CN101668718A - Boron suboxide composite material - Google Patents

Abstract

The invention provides a boron suboxide composite material comprising boron suboxide and a secondary phase, wherein the secondary phase contains a rare earth metal oxide. The rare earth metal oxide may be selected from the oxides of scandium, yttrium, which is preferred, and elements of the lanthanide series, and may be a mixture of rare earth metal oxides. The secondary phase may also include, inaddition to the rare earth metal oxide(s), a further oxide or mixture of oxides of an element of the Groups IA, MA, MIA, and IVA of the periodic table. Moreover, the secondary phase may also containa boride, and particularly a boride selected from the borides of transition metals of the fourth to eighth groups of the periodic table.

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 KHN of 34GPa-36GPa ₁₀₀Value.

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.

Summary of the invention

According to the present invention, the boron suboxide composite material that comprises boron suboxide and two second phases (secondary phase) is provided, wherein said two second phases contain the mixture of at least two kinds of metal oxides, and described metal oxide all is not to contain boron oxide compound.

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.

At least a oxide compound that can be selected from IA, IIA, IIIA and the IVA family element of periodictable in the described oxide compound can be selected from Al especially ₂O ₃, SiO ₂, MgO, CaO, BaO and SrO.

In a form of the present invention, at least a in the described oxide compound can be rare-earth oxide.This rare-earth oxide can be selected from the oxide compound of scandium, yttrium (it is for preferred) and lanthanon, and can be the mixture of rare-earth oxide.

Remove the burning beyond the region of objective existence, two second phases can also contain for example B of boron oxide compound ₂O ₃Or borate.

In a preferred form of the present invention, one of described oxide compound is Al ₂O ₃, and another kind of oxide compound is selected from SiO ₂, MgO, CaO, BaO and SrO.

In another preferred form of the present invention, one of described oxide compound is a rare-earth oxide, and another kind of oxide compound is selected from Al ₂O ₃, SiO ₂, MgO, CaO, BaO and SrO.

The amount of the oxide compound in the matrix material of the present invention will depend on the desired properties (particularly hardness and fracture toughness property) of this matrix material and oxide type and change.Usually, the amount of described oxide mixture is the 20 volume % at the most of matrix material.For many oxide compounds, the amount of described oxide compound is the 10 volume % at the most of matrix material normally, and for other oxide compound, the amount of described oxide compound is the 5 volume % at the most of matrix material normally.

Two second phases of matrix material can also contain boride, and this boride is selected from the boride of the 4th to the 8th group 4 transition metal of periodictable especially.Any citation to " boride " comprises the boride that refers to a boride, diboride and any other form.More particularly, boride can chosen from Fe, the boride of cobalt, nickel, titanium, tungsten, tantalum, hafnium, zirconium, rhenium, molybdenum and chromium.Boride can also be the platinum metals boride, preferred boronation palladium.Hard borides such as TiB ₂, W ₂B ₅And ReB ₂Amount in matrix material can be greater than the amount of softer relatively boride (for example those borides that formed by Fe, Ni and Co).

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 metal oxide mixture, at least two kinds of oxide compounds in the described metal oxide mixture are boracic not, and 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:

$\left(1\right),K_C=\mathrm{\&delta;}{\left(\frac{E}{H}\right)}^{\frac{1}{2}}\frac{\mathrm{<figure-callout\; id="3"\; label="P\; c"\; filenames="A2008800136900018H1.png"\; state="\{\{state\}\}">P</figure-callout>}}{c^{}}$

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 5 measured hardness values 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 to contain two second phases of at least two kinds of oxide compounds (all not being to contain boron oxide compound) mixture, strengthened effective densification of matrix material during preparing by use.During liquid phase of densification, can realize surpassing the density of 95% theoretical density, and can under relatively mild temperature and pressure condition, add oxide compound and obtain, this density obtainable density when not having oxide compound in two second phases.Especially, obtained the density of 98%-99%.

Matrix material of the present invention can followingly make: provide the boron suboxide source, preferably with particle or crystal grain; Thereby this boron suboxide source is contacted produce reaction mass with oxide mixture, in the wherein said oxide compound at least two kinds boracics not; 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 15-25 minute, 20 minutes isothermal hold-time of typical case.

