Patent Application
20100304138
The invention relates to a boron suboxide composite material.
The development of synthetic ultrahard materials which have hardness values approaching or even exceeding that of diamond has been of great interest to material scientists. With a Vickers hardness of between 70 to 100 GPa, diamond is the hardest material known, followed by cubic boron nitride (HV˜60 GPa) and boron suboxide herein referred to as B6O. Hardness values of 53 GPa and 45 GPa have been determined at 0.49N and 0.98N load respectively for B6O single crystals, which are similar to those of cubic boron nitride [9].
It is known that B5O may also be non-stoichiometric i.e. exist as B6O1-x (where x is in the range 0 to 0.3). Such non-stoichiometric forms are included in the term B6O. The strong covalent bonds and short interatomic bond length of these materials contribute to the exceptional physical and chemical properties such as great hardness, low mass density, high thermal conductivity, high chemical inertness and excellent wear resistance [1, 2]. In U.S. Pat. No. 5,330,937 to Ellison-Hayashi et al the formation of boron suboxide powders of nominal composition B3O, B4O, B6O, B7O, B8O, B12O, B16O and B18O was reported. Potential industrial applications have been discussed by Kurisuchiyan et al (Japan Patent No. 7,034,063) and Ellison-Hayashi et al (U.S. Pat. No. 5,456,735) and include use in grinding wheels, abrasives and cutting tools.
Several techniques have been employed for producing boron suboxide and include such procedures as reacting elemental boron (B) with boron oxide (B2O3) under suitably high pressure and high temperature conditions [1]. In U.S. Pat. No. 3,660,031 to Holcombe Jr. et al other methods of producing boron suboxides such as reducing boron oxide (B2O3) with magnesium, or by reducing zinc oxide with elemental boron are mentioned. With each of these known procedures however, there are drawbacks which retard the usefulness of the material in industry. For example, the reduction of B2O3 with magnesium produces a solid solution of magnesium and magnesium boride contaminants in the suboxide, while the reduction of magnesium oxide with boron produces only a relatively small yield of boron suboxide and is very inefficient. Holcombe Jr. et al (U.S. Pat. No. 3,660,031) produced B7O by reducing zinc oxide with elemental boron at temperatures of between 1200° C. to 1500° C. A hardness value of 38.2 GPa under 100 g load and density of 2.6 g.cm−3 is reported for this material. The fracture toughness for this material is not discussed.
Petrak et al [3] investigated the mechanical and chemical properties of hot-pressed B6O and reported micro-hardness values as high as 34-38 GPa. Ellison-Hayashi et al (U.S. Pat. No. 5,330,937) produced B6O with a magnesium addition (approximately 6%) which yielded average KHN100 values of 34 GPa to 36 GPa.
Efforts have been made to enhance the mechanical properties of B6O, especially its fracture toughness, by forming B6O composites with other hard materials such as diamond [4], boron carbide [5], and ON [6]. The diamond and cBN-containing composites were made under extremely high temperature and pressure conditions. The intention was to form pseudo-binary composite systems, stronger at the grain boundaries than those of pure B6O. Even though high hardness values were recorded for the composites (HV˜46 GPa), again, fracture toughness values did not exceed 1.8 MPa.m0.5. The best value here was obtained with B6O-cBN composites.
Shabalala et al (WO 2007/029102 and [7]) produced B8O composites with aluminium compounds which resulted in an aluminium borate phase at the grain boundary. A fracture toughness of about 3.5 MPa.m0.5 with a corresponding hardness of 29.3 GPa was obtained. The aluminium phases present in the composite are soft and although they may improve the fracture toughness of the resulting composite, they do not contribute to the overall hardness of the composite. Moreover, in addition to a crystalline aluminium borate, a boron oxide rich, chemically unstable amorphous phase and microporosity was formed, further resulting in reduced hardness [10, 11].
According to the invention there is provided a boron suboxide composite material comprising boron suboxide and a secondary phase, the secondary phase containing a mixture of at least two metal oxides, neither of which is a boron-containing oxide.
For the purpose of this specification, “secondary phase” means everything in the composite material but the boron suboxide, and may be wholly or partially crystalline or amorphous, and may include more than one thermodynamic phase.
At least one of the oxides may be selected from oxides of elements of Groups IA, IIA, IIIA, and IVA of the periodic table, and particularly may be selected from Al2O3, SiO2, MgO, CaO, BaO and SrO.
In one form of the invention, at least one of the oxides may be 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.
In addition to the metal oxides, the secondary phase also may contain a boron-containing oxide such as B2O3 or a borate.
In one preferred form of the invention, one of the oxides is Al2O3 and another oxide is selected from SiO2, MgO, CaO, BaO and SrO.
In yet a further preferred form of the invention, one of the oxides is a rare earth metal oxide and another oxide is selected from Al2O3, SiO2, MgO, CaO, BaO and SrO.
