CN103588216A - Method for preparing zirconium boride powder at low temperature according to boron/carbon thermal reduction method - Google Patents
Method for preparing zirconium boride powder at low temperature according to boron/carbon thermal reduction method Download PDFInfo
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Abstract
The invention relates to a method for preparing a zirconium boride (ZrB2) powder at a low temperature according to a boron/carbon thermal reduction method and belongs to the technical field of super-high temperature functional/structural ceramics. The method is characterized in that cane sugar, phenolic resin, epoxy resin or pitch is used as a carbon source, and zirconium oxide (ZrO2) and boron carbide (B4C) are used as a zirconium source and a boron source, respectively. According to the method, the cane sugar, phenolic resin, epoxy resin or pitch, the zirconium oxide and the boron carbide are used as the raw materials; the raw materials are low in cost; cane sugar, phenolic resin, epoxy resin or pitch is wet mixed with the zirconium oxide and the boron carbide; all the raw materials are mixed evenly and hardly aggregate; the synthesis process is carried out in a high-purity argon environment or in vacuum; and ZrB2 powder is synthesized through a reduction reaction at a low temperature; and therefore, the method is simple in process, low in temperature and low in time consumption.
Description
Technical field
The present invention relates to a kind of boron/carbothermic method low temperature and prepare zirconium boride 99.5004323A8ure (ZrB
2) method of powder, belong to ultrahigh-temperature function/structural ceramics technical field.
Background technology
ZrB
2pottery has high-melting-point (3245 ℃), high rigidity (23GPa), high strength, good thermal conductivity (60W (mK)
-1) and electroconductibility (1.0 * 10
7s/m), the feature such as good Burning corrosion resistance and heat-shock resistance, in the fields such as aerospace high-temperature structural material, superhard cutter material, matrix material, refractory materials and electrode materials, obtain application widely, become a kind of very potential ultrahigh-temperature structural ceramic material.But due to commercial ZrB
2the oxygen contamination of powder surface is (by amorphous B
2o
3with crystalline state ZrO
2form) cause its very difficult sintering densification, only have the process of ability accelerated material densification after these oxygen contaminations are removed at a lower temperature.B
2o
3volatile in the environment of high-temperature vacuum, and ZrO
2volatilization temperature will be more than 2000 ℃, ZrB now
2powder generation alligatoring, therefore need to add the compound containing C or B, as C, B, B
4c, transition metal carbide (VC, WC, NbC, Mo
2c, Cr
2c
3), silicide and nitride etc. effectively deoxygenation auxiliary agent by chemical reaction, realize ZrO
2low temperature is removed, thereby effectively promotes material densification.As can be seen here, high pure and ultra-fine powder is most important to the superhigh temperature ceramic material of processability excellence, and therefore, low-cost, high-quality ultrahigh-temperature powder preparation becomes the Research foundation of superhigh temperature ceramic material.
Report at present ZrB
2the preparation method of powder mainly contains: direct synthesis technique, self propagating high temperature synthesis method, carbothermic method, boron thermal reduction method, boron/carbothermic method, sol-gel method, high frequency heat plasma method etc.Direct synthesis technique is prepared ZrB
2powder purity is high, and synthesis condition and process are simple, but raw material is expensive, cost is high, and synthetic ZrB
2powder granularity is thick, active low, is unfavorable for sintering and the post-treatment processing of powder.In addition, reaction process needs high temperature, and energy consumption is high, is unsuitable for suitability for industrialized production.And self propagating high temperature synthesis method has, process is simple, speed of response is fast, the time is short, energy consumption is little, production efficiency is high, cost is low, granularity is little, powder active advantages of higher, but because its speed of response is too fast, what reaction was carried out sometimes is not very complete, impurity accordingly also can be many, and its reaction process, product structure and performance are all not easy to control.For carbothermic reduction reaction, due to B
2o
3steam force down, loss through volatilization is serious, causes boron source not enough, in product, carbon content is higher, for guaranteeing to react completely, need add excessive B
2o