Corresponding to this method based on oxide compound is to form the stable oxide liquid phase during sintering, thereby described liquid phase is cooled off formation crystalline state and/or amorphous oxide compound two second phases in final product then.This oxide compound is (especially, if they are Al ₂O ₃And SiO ₂Mixture the time) with remaining B ₂O ₃Reaction and form the non-crystalline state phase at boron suboxide particles or intergranule.

Being added on of mixed oxide chemically makes amorphous grain boundary stable, and matrix material is more resistance to worn.This amorphous grain boundary produces oxide compound and B during the liquid phase of densification ₂O ₃Between reaction.For improving abrasion resistance, chemical stability and the high-temperature stability of material, the B in the preferred crystal boundary ₂O ₃Content is 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.

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.

Though before sintering, these two minor phase constituents can be introduced with their oxidised form, but described two minor phase constituents also can be present in the reaction mass and can allow oxidation is taking place in reaction mass during the sintering by other form (for example form nitrate, carbonate or the oxalate of oxide compound during decomposing, perhaps be in their metallic state).

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 2.62 weight %Al ₂O ₃With 2.65 weight %Y ₂O ₃B ₆The SEM image of the sintered composite materials of O preparation.

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

Fig. 4 is by being mixed with 4 weight %WO ₃, 2.0 weight %Al ₂O ₃And the B of 0.53%MgO (from powder) ₆The SEM image of the sintered composite materials of O preparation has shown submicron W ₂B ₅The oxide compound crystal boundary that precipitate (white phase) and part are wiped.

Fig. 5 is the B of doped with Al-Y-Si ₆The SEM image of O hot pressing matrix material has shown at higher SiO ₂Grain growing under the content.

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 masher to utilize steel ball with B ₆The O initial powder was milled 50 hours.Remove iron contaminants by washing in HCl.In methyl alcohol, wash this powder subsequently to remove any B that exists ₂O ₃Average particle size particle size after milling is 500nm.

The powder that in methyl alcohol, will mill and 2 weight %Al ₂O ₃With 2.65 weight %Y ₂O ₃Mixing and use planetary mill were milled 2 hours.Use the mixture that the rotatory evaporator drying mills and be placed on then in the boron nitride cell (in the inside of graphite mo(u)ld), and under argon atmospher, under the pressure of 1800 ℃ temperature and 50MPa, use hot pressing to carry out sintering to continue about 20 minutes.Make the matrix material of the abundant densification that comprises boron suboxide particles, two second phases are evenly dispersed in this matrix material.Confirm there is not the crystalline state phase in two second phases by XRD.Crystal boundary is to contain Y ₂O ₃, Al ₂O ₃With residue B ₂O ₃The amorphous grain boundary phase.

The cross section of polishing sample is also used Vickers impression instrument tested for hardness and fracture toughness property then.Find that hardness is about 33.2GPa under 5kg load, and fracture toughness property is about 6.3MPa.m ^0.5

Table 1 has gathered the measured performance of this boron suboxide composite material.Than pure B ₆The matrix material of people such as O and Shabalala (WO 2007/029102) preparation, hot pressing B of the present invention ₆The O matrix material has higher hardness and fracture toughness property.

Embodiment 2

Use with component and condition identical described in the embodiment 1 to prepare boron suboxide composite material, difference is Y ₂O ₃And Al ₂O ₃The amount of component reduces by half, and ratio between the two remains unchanged.The abundant densification of the matrix material that makes and find that it contains Y ₂O ₃, Al ₂O ₃With residue B ₂O ₃It has hardness and the 6.0MPa.m of 30.4GPa ^0.5Fracture toughness property.

Embodiment 3

Use with component and condition identical described in the embodiment 1 to prepare boron suboxide composite material, difference is that the component of two second phases comprises 1.0 other weight %SiO ₂The abundant densification of the matrix material that makes and find that it comprises following amorphous grain boundary phase, this amorphous grain boundary contains Y mutually ₂O ₃, Al ₂O ₃With residue B ₂O ₃It has hardness and the 5.0MPa.m of 33.5GPa ^0.5Fracture toughness property.