The amount of oxide present in the composite material of the invention will vary according to the properties desired for the composite material, particularly hardness and fracture toughness, and the type of oxide. Generally the mixture of oxides will be present in amount of up to 20 volume % of the composite. For many oxides, the oxides will generally be present in an amount of up to 10 volume % of the composite material and for yet other oxides the oxides will generally be present in an amount of up to 5 volume % of the composite material.
The secondary phase of the composite material may also contain a boride, and particularly a boride selected from the borides of transition metals of the fourth to eighth groups of the periodic table. Any reference to “boride” includes a reference to a monoboride, diboride and any other form of boride. More particularly, the boride may be selected from the borides of iron, cobalt, nickel, titanium, tungsten, tantalum, hafnium, zirconium, rhenium, molybdenum and chromium. The boride may also be a platinum group metal boride, preferably palladium boride. Hard borides like TiB2, W2B5 and ReB2 may be present in the composite material in a larger amount than the relative soft borides, such as those borides formed from Fe, Ni and Co.
The boron suboxide may be particulate or granular boron suboxide. The mean grain size of the boron suboxide particles or granules themselves is preferably fine and may range from 100 nm to 100 μm, preferably 100 nm to 10 μm.
Finely particulate boron suboxide may be produced, for example, by subjecting a source of boron suboxide to milling. If milling takes place in the presence of an iron or cobalt containing milling medium, some iron and/or cobalt will be introduced into the material which is sintered. For an iron-free material, the milled powder can be washed with hydrochloric acid, or the milling can be carried out with alumina pots and milling balls. It has been found to be advantageous to wash the milled powder in warm water or alcohols to remove any excess of B2O3 or H3BO3.
The composite material of the invention comprises boron suboxide, generally in particulate or granular form, and the secondary phase in a bonded, coherent form. The secondary phase will preferably be present in a volume percent less than that of the boron suboxide and will be uniformly dispersed among the boron suboxide. The secondary phase can be amorphous or partially crystalline.
The invention provides a composite material containing boron suboxide and a mixture of metal oxides, of which at least two oxides do not contain boron, and which has both high fracture toughness and high hardness. In particular, the composite material generally has a fracture toughness greater than 3.5 MPa.m0.5 in combination with a Vickers Hardness (HV) greater than 25 GPa. Preferably the fracture toughness of the composite material is greater than 3.5 MPa.m0.5, and more preferably at least 4.0 MPa.m0.5 and still more preferably at least 5.0 MPa.m0.5. The fracture toughness (KIC), as used herein, was measured at indentations generally with a load of 5 kg. The average of five measured was used to determine the properties of the B6O samples discussed hereinafter. The KIC was measured via the DCM method, using Anstis' equation [8]:
where E is the Young's modulus, H the hardness and δ is a constant, which only depends on the geometry of the indenter. A value of 470 GPa was used for the Young's modulus value in this equation. For the standard Vickers diamond pyramid indenter, Anstis et al established a value of δ=0.016±0.004 as the calibration constant which was also used for these measurements.
The hardness of the composite material is preferably greater than 25 GPa and more preferably at least 30 GPa. The Vickers hardness was measured using an indentation load of 5 kg. The average of five measured hardness values was used to determine the properties of the B6O composite samples.
The composite material of the invention may be made by providing a source of boron suboxide, preferably as particles or granules; contacting the source of boron suboxide with a mixture of oxides, wherein at least two of the oxides do not contain boron, to create a reaction mass; and sintering the reaction mass to produce the boron suboxide composite material. This method forms another aspect of the invention.
Sintering preferably takes place at a relatively low temperature and pressure, i.e. a pressure of less than 200 MPa and a temperature of not exceeding 1950° C. Low pressure sintering processes such as hot pressing (HP), gas pressure sintering, hot isostatic pressing (HIP) or spark plasma sintering (SPS) are preferred. The SPS process is characterised by very fast heating and short isothermal holding times, in particular with heating rates of 50-400 K/minute and isothermal holding times of 5 minutes or less. The hot pressing process is characterised by heating rates of 10-20 K/minute, and isothermal holding times of 15 to 25, typically 20 minutes.
Consistent with this oxide-based approach is the formation of a stable oxide liquid phase during sintering which then cools to form crystalline and/or amorphous oxide secondary phases in the final product. The oxides, especially if they are a mixture of Al2O3 and SiO2, react with the remaining B2O3 and form amorphous phases between the boron suboxide particles or granules.
The addition of mixed oxides chemically stabilizes the amorphous grain boundary, and makes the composite material more wear resistant. This amorphous grain boundary results from a reaction between the oxides and B2O3 during the liquid phase of densification. To increase wear resistance, chemically stability and high temperature stability of the material, it is preferable that the B2O3 content in the grain boundary is low. A mol ratio of B2O3/(B2O3+ other oxides) of less than 60 is preferable, more preferably a mol ratio of less than 30, and even more preferably a mol ratio of less than 20.
