, to identical density, show and add ZrO for two kinds of temperature observations ₂The time the densification behavior be better than adding HfO a little ₂Or WO ₃The time densification behavior that obtained.

In described sample, also formed Al ₁₈B ₄O ₃₃And boride.As in (WO 2007/029102 and [9]) such as Shabalala, do not form microvoid structure, thereby demonstrate more stable crystal boundary phase.Except that oxide compound mutually, also formed boride (HfB in all embodiments ₂, W ₂B ₅, it is to have the composition of homogeneous scope and also be known as WB sometimes ₂One because do not carry out the detailed mensuration of lattice parameter, so W ₂B ₅And WB ₂Use as equivalent).

Embodiment 5-7

Use with condition identical described in the embodiment 1 to prepare boron suboxide composite material, difference be the powder of will mill in embodiment 5 with 10%TiB ₂Mix or in embodiment 6 with 5%TiH ₂And 2%Al ₂O ₃(comprising the wearing and tearing of aluminum oxide during milling) mixes.Matrix material among the embodiment 7 is with B and TiO ₂Begin to make by the direct reaction sintering.

Material, density, phase composite and performance have been provided in the table 1.These data presentation are added Y ₂O ₃/ Al ₂O ₃Significantly improve densification.For composition with described additive, under 1850 ℃, can finish densification, and only can be with pure B under this temperature ₆The O powder densification is to 95% of theoretical density.Under low 50-100 ℃ temperature, can reach the density identical with pure material.For having Y ₂O ₃/ Al ₂O ₃The material of additive, at 1350-1370 ℃ of beginning quick densifying, and the densification of pure material only begins under 1450 ℃.Be added with Y ₂O ₃/ Al ₂O ₃The microstructure of material disclose and to have such liquid because do not find crystalline state crystal boundary phase (two second phases).SEM figure shows Y ₂O ₃/ Al ₂O ₃The uniform distribution of additive in triple junction (triple junction).Can not measure the granularity of material, but go out granularity less than 1 μ m, promptly not have grain growing to take place by the deducibility of SEM Photomicrograph.

To B ₆O+Y ₂O ₃/ Al ₂O ₃Composition in add 10 weight %TiB ₂Do not change the densification behavior.

Fig. 3 has shown the microstructure of the material of embodiment 10, shows TiB ₂Particle is 1-2 μ m and can sees the oxide compound crystal boundary.

In Fig. 4, provided and be added with WO ₃The microstructure of material (embodiment 9).This material is fine and close and can see the formation of boride near 100%.The particle size of the boride of separating out is less than 1 μ m.

The result has shown the fine and close superhard B of preparation under no high pressure ₆The possibility of O material.These materials are than pure B ₆The formation of liquid phase is relevant during the densification of the improvement of O and the densification.

Embodiment 8-11

According to the method for reporting in the document, by boric acid and the synthetic B of amorphous boron powder ₆The O powder.The average particle size particle size of synthetic powder is 1-2 μ m.Use PdCl ₂As at B ₆The source of precipitation Pd on the O powder.With PdCl ₂(weight shows the Pd of 2 and 5 volume %) is dissolved among the 1M HCl and adds B ₆The O powder.Stir this mixture and use rotatory evaporator to be dried.With exsiccant Pd/B ₆The O powder is put into alumina boat and is placed tube furnace.This stove is heated to 400 ℃ and continue 1 hour so that with PdCl ₂Be decomposed into Pd.With this stove cool to room temperature.

Use hot uniaxial pressing for all hot pressing experiments.In argon atmospher, carry out hot pressing.Use hBN plunger and graphite mo(u)ld for hot pressing with hBN inlay.Preparation has the sample of 18mm diameter and 3-4mm height.Hot pressing Pd/B under the pressure of 1900 ℃ temperature and 50MPa at the most ₆The O powder.The composition and the compacting parameter of sample have been provided in the table 1.Fig. 4 comprises pure B ₆O and doping B ₆5 SEM images of O hot pressed samples.

At first under 50MPa pressure in 1600 ℃ to being doped with the B of 5 volume %Pd ₆O carried out hot pressing 30 minutes.This sample (16B ₆O5Pd) have 26.7% open porosity and 1.75g/cm ³Density.High porosity is tangible in SEM.Because low-down density is not measured mechanical property.Hot pressed sample (19B under 1900 ℃ ₆O ₅Pd) ^-The density that obtains has reached theoretical density.Also observe grain growing.