Embodiment 4

In alcohol solvent, utilize masher to use the alumina balls B that mills ₆The O initial powder.Use the dry suspensoid of rotatory evaporator in the back of milling.The wearing and tearing of alumina balls are included in total composition of material in the table 1.

The powder that in Virahol, will mill and 2.62 weight %Al ₂O ₃With 2.65 weight %Y ₂O ₃Mix and use planetary mill to mill and continue 2 hours.The mixture that uses the rotatory evaporator drying to mill uses the graphite mo(u)ld with graphite foil to carry out the rapid discharge plasma agglomeration thereafter.Described graphite foil scribbles the BN suspensoid to prevent the interaction with graphite.Under argon atmospher, use the SPS method with the pressure of 50K/ minute heating rate, 1740 ℃ temperature and 115MPa with about 5 minutes of the mixture sintering of milling.Heating rate is 50K/ minute.Because used nonconducting hBN lining or coating, fast hot-press method is with to be characterised in that electric current is compared density through the SPS method of powder bigger.

Make the matrix material of the abundant densification that comprises boron suboxide particles, two second phases are evenly dispersed in this matrix material.The cross section of polishing sample is also used Vickers impression instrument tested for hardness and fracture toughness property then.Discovery hardness under 0.4kg load is about 33.4 ± 0.6GPa, and fracture toughness property is about 4.3MPa.m ^0.5

Embodiment 5

Use with component and condition identical described in the embodiment 4 to prepare boron suboxide composite material the mixture that identical SPS method among use and the embodiment 4, difference are to use the pressure of 1800 ℃ temperature and 80MPa to come sintering to mill.The abundant densification of the matrix material that makes.It has the hardness of 33GPa under the 0.4kg, and 4MPa.m ^0.5Fracture toughness property.

Embodiment 6

Use with component and condition identical described in the embodiment 4 to prepare boron suboxide composite material, difference is powder and the 2.0 weight %Al that will mill ₂O ₃With 2.0 weight %Y ₂O ₃Mix, and carry out sintering in 1850 ℃ temperature and the pressure of 50MPa.The abundant densification of the matrix material that makes and find that it contains Y ₂O ₃, Al ₂O ₃With some residual B ₂O ₃It has hardness and the 4MPa.m of 32.1GPa ^0.5Fracture toughness property.

Embodiment 7

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, 2 weight %Y ₂O ₃With 2 weight %ZrO ₂(promptly carrying out stable TZP with 3 moles of % yttrium oxide) mixes in Virahol and uses masher to utilize Al ₂O ₃Ball was milled 6 hours.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.

Remove and contain Y ₂O ₃Sample (embodiment 7a) outside, prepare no Y ₂O ₃Sample (embodiment 7b).Make the matrix material of the abundant densification that comprises boron suboxide particles, two second phases are evenly dispersed in this matrix material.Has Y ₂O ₃Sample in, remove ZrB ₂ZrB partly ₁₂Also observe amorphous oxide compound crystal boundary outward.Do not adding Y ₂O ₃The material of embodiment 7b in two second phases, detect crystalline oxide phase (Al by XRD ₁₈B ₄O ₃₃).MgO and remaining B ₂O ₃With some Al ₂O ₃Form the amorphous grain 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 is also used Vickers impression instrument tested for hardness and fracture toughness property then.Discovery hardness under 0.4kg load is about 36.9GPa (sample 7b) and 34.2GPa (sample 7a), and fracture toughness property is about 4MPa.m ^0.5

Embodiment 8-10

Use with condition identical described in the embodiment 7 to prepare boron suboxide composite material, difference is with using HfO respectively ₂, WO ₃And TiB ₂Substitute ZrO in the ratio that provides in the table 1 ₂Under the temperature of 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 7b, to identical density, show and add ZrO for two kinds of temperature observations ₂The time the densification behavior be better than adding HfO slightly ₂Or WO ₃The time densification behavior that obtained.