The boron suboxide may be mixed with the components necessary to produce the secondary phase prior to the sintering step. The boron suboxide may alternatively be coated with the secondary phase components prior to sintering.
Whilst it may be preferable to introduce these secondary phase components in their oxidised form prior to sintering, the secondary phase components may also be present in the reaction mass in another form (e.g. nitrates, carbonates or oxalates forming oxides during decomposition or in their metallic state) and be allowed to oxidise within the reaction mass during sintering.
The composite material according to the invention may be used in cutting applications and in wear parts. It may also be crushed to grit form and used in grit applications. Moreover, the composite material may be used in armour applications, such as ballistic armour, and particularly body armour.
The invention will now be illustrated by the following examples. Table 1 summarises these materials and their measured hardness and toughness properties for comparative purposes. In these examples the terms “secondary phase” and “grain boundary phase” are both used. The terms are used interchangeably and refer to the same phase.
For the purpose of this specification, “secondary phase” means everything in the composite material but the boron suboxide, and may be wholly or partially crystalline or amorphous, and may include more than one thermodynamic phase.
B6O starting powder was milled using an attritor mill with steel balls for 50 hours. The iron contaminants were removed by washing in HCl. The powder was subsequently washed in methanol to remove any B2O3 present. The average particle size after milling was 500 nm.
The milled powder was admixed with 2% by weight of Al2O3 and 2.65% by weight of Y2O3 in methanol and milled for two hours using a planetary mill. The milled mixture was dried using a rotary evaporator and then placed in a boron nitride cell (inside a graphite die) and sintered using a hot press at a temperature of 1800° C. and a pressure of 50 MPa, under an argon atmosphere for about 20 minutes. A fully densified composite material comprising boron suboxide particles was produced within which a secondary phase was uniformly dispersed. No crystalline phase in the secondary phase was identified by XRD. The grain boundary was an amorphous grain boundary phase containing Y2O3, Al2O3 and remaining B2O3.
A cross-section of the sample was polished and then tested for hardness and fracture toughness with Vickers indenter. The hardness was found to be about 33.2 GPa at a load of 5 kg and a fracture toughness of about 6.3 MPa.m0.5.
Table 1 summarises the measured properties of this boron suboxide composite material. The hot pressed B6O composite of the invention had a higher hardness and fracture toughness compared to both pure B6O and the composite material produced by Shabalala et al (WO 2007/029102).
A boron suboxide composite material was produced using the same components and conditions set out in Example 1, save that the amount of Y2O3 and Al2O3 components was reduced by half, with the ratio between the two being kept the same. The composite material produced was fully densified and was also found to contain Y2O3, Al2O3 and remaining B2O3. It had a hardness of 30.4 GPa and a fracture toughness of 6.0 MPa.m0.5.
A boron suboxide composite material was produced using the same components and conditions set out in Example 1, save that the components for the secondary phase included an additional 1.0 weight % SiO2. The composite material produced was fully densified and was found to contain an amorphous grain boundary phase containing Y2O3, Al2O3 and remaining B2O3. It had a hardness of 33.5 GPa and a fracture toughness of 5.0 MPa.m0.5.
B6O starting powder was milled using an attritor mill with alumina balls, in an ethanol solvent. After milling the suspension was dried using a rotation evaporator. The wear of the alumina balls was included in the overall composition of the materials in Table 1.
The milled powder was admixed with 2.62% by weight of Al2O3 and 2.65% by weight of Y2O3 in isopropanol and milled for two hours using a planetary mill. The milled mixture was dried using a rotary evaporator, after which fast spark plasma sintering was carried out using graphite dies with graphite foils. The graphite foils were coated with a BN suspension to prevent interaction with the graphite. The milled mixture was sintered using the SPS method with a heating rate of 50 K/min, a temperature of 1740° C. and a pressure of 115 MPa, under an argon atmosphere for about 5 minutes. The heating rate was 50 K/min. Since a nonconductive hBN lining or coating was used, the densification was more a fast hot pressing than a SPS-process, which is characterized by a current going through the powder.
A fully densified composite material was produced comprising boron suboxide particles within which a secondary phase was uniformly dispersed. A cross-section of the sample was polished and then tested for hardness and fracture toughness with a Vickers indenter. The hardness was found to be about 33.4±0.6 GPa at a load of 0.4 kg and a fracture toughness of about 4.3 MPa.m0.5.
A boron suboxide composite material was produced using the same components and conditions set out in Example 4, save that the milled mixture was sintered using a temperature of 1800° C. and a pressure of 80 MPa, using the same SPS method as in example 4. The composite material produced was fully densified. It had a hardness of 33 GPa at 0.4 kg and a fracture toughness of 4 MPa.m0.5.