3, its content changes with temperature is different with vacuum tightness, because B, C light element are difficult to analyze, measures, and is therefore difficult to accurately determine Zr/B/C ratio, and synthesized powder quality is stable not.Boron thermal reduction method synthesis temperature is relatively low, synthetic powder particle diameter is little, for low temperature is prepared ultra-fine ZrB
2powder provides a kind of new approach, but in reaction process, generates B
2o
3phase, easily causes powder granule to be grown up, and affects its sintering activity, needs washing or vacuum to remove and could obtain high-purity ZrB
2powder, its raw materials cost costliness has limited industrial applications.Sol-gel method is synthesized ZrB
2powder temperature is low, has chemical uniformity high, and chemical purity is high, and synthetic powder particle diameter is little, and large, the active advantages of higher of specific surface area, is the common method that low temperature is prepared superfine powder.But sol-gel method is raw materials used is all inorganic salt or alkoxide mostly, and raw materials cost is higher, and the production cycle is long, complex technical process, relate to a large amount of process variables, be vulnerable to the uncertain factor impacts such as external environment and control, and organic solvent has certain hazardness to human body; Contaminate environment; Can not scale operation.For emerging high frequency induction thermal plasma legal system for ZrB
2powder, belong to electrodeless heating, can avoid electrode fouling, plasma reaction system atmosphere is controlled, can be used to synthetic high-purity powder, reactor temperature is high, and the temperature difference is very large, does not need high-temperature heat treatment in preparation process, powder granule produces in air-flow, can effectively prevent particle agglomeration, be conducive to obtain the superfine powder that uniform particles is disperseed, be the approach of the ultra-fine pyroceramic powder of a kind of effective preparation.But need to carrying out the aftertreatments such as pickling, alcohol wash, synthetic powder just can obtain the ZrB that purity is higher
2powder, this technique is a kind of novel Preparation Technique of Powders, and theory and technique are also immature, and suitability for industrialized production also needs for some time.
Boron/carbothermic method of using for industrialization, synthetic ZrB
2the method of powder adopts carbon black and norbide reduction-oxidation zirconium method more, and its chemical equation is as follows:
2ZrO
2(s)+B
4C(s)+3C(s)→2ZrB
2(s)+4CO(g) (1)
At standard atmosphere, depress, the reaction Gibbs free energy of formula (1) is negative in the time of temperature >1424 ℃, reaction may occur, according to calculation of thermodynamics, when reaction environment is high vacuum or mobile high-purity gas, temperature of reaction can reduce, and this just effectively reduces the particle diameter of synthetic powder.But carbon black, norbide and zirconium white are solid-state mixing in this method, and homogeneity is poor, cause synthetic ZrB
2powder purity is not high.Therefore, the present invention adopts organism to be evenly coated on around zirconium white and boron carbide particles, reaches mixed uniformly object, prepares high-purity ZrB
2powder.
Summary of the invention
The object of the present invention is to provide a kind of boron/carbothermic method low temperature to prepare zirconium boride 99.5004323A8ure (ZrB
2) method of powder, its technique is simple, temperature is low, consuming time short, can obtain high pure and ultra-fine ZrB
2powder.
The object of the invention is to be achieved through the following technical solutions.
A kind of boron/carbothermic method low temperature of the present invention is prepared the method for zirconium boride powder, and the method is usingd sucrose, resol, epoxy resin or pitch as carbon source, with zirconium white (ZrO
2) and norbide (B
4c) respectively as He Peng source, zirconium source, the step of the method comprises:
1) zirconium white and norbide are put into ball grinder, add dehydrated alcohol, add zirconia ball grinding media, ball milling mixing 6-48h, moves to the mixed solution after mixing in the vessel that dehydrated alcohol is housed, and ultrasonic dispersion, obtains mixing suspension;
2) carbon source is dissolved in solvent, is then poured in the mixing suspension in step 1); Then heat, stir, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible, and heat treatment furnace or the vacuum oven of plumbago crucible being put into the argon shield of flowing heat, and then cool to room temperature with the furnace, then obtain ZrB through grinding
2powder, the particle diameter of the powder obtaining is 100～500nm.