Do not adding Y ₂O ₃Sample in, also formed some 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 (Fig. 4).Except that the oxide compound phase, 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 ₂-because do not carry out the detailed mensuration of lattice parameter, so W ₂B ₅And WB ₂All be used).Y ₂O ₃Adding suppressed Al ₁₈B ₄O ₃₃Crystallization in amorphous oxide attitude crystal boundary or two second phases.

Embodiment 11-13

Use the boron suboxide composite material for preparing embodiment 11 with condition identical described in the embodiment 1, difference is to use SiO ₂Y in the alternate embodiment 1 ₂O ₃Embodiment 12-13 prepares by the mode identical with embodiment 7.The abundant densification of the matrix material that makes.

Material, density, phase composite and the performance of all matrix materials that make have been provided in the table 1.These data presentation add Y ₂O ₃/ Al ₂O ₃Significantly improve densification.For composition with described additive, under 1850 ℃, can finish densification, and at pure B ₆In the powder, under this temperature, only can be densified to 95% of theoretical density among the O.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 pure material is only 1450 ℃ of beginning densifications.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, grain growing does not promptly 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 9c).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.

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 1	??B 6O+Al 2O 3+Y 2O 3??(1800℃)	??2∶2.65	??33.2±2.79	??6.3±0.99	?B 6O non-crystalline state two second phases	??2.53
Embodiment 2	??B 6O+Al 2O 3+Y 2O 3??(1800℃)	??1∶1.32	??30.4±1.8	??6.0±0.4	?B 6O non-crystalline state two second phases	??2.41
							Embodiment 3	??B 6O+Al 2O 3+Y 2O 3+SiO 2??(1800℃)	??2∶2.65∶1	??33.5±2.2	??5.0±1.0	?B 6O non-crystalline state two second phases	??2.46
Embodiment 4	??B 6O+Al 2O 3+Y 2O 3??(1740℃)	??2.62∶2.65	??33.4±0.6 **	??4.3±0.7	?B 6O non-crystalline state two second phases	??2.56
							Embodiment 5	??B 6O+Al 2O 3+Y 2O 3??(1800℃)	??2.62∶2.65	??33.0±0.7 **	??4.0±0.4 ***	?B 6O non-crystalline state two second phases	??2.60
Embodiment 6	??B 6O+Al 2O 3+Y 2O 3??(1850℃)	??2∶2	??32.1±0.7 **	??4.0±0.4 ***	?B 6O non-crystalline state two second phases	??2.53
							Embodiment 7a	??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 7b	??B 6O+Al 2O 3+ZrO 2+MgO??(1850℃)	??2∶2∶0.53	??36.9±0.6 **	??4	?B 6O，ZrB 2，ZrB 12，?Al 18B 4O 33Non-crystalline state two second phases	??2.60
							Embodiment 8a	??B 6O+Al 2O 3+Y 2O 3+HfO 2+MgO??(1900℃)	??2∶2∶2∶0.53	??34.2±0.6 **	??4	?B 6O，HfB 2Non-crystalline state two second phases	??2.52
Embodiment 8b	??B 6O+Al 2O 3+HfO 2+MgO??(1850℃)	??2∶2∶0.53	??36.1±0.6 **	??4	?B 6O，HfB 2?Al 18B 4O 33Non-crystalline state two second phases	??2.56
							Embodiment 9a	??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 9b	??B 6O+Al 2O 3+Y 2O 3+WO 3+MgO??(1850℃)	??2∶2∶4∶0.53	??34.2±0.5 **	??4	?B 6O，W 2B 2Non-crystalline state two second phases	??2.61
							Embodiment 9c	??B 6O+Al 2O 3+WO 3+MgO??(1850℃)	??2∶4∶0.53	??34.0±0.6 **	??4	?B 6O，W 2B 2Non-crystalline state two second phases	??2.61
Embodiment 10a	??B 6O+Al 2O 3+Y 2O 3+TiH 2+MgO??(1900℃)	??2∶2∶5∶O.53	??36.1±0.6 **	??4	?B 6O，TiB 2Non-crystalline state two second phases	??2.49
							Embodiment 10b	??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 2Non-crystalline state two second phases	??2.68
Embodiment 10c	??B+TiO 2+0.4％MgO+0.5％??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 2Non-crystalline state two second phases	??2.79
							Embodiment 11	??B 6O+Al 2O 3+SiO 2??(1800℃)	??2∶1	??29.5±1.60	??4.8±0.65	?B 6O，Al 18B 4O 33Non-crystalline state two second phases	??2.42
Embodiment 12	??B 6O+Al 2O 3+Sc 2O 3+MgO??(1900℃)	??2∶2∶0.53	??36.7±0.6 **	??4	?B 6O non-crystalline state two second phases	??2.57
							Embodiment 13	??B 6O+Al 2O 3+Y 2O 3+BN??(1900℃)	??2∶2∶2	??3l.3±0.8 **	??3.6	?B 6O non-crystalline state two second phases	??2.45