Facies analysis has mainly shown the Pd as crystal boundary phase (two second phases) ₂B.At all other Pd/B ₆Observe identical boride phase in the O hot pressed samples.Under 1900 ℃ for Pd/B ₆The O hot pressed samples records the hardness of 22.5GPa, and this is than pure B ₆The hardness of O is much lower.Yet, obtain very high fracture toughness property (13.5MPa.m ^0.5).

Because the grain growing that increases, sintering temperature reduces when having 2 volume %Pd.Do not have in 20 minutes to produce fully fine and close sample at 1750 ℃ of following sintering yet, but be better than the sample (seeing Table 1) that has 5 volume %Pd at 1600 ℃ of following agglomerating.High porosity (7.3%) is tangible in the SEM image.Produce near fine and close fully material 1800 ℃ of following hot pressing.Arrived the hardness Hv of 28GPa for this sample record ₅And 5.1MPa.m ^0.5Fracture toughness property.These value ratios are at 1750 ℃ of following agglomerating sample 175B ₆The value that O2Pd obtained is higher.

The density of material is presented at 1750 ℃-1900 ℃ temperature generation densification.These two samples 1750 ℃ and 1900 ℃ following densifications demonstrate some residual porositys.During densification, even form Pd being low to moderate under 1600 ℃ the temperature ₂B.This proof Pd and B ₆The O reaction forms boron-bearing liquid phase (Pd ₂The fusing point of B is 994 ℃).Yet, densification takes place being higher than under 1600-1700 ℃ the temperature only.The SEM image of sample shows that reason may be that (at least at low temperatures) is inadequate a little wetting.Strong grain growing under the hot pressing temperature (1800-1900 ℃) shows B under higher temperature at least ₆O is present in the solvability in the formed liquid, and this helps sintering, because its temperature that can prepare fine and close sample has reduced about 100 ℃.As in the XRD figure case as seen, thereby formed liquid during cooling recrystallize form Pd at the crystal boundary place ₂B.

For 19B ₆The hardness value that O5Pd recorded is lower than 18B ₆The hardness value of O2Pd sample.Reduce Pd ₂The amount of B and reduction sintering temperature have been improved hardness (table 1).What also should emphatically point out is to use 5kg load to carry out hardness measurement.Except that Shabalala uses 0.5kg and 5kg load report hardness value, use maximum 200g load to carry out in the document with regard to B ₆The value that the O matrix material is reported.

With regard to 19B ₆Very high (the 13.5MPa.m of the fracture toughness property that O5Pd obtained ^0.5).Yet hardness is reduced to 22GPa.The reduction of Pd content improves hardness consumingly, but also reduces fracture toughness property.

Embodiment 12-22

According to the method for report in the document [7], by boric acid and the synthetic B of amorphous boron powder ₆The O powder.The average particle size particle size of this synthetic powder is 1-2 μ m.In masher, use the steel ball B that mills ₆The O powder is up to the average particle size particle size that obtains 500nm.By remove pollutent with the HCl washing from steel ball.Add Fe and Cr, Fe, FeO, FeB, Ni, NiO, NiB, Cr, CrO in the ratio shown in the table 1 subsequently ₃, CrB ₂, and the additive of Co.Use hot uniaxial pressing for all hot pressing experiments.In argon atmospher, carry out hot pressing.Preparation has the sample of 18mm diameter and 3-4mm height.The described mixture of sintering under the condition shown in the table 1.Can obtain high density down at 1850 ℃.

The result has shown the fine and close superhard B of preparation under no high pressure ₆The possibility of O material.Phase that exists in the gained pottery and the character that records have been provided in the table 1.Two second phases are evenly distributed in B ₆In the O matrix.Granularity is that the 1-5 micron does not wait.In embodiment 12, do not detect except that B ₆Crystalline state phase (this may be by due to the concentration that is lower than limit of detection) beyond the O.Irrelevant with initial composition (being oxide compound, metal or boride), Fe, Co, Ni and Pd additive have formed boride in two second phases.These borides are liquid under sintering condition, and this metal liquid quickens the densification behavior.During cooling, boride crystallization from melt goes out.These borides are not as TiB ₂Amount hard and therefore these admixtures is preferably minimum, is preferably 1-2 volume %.If have stable oxide in addition in forming, such oxide compound forms isolating oxide melt, and this can pro help hardness and densification.