Above-mentioned steps 1) in, in mixed solution, the concentration of zirconia solution is 0.5～5mol/L, and the concentration of norbide solution is 0.3～3mol/L, and ultrasonic jitter time is 0.5～4h; Zirconic purity >=99.9wt.%, particle diameter is≤100nm that the purity of norbide is >=95.0wt.% that particle diameter is≤2 μ m;
Above-mentioned steps 2) in, the concentration of carbon source solution is 0.1～2mol/L, and when carbon source is sucrose, solvent is water, and when carbon source is resol, epoxy resin or pitch, solvent is ethylene glycol, normal hexane or hexanaphthene; Carbon source is analytical pure; Heating temperature is 100～250 ℃, and be 0.5～8h heat-up time; Alr mode is magnetic agitation;
Step 2) in, in the molar weight of carbon and step 1), the ratio of the molar weight in zirconium source is 3～5:1 in carbon source
Above-mentioned steps 3) in, heating schedule, for the temperature rise rate with 10 ℃/min is heated to 1200～1600 ℃ of insulation 0.5～2h, is Ar or the vacuum of flowing in heat treatment furnace.
In the present invention, batch mixing process adopts zirconium white and boron carbide powder and sucrose (or resol, epoxy resin, pitch etc.) solution to carry out wet mixing, mixes, and having solved pure solid phase powder mixes inequality, and purity is the problem of high easy reunion not; In preparation process, adopt high-purity argon gas, reduction reaction can occur at a lower temperature and prepare ultra-fine ZrB
2powder.
Beneficial effect
In the present invention, adopting sucrose, epoxy resin, resol or pitch and zirconium white and norbide is raw material, raw materials cost is low, and sucrose, epoxy resin, resol or pitch and zirconium white and norbide be mixed into wet mixing, mix, be difficult for reuniting, building-up process is carried out under high-purity argon gas environment or in vacuum, and the synthetic ZrB of reduction reaction can occur at a lower temperature
2powder, the method technique is simple, temperature is low, consuming time short.
Accompanying drawing explanation
Fig. 1 is the ZrB of the present embodiment 1 preparation
2the X ray diffracting spectrum of powder.
Fig. 2 is the ZrB of embodiment 1 preparation
2the stereoscan photograph of powder.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using sucrose as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 50nm, takes 22.4g norbide (B
4c) powder, its purity is 96wt%, median size is 1 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 800ml, add zirconia ball grinding media, ball milling mixing 24h, moves to the mixture after mixing in the vessel that 250ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 0.5h;
2) take 35.0g sucrose and join in 200ml water, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 100 ℃, and be 8h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible, then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats, heating schedule is incubated 1h for the temperature rise rate with 10 ℃/min is warming up to 1600 ℃, then cool to room temperature with the furnace, then obtain powder body material through grinding; As shown in Figure 1, its stereoscan photograph as shown in Figure 2 for the X-ray diffractogram of the powder body material obtaining.As shown in Figure 1, the powder body material obtaining is ZrB
2powder, the oxygen level of powder is very low; As shown in Figure 2, ZrB
2the median size of powder is 100nm.
Embodiment 2
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using sucrose as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 70nm, takes 28.0g norbide (B
4c) powder, its purity is 95.6wt%, median size is 0.8 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 600ml, add zirconia ball grinding media, ball milling mixing 12h, moves to the mixture after mixing in the vessel that 200ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 1h;
2) take 81.1g sucrose and join in 200ml water, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 160 ℃, and be 4h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1500 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 3
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using sucrose as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 80nm, takes 26.9g norbide (B
4c) powder, its purity is 96wt%, median size is 1 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 1000ml, add zirconia ball grinding media, ball milling mixing 24h, moves to the mixture after mixing in the vessel that 300ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 0.5h;
2) take 69.5g sucrose and join in 200ml water, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 120 ℃, and be 8h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1400 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 4
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using sucrose as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 100nm, takes 30.0g norbide (B
4c) powder, its purity is 96wt%, median size is 2 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 700ml, add zirconia ball grinding media, ball milling mixing 14h, moves to the mixture after mixing in the vessel that 400ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 0.5h;
2) take 104.3g sucrose and join in 400ml water, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 180 ℃, and be 5h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1550 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 5
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using epoxy resin as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 60nm, takes 25.4g norbide (B