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

* records under 0.4Kg load

* * records with 30 μ m root radiuss with the SENB method

Reference

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Claims (27)

1. comprise the boron suboxide composite material of boron suboxide and two second phases, wherein said two second phases contain the mixture of at least two kinds of metal oxides, and described metal oxide all is not to contain boron oxide compound.

2. according to the matrix material of claim 1, at least a oxide compound that is selected from IA, IIA, IIIA and the IVA family element of periodictable in the wherein said oxide compound.

3. according to the matrix material of claim 1 or claim 2, at least a in the wherein said oxide compound is rare-earth oxide.

4. according to the matrix material of claim 3, wherein said rare-earth oxide is selected from the oxide compound of yttrium oxide, Scium trioxide and lanthanon.

5. according to each matrix material in the aforementioned claim, at least a Al that is selected from the wherein said oxide compound ₂O ₃, SiO ₂, MgO, CaO, BaO and SrO.

6. according to each matrix material in the aforementioned claim, a kind of in the wherein said oxide compound is Al ₂O ₃, another kind of oxide compound is selected from SiO ₂, MgO, CaO, BaO and SrO.

7. according to each matrix material in the claim 1 to 5, a kind of in the wherein said oxide compound is rare-earth oxide, and another kind of oxide compound is selected from Al ₂O ₃, SiO ₂, MgO, CaO, BaO and SrO.

8. according to each matrix material in the aforementioned claim, wherein said two second phases also contain boron oxide compound.

9. according to each matrix material in the aforementioned claim, wherein said two second phases also contain boride.

10. according to the matrix material of claim 9, wherein said boride is selected from the boride of the 4th to the 8th group 4 transition metal of periodictable.

11. according to the matrix material of claim 10, the boride of wherein said boride chosen from Fe, cobalt, nickel, titanium, tungsten, tantalum, hafnium, zirconium, rhenium, molybdenum and chromium.

12. according to the matrix material of claim 9, wherein said boride is the platinum metals boride.

13. according to the matrix material of claim 12, wherein said platinum metals boride is the boronation palladium.

14. according to each matrix material in the aforementioned claim, the amount of wherein said hopcalite is the 20 volume % at the most of this matrix material.

15. according to each matrix material in the aforementioned claim 1 to 13, the amount of wherein said hopcalite is the 10 volume % at the most of this matrix material.

16. according to each matrix material in the aforementioned claim 1 to 13, the amount of wherein said hopcalite is the 5 volume % at the most of this matrix material.

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 claim 9 to 19, the amount of wherein said boron suboxide is at least 50 volume % of this matrix material.

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

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

23. preparation is according to the method for each boron suboxide composite material in the aforementioned claim, this method comprises the following steps: to provide the boron suboxide source; Make this boron suboxide source and oxide mixture or can produce the compound of such oxide mixture or thereby metallic contact produces reaction mass, at least two kinds in the wherein said oxide compound do not contain boron; Thereby produce boron suboxide composite material with this reaction mass of sintering.

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

25., 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 23.

26. according to the method for claim 23, wherein by 10-20K/ minute heating rate and 15-60 minute isothermal hold-time sintering reaction material.

27., wherein carry out contacting of boron suboxide and oxide mixture or compound or metal by mixing according to each method in the aforementioned claim 23 to 26.

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