Table 1

Numbering	Material component (sintering temperature, ℃)	Additive ratio (weight %)	??H V(5kg)，??(GPa)	??K IC，??(MPa.m 0.5)	Phase (behind the sintering)	Density (g/cm 3)
							With reference to *	??B 6O	??-	(30.1 1kg load)	Crisp	??B 6O	??2.5
Prior art *	??B 6O+Al 2O 3	??-	??29.3	??3.5	??B 6O??Al 4B 2O 9
							Embodiment 1a	??B 6O+Al 2O 3+Y 2O 3+ZrO 2+MgO??(1850℃)	??2∶2∶2∶0.53	??34.2±0.6 **	??4	??B 6O，ZrB 2，ZrB 12Non-crystalline state two second phases	??2.60
Embodiment 2	??B 6O+Al 2O 3+ZrO 2+MgO??(1850℃)	??2∶2∶0.53	??36.9±0.6 **	??4	??B 6O，ZrB 2ZrB 12，??Al 18B 4O 33Non-crystalline state two second phases	??2.59
							Embodiment 3a	??B 6O+Al 2O 3+Y 2O 3+HfO 2+MgO??(1900℃)	??2∶2∶2∶0.53	??34.2±0.5 **	??4	??B 6O，HfB 2Non-crystalline state two second phases	??2.52
Embodiment 3b	??B 6O+Al 2O 3+HfO 2+MgO??(1850℃)	??2∶2∶2∶0.53	??36.1±0.6 **	??4	??B 6O，HfB 2Al 18B 4O 33Non-crystalline state two second phases	??2.56
							Embodiment 4a	??B 6O+Al 2O 3+Y 2O 3+WO 3+MgO??(1900℃)	??2∶2∶4∶0.53	??35.6±0.4 **	??4	??B 6O，W 2B 5Non-crystalline state two second phases	??2.61

Embodiment 4b	??B 6O+Al 2O 3+Y 2O 3+WO 3+MgO??(1850℃)	??2∶2∶4∶0.53	??34.0±0.5 **	??4	??B 6O，W 2B 2Non-crystalline state two second phases	??2.61
							Embodiment 4c	??B 6O+Al 2O 3+WO 3+MgO??(1850℃)	??2∶4∶0.53	??34.2±0.6 **	??4	??B 6O，W 2B 2Non-crystalline state two second phases	??2.61
Embodiment 5	??B 6O+Al 2O 3+Y 2O 3+TiB 2+MgO??(1900℃)	??2∶2∶10∶0.53	??36.8±0.5 **	??4	??B 6O，TiB 2.Non-crystalline state two second phases	??2.68
							Embodiment 6a	??B 6O+Al 2O 3+Y 2O 3+TiH 2+MgO??(1900℃)	??2∶2∶5∶0.53	??36.1±0.6 **	??4	??B 6O，TiB 2Non-crystalline state two second phases	??2.49
Embodiment 6b	??B 6O+Al 2O 3+TiH 2+MgO??(1850℃)	??2∶5∶0.53	??33.6±0.6 **	??4	??B 6O，TiB 2Non-crystalline state two second phases	??2.51
							Embodiment 7	??B+TiO 2+MgO+Al 2O 3(wearing and tearing of ball) (1850 ℃)	??65.44∶34.55∶??0.4∶0.5	??28.2±0.6 **	??4	??B 6O，TiB 2.Non-crystalline state two second phases	??2.79
Embodiment 8	??B 6O+Pd (1600 ℃, 30 minutes)	??16∶5	???-	???-	??B 6O，PdB 2	??1.75
							Embodiment 9	??B 6O+Pd (1900 ℃, 30 minutes)	??19∶5	??22.5±0.9	??13.5±3.2	??B 6O，PdB 2	??2.82
Embodiment 10	??B 6O+Pd (1800 ℃, 20 minutes)	??18∶2	??28.0±1.2	??5.1±0.8	??B 6O，PdB 2	??2.61
							Embodiment 11	??B 6O+Pd (1750 ℃, 20 minutes)	??175∶2	??25.0±1.1	??3.9±0.2	??B 6O，PdB 2	??2.41
Embodiment 12	Pure B 6O+Fe，Cr??(1900℃)	??1∶1.2	??34.7±1.1	??3.7±0.10	??B 6O	??2.48
							Embodiment 13	??B 6O+Fe??(1850℃50MPa)	??1.17	??27.4	??3.3	??B 6O，FeB	??2.53
Embodiment 14	??B 6O+FeO??(1850℃50MPa)	??1.5	??28.3	??3.1	??B 6O，FeB	??2.51
							Embodiment 15	??B 6O+FeB??(1850℃50MPa)	??1.4	??27.2	??7.6	??B 6O，FeB	??2.56
Embodiment 16	??B 6O+Cr??(1850℃50MPa)	??1.07	??29.4	??5.5	??B 6O，CrB 2	??2.57
							Embodiment 17	??B 6O+CrB 2??(1850℃50MPa)	??1.7	??32.0	??4.5	??B 6O，CrB 2	??2.51
Embodiment 18	??B 6O+Co??(1850℃80MPa)	??1.33	??33.9	??5.3	??B 6O，CoB	??2.49
							Embodiment 19	??B 6O+CrO 3??(1850℃50MPa)	??1.4	??30.4	??4.8	??B 6O，CrB 2	??2.53
Embodiment 20	??B 6O+Ni??(1850℃80MPa)	??3.7	??30.6	??6.4	??B 6O，NiB	??2.53
							Embodiment 21	??B 6O+NiB??(1850℃80MPa)	??1.5	??31.8	??6.5	??B 6O，NiB	??2.57
Embodiment 22	??B 6O+NiO??(1850℃80MPa)	??2.8	??27.1	??6.1	??B 6O，NiB	??2.54