4c) powder, its purity is 95wt%, median size is 1.5 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 500ml, add zirconia ball grinding media, ball milling mixing 12h, moves to the mixture after mixing in the vessel that 300ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 2h;
2) take 12.3g epoxy resin and join in 200ml ethylene glycol, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 110 ℃, and be 4h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1500 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 6
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using epoxy resin as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 80nm, takes 25.1g norbide (B
4c) powder, its purity is 94wt%, median size is 0.5 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 200ml, add zirconia ball grinding media, ball milling mixing 18h, moves to the mixture after mixing in the vessel that 200ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 3h;
2) take 20.4g epoxy resin and join in 300ml ethylene glycol, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 150 ℃, and be 6h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1550 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 7
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using epoxy resin as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 70nm, takes 28.1g norbide (B
4c) powder, its purity is 96wt%, median size is 1 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 900ml, add zirconia ball grinding media, ball milling mixing 16h, moves to the mixture after mixing in the vessel that 300ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 2h;
2) take 31.6g epoxy resin and join in 300ml ethylene glycol, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 180 ℃, and be 2h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1600 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 8
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using pitch as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 60nm, takes 24.6g norbide (B
4c) powder, its purity is 93wt%, median size is 0.5 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 300ml, add zirconia ball grinding media, ball milling mixing 16h, moves to the mixture after mixing in the vessel that 200ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 2.5h;
2) take 40.2g pitch and join in 200ml hexanaphthene, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 100 ℃, and be 3h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1500 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 9
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using pitch as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 50nm, takes 24.3g norbide (B
4c) powder, its purity is 97wt%, median size is 1.5 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 400ml, add zirconia ball grinding media, ball milling mixing 8h, moves to the mixture after mixing in the vessel that 300ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 0.5h;
2) take 47.5g pitch and join in 300ml hexanaphthene, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 160 ℃, and be 5h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1550 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material;
Embodiment 10
With zirconium white (ZrO
2) as zirconium source, with norbide (B
4c), as boron source, using resol as carbon source;
1) take 100g ZrO
2powder, its purity is 99.9wt%, median size is 80nm, takes 26.9g norbide (B
4c) powder, its purity is 96wt%, median size is 1 μ m, two kinds of powder are put into ball grinder together, add dehydrated alcohol 800ml, add zirconia ball grinding media, ball milling mixing 20h, moves to the mixture after mixing in the vessel that 300ml dehydrated alcohol is housed, and ultra-sonic oscillation are disperseed 0.5h;
2) take 18.5g resol and join in 200ml normal hexane, stir it is mixed, then join in the solution that step 1) obtains, heating is magnetic agitation simultaneously, and Heating temperature is 140 ℃, and be 4h heat-up time, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible; then the heat treatment furnace of plumbago crucible being put into high-purity argon gas protection heats; heating schedule, for the temperature rise rate with 10 ℃/min is warming up to 1400 ℃ of insulation 1h, then cools to room temperature with the furnace, then obtains ZrB through grinding
2powder body material.
Claims (7)
1. boron/carbothermic method low temperature is prepared a method for zirconium boride powder, it is characterized in that: the method is usingd sucrose, resol, epoxy resin or pitch as carbon source, usings zirconium white and norbide respectively as He Peng source, zirconium source, steps of the method are:
1) zirconium white and norbide are put into ball grinder, add dehydrated alcohol, add zirconia ball grinding media, ball milling mixing 6-48h, moves to the mixed solution after mixing in the vessel that dehydrated alcohol is housed, and ultrasonic dispersion, obtains mixing suspension;
2) carbon source is dissolved in solvent, is then poured in the mixing suspension in step 1); Then heat, stir, the reactant that obtains mixing;
3) by step 2) reactant that obtains packs in plumbago crucible, and heat treatment furnace or the vacuum oven of plumbago crucible being put into the argon shield of flowing heat, and then cool to room temperature with the furnace, then obtain ZrB through grinding
2powder, the particle diameter of the powder obtaining is 100～500nm.