A boron suboxide composite material was produced using the same components and conditions set out in Example 4, except that the milled powder was admixed with 2.0% by weight of Al2O3 and 2.0% by weight of Y2O3, and sintered at a temperature of 1850° C. and a pressure of 50 MPa. The composite material produced was fully densified and was also found to contain Y2O3, Al2O3 and some residual B2O3. It had a hardness of 32.1 GPa and a fracture toughness of 4 MPa.m0.5.
B6O starting powder was milled using a jet mill. The average particle size after milling was 2.3 μm. The milled B6O powder was admixed with 2% by weight of Al2O3, 2% by weight of Y2O3 and 2% by weight of ZrO2 (i.e. TZP stabilised with 3 mol % yttria) in isopropanol and milled for six hours using an attrition mill with Al2O3 balls. The milled mixture was dried using a rotary evaporator and then placed in a graphite die coated with hexagonal BN, and sintered using the SPS method with a heating rate of 50 K/minute and a holding time of 5 minutes, under an argon atmosphere.
In addition to the sample containing Y2O3 (example 7a), a sample without Y2O3 was produced (example 7b). A fully densified composite material comprising boron suboxide particles was produced within which a secondary phase was uniformly dispersed. In the sample with Y2O3 an amorphous oxide grain boundary phase was observed, in addition to ZrB2 and partially ZrB12. A crystalline oxide phase (Al18B4O33) was detected by XRD in the secondary phase in the material of example 7b without Y2O3 additions. The MgO together with the remaining B2O3 and some Al2O3 formed an amorphous grain boundary phase. This amorphous grain boundary phase is more stable than that formed with only Al2O3 (Shabalala). The typical feature of formation of micropores was not observed, resulting in higher hardness values. The ZrO2 transforms into ZrB2 and partially ZrB12. It has to be mentioned that the peaks of ZrB12 are slightly shifted in comparison to the standard values, indicating that there may be some yttrium or aluminum dissolved in the lattice.
A cross-section of the sample was polished and then tested for hardness and fracture toughness with Vickers indenter. The hardness was found to be about 36.9 GPa (sample 7b) and 34.2 GPa (sample 7a) at a load of 0.4 kg and a fracture toughness of about 4 MPa.m0.5.
Boron suboxide composite materials were produced using the same conditions set out in Example 7, but replacing the ZrO2 with HfO2, WO3 and TiB2 respectively in the ratios provided in Table 1. Densification was carried out at 1850° C. and 1900° C. At 1850° C. densities of 96-98% were observed. At 1900° C. densities of more than 98% were observed. In example 7b, the same densities were observed for both temperatures, indicating slightly better densification behaviour with ZrO2 additions than what is achieved with the addition of HfO2 or WO3.
In the samples without Y2O3 additions, some Al18B4O33 and a boride was also formed. There was no formation of microporosity as in Shabalala et al (WO 2007/029102 and [9]) indicating a more stable grain boundary phase (
A boron suboxide composite material of example 11 was produced using the same conditions set out in Example 1, save that the Y2O3 of Example 1 was replaced with SiO2, Examples 12-13 were produced in the same way as Example 7. The composite material produced was fully densified.
The materials, densities, phase compositions and properties of all composites produced are given in Table 1. The data showed that the addition of Y2O3/Al2O3 increases densification substantially. The densification at 1850° C. can be completed for the compositions with the additives, whereas the pure B6O powders can only be densified to 95% of theoretical densities at this temperature. The same density as for the pure material can be reached at 50-100° C. lower temperatures. Fast densification starts at 1350-1370° C. for the material with the Y2O3/Al2O3 additives whereas the densification of the pure material starts only at 1450° C. The microstructures of the materials with addition of Y2O3/Al2O3 reveal the existence of such a liquid, because no crystalline grain boundary phases (secondary phase) are found. SEM figures show a homogeneous distribution of the Y2O3/Al2O3 additives in the triple junctions. The grain size of the material cannot be determined, but from the SEM micrographs it can be concluded that the grain size is less than 1 μm, i.e. no grain growth occurs.
The addition of 10 wt % TiB2 to the composition of the B6O+Y2O3/Al2O3 does not change the densification behaviour.
The microstructure of the material with WO3 (example 9c) additions are given in
The results show the possibility of producing dense superhard B6O materials without high pressure. The improved densification of these materials in comparison to pure B6O is connected with the formation of a liquid phase during densification.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007 03437 | Apr 2007 | ZA | national |
| 0711773.2 | Jun 2007 | GB | national |
| 0802949.8 | Feb 2008 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/IB2008/051587 | 4/24/2008 | WO | 00 | 8/13/2010 |