* derive from the reference of (WO2007/029102) such as Shabalala and the data of prior art sample

* records with 0.4Kg load

Reference

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Claims (26)

1. the boron suboxide composite material that comprises boron suboxide and two second phases, wherein said two second phases contain boride.

2. according to the matrix material of claim 1, wherein said boride is selected from the boride of the 4th to the 8th group 4 transition metal of periodictable.

3. according to the matrix material of claim 2, the boride of wherein said boride chosen from Fe, cobalt, nickel, titanium, tungsten, hafnium, tantalum, zirconium, rhenium, molybdenum and chromium.

4. according to the matrix material of claim 2, wherein said boride is the platinum metals boride.

5. according to the matrix material of claim 4, wherein said platinum metals boride is the boronation palladium.

6. according to each matrix material in the aforementioned claim, wherein said boride is that hard borides and amount are the 50 volume % at the most of matrix material.

7. according to the matrix material of claim 6, wherein said boride is selected from ZrB ₂, HfB ₂, W ₂B ₅, Mo ₂B ₅, CrB ₂, TiB ₂, ReB ₂, TaB ₂And NbB ₂

8. according to each matrix material in the claim 1 to 5, the amount of wherein said boride is 10 volume % at the most.

9. matrix material according to Claim 8, wherein said boride is selected from the boride of nickel, cobalt, iron, manganese, palladium and platinum.

10. according to each matrix material in the aforementioned claim, wherein said two second phases also contain one or more oxide compounds.

11. according to the matrix material of claim 10, wherein said oxide compound is a rare-earth oxide.

12. according to the matrix material of claim 11, wherein said rare-earth oxide is selected from the oxide compound of scandium, yttrium and lanthanon.

13. according to the matrix material of claim 12, wherein said rare-earth oxide is a yttrium oxide.

14. according to the matrix material of claim 10, wherein said oxide compound is the oxide compound of IA, IIA, IIIA and the IVA family element of periodictable.

15. according to the matrix material of claim 14, wherein said other oxide compound is selected from Al ₂O ₃, SiO ₂, MgO, CaO, BaO and SrO.

16. according to each matrix material in the claim 10 to 15, wherein said two second phases contain hopcalite.

17. according to each matrix material in the aforementioned claim, wherein said boron suboxide is the boron suboxide of particulate state or grains.

18. according to each matrix material in the aforementioned claim, the mean particle size of wherein said boron suboxide particles or crystal grain is 100nm-100 μ m.

19. according to the matrix material of claim 18, the mean particle size of wherein said boron suboxide particles or crystal grain is 100nm-10 μ m.

20. according to each matrix material in the aforementioned claim, wherein the fracture toughness property of matrix material is greater than 3.5MPa.m ^0.5

21. according to each matrix material in the aforementioned claim, wherein the hardness of matrix material is greater than 25GPa.

22. preparation is according to the method for each boron suboxide composite material in the aforementioned claim, this method comprises following step: the boron suboxide source is provided; This boron suboxide source is contacted with the compound that boride maybe can produce boride, thereby produce reaction mass; Thereby produce boron suboxide composite material with this reaction mass of sintering.

23. according to the method for claim 22, wherein less than the pressure of 200MPa be no more than 1950 ℃ sintering temperature reaction mass.

24., wherein pass through 50-400K/ minute heating rate and 5 minutes or isothermal hold-time sintering reaction material still less according to the method for claim 22.

25. according to the method for claim 22, wherein by 8-10K/ minute heating rate and 15-25 minute isothermal hold-time sintering reaction material.

26., wherein carry out contacting of boron suboxide and boride or compound by mixing according to each method in the claim 22 to 25.

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