2. a kind of boron/carbothermic method low temperature according to claim 1 is prepared the method for zirconium boride powder, it is characterized in that: in step 1), in mixed solution, the concentration of zirconia solution is 0.5～5mol/L, the concentration of norbide solution is 0.3～3mol/L, and ultrasonic jitter time is 0.5～4h; Zirconic purity >=99.9wt.%, particle diameter is≤100nm that the purity of norbide is >=95.0wt.% that particle diameter is≤2 μ m.
3. a kind of boron/carbothermic method low temperature according to claim 1 is prepared the method for zirconium boride powder, it is characterized in that: step 2) in the concentration of carbon source solution be 0.1～2mol/L, carbon source is analytical pure; Heating temperature is 100～250 ℃, and be 0.5～8h heat-up time; Alr mode is magnetic agitation.
4. according to a kind of boron/carbothermic method low temperature described in claim 1,2 or 3, prepare the method for zirconium boride powder, it is characterized in that: carbon source is sucrose, solvent is water.
5. according to a kind of boron/carbothermic method low temperature described in claim 1,2 or 3, prepare the method for zirconium boride powder, it is characterized in that: carbon source is resol, epoxy resin or pitch, solvent is ethylene glycol, normal hexane or hexanaphthene.
6. a kind of boron/carbothermic method low temperature according to claim 1 is prepared the method for zirconium boride powder, it is characterized in that: step 2) in carbon source in molar weight and the step 1) of carbon the ratio of the molar weight in zirconium source be 3～5:1.
7. a kind of boron/carbothermic method low temperature according to claim 1 is prepared the method for zirconium boride powder, it is characterized in that: in step 3), heating schedule, for the temperature rise rate with 10 ℃/min is heated to 1200～1600 ℃ of insulation 0.5～2h, is Ar or the vacuum of flowing in heat treatment furnace.
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| CN112898025A (en) * | 2021-02-02 | 2021-06-04 | 中冶节能环保有限责任公司 | Method for preparing vanadium boride ultrafine powder by carbon-thermal boron-thermal method |
| CN116253568A (en) * | 2022-12-30 | 2023-06-13 | 北京航空航天大学 | Construction of ZrBC organic precursor by coprecipitation method and synthesis of ZrB by synergistic carbothermal reduction 2 Method |
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| CN104043882A (en) * | 2014-07-07 | 2014-09-17 | 牡丹江金钢钻碳化硼有限公司 | Boron carbide-zirconium boride-copper nickel electrode material and preparation method and application thereof |
| CN104961138A (en) * | 2015-06-30 | 2015-10-07 | 莱芜亚赛陶瓷技术有限公司 | Preparation method of <10>B-enriched zirconium diboride powder |
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| CN107814570A (en) * | 2016-09-12 | 2018-03-20 | 中国科学院金属研究所 | The method that Peng ∕ carbothermic methods prepare the ceramic powder of two boron of ternary RE two |
| CN106478110A (en) * | 2016-10-12 | 2017-03-08 | 黑龙江科技大学 | A kind of ZrB2The preparation method of SiC composite ceramicses |
| CN110511035A (en) * | 2019-08-05 | 2019-11-29 | 广东工业大学 | A kind of high entropy ceramics of high-ductility high wear-resistant and its preparation method and application |
| CN112239211A (en) * | 2020-09-11 | 2021-01-19 | 辽宁工业大学 | Synthetic method of high-activity zirconium boride |
| CN112250080A (en) * | 2020-09-17 | 2021-01-22 | 北京科技大学 | Method for preparing refractory metal boride in two steps |
| CN112250080B (en) * | 2020-09-17 | 2022-02-25 | 北京科技大学 | Method for preparing refractory metal boride in two steps |
| CN112898025A (en) * | 2021-02-02 | 2021-06-04 | 中冶节能环保有限责任公司 | Method for preparing vanadium boride ultrafine powder by carbon-thermal boron-thermal method |
| CN116253568A (en) * | 2022-12-30 | 2023-06-13 | 北京航空航天大学 | Construction of ZrBC organic precursor by coprecipitation method and synthesis of ZrB by synergistic carbothermal reduction 2 Method |
| CN116253568B (en) * | 2022-12-30 | 2023-12-15 | 北京航空航天大学 | Construction of ZrBC organic precursor by coprecipitation method and synthesis of ZrB by synergistic carbothermal reduction 2 Method |
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