CN104045093A - Method for preparing nanometer ZrB2 powder through assistance of microwave-hydrothermal treatment - Google Patents

Method for preparing nanometer ZrB2 powder through assistance of microwave-hydrothermal treatment Download PDF

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CN104045093A
CN104045093A CN201410273923.4A CN201410273923A CN104045093A CN 104045093 A CN104045093 A CN 104045093A CN 201410273923 A CN201410273923 A CN 201410273923A CN 104045093 A CN104045093 A CN 104045093A
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powder
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zrb
microwave
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CN104045093B (en
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李翠艳
欧阳海波
黄剑锋
费杰
张沛东
孔新刚
卢靖
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a method for preparing nanometer ZrB2 powder through assistance of microwave-hydrothermal treatment, belonging to the technical field of ultrahigh-temperature functional/structural ceramics. The adopted technical scheme is that the method comprises the following steps: dissolving a biomass carbon source in water to obtain a solution A, subsequently adding B4C into the solution A and uniformly stirring to obtain suspension liquid; adding inorganic salt containing Zr into the suspension liquid to obtain a solution B; treating the solution B through a microwave-hydrothermal reaction to obtain an intermediate product; centrifugally separating the intermediate product to obtain a solid, roasting the solid in an argon atmosphere and then naturally cooling to room temperature to obtain the nanometer ZrB2 powder. The method disclosed by the invention has the advantages of high efficiency and low cost, and is applicable to industrial production. In addition, the nanometer ZrB2 powder prepared by the method disclosed by the invention has the characteristics of high purity, small particle size and uniform distribution in particle size. The nanometer ZrB2 powder can be used as a raw material for developing or producing high temperature resisting products including ultrahigh-temperature ceramics, high temperature resisting coatings and the like.

Description

The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder
Technical field
The invention belongs to ultrahigh-temperature function/structural ceramics technical field, relate to a kind of nanometer ZrB for preparing 2the method of powder, is specifically related to the auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder.
Background technology
Zirconium diboride (ZrB 2) as superhigh temperature ceramic material, there is high-melting-point, high rigidity, excellent thermal conductivity and specific conductivity, the good anti-ablation of thermal shock performance, superhigh temperature resistant and high-temperature oxidation resistance, therefore become the candidate material of component under the extreme ultrahigh-temperature service condition such as rocket engine, supersonic plane and refractory materials.Yet, ZrB 2the sintering character of stupalith is subject to the restriction of starting powder characteristic, as the particle size of powder, purity etc.Current ZrB 2the preparation method of powder mainly contains: solid reaction process, self-propagating high-temperature method, mechanochemical reaction, sol-gel method and chemical coprecipitation etc.Therefore prepare the ZrB of high pure and ultra-fine 2powder just seem in the urgent need to.
China's invention bulletin patent discloses a kind of method that boron/carbothermic method low temperature is prepared zirconium boride powder for No. 201310504553, 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, under high-purity argon gas environment or in vacuum, carry out the synthetic ZrB of reduction reaction 2powder.China's invention bulletin patent discloses a kind of method that zirconium diboride nano-powder is prepared in sorbyl alcohol complexing-polymerization No. 201310540670, through preparation boron zirconium mixed sols, gel, acquisition ZrB 2nano-powder.There is prepared ZrB in aforesaid method 2the problems such as powder granule is thick, active low, and synthetic product purity is low, easy reunion.
In view of above defect, be necessary in fact to provide a kind of method that can solve above technical problem with preparation ZrB2 nano-powder.
Summary of the invention
The object of the present invention is to provide the auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, the method is simple to operate efficient, is applicable to suitability for industrialized production, the nanometer ZrB making through the method 2powder purity is high, granularity is little, size distribution is even.
The present invention is achieved through the following technical solutions:
The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, comprises the following steps:
1) making the solution A that concentration is 10～100g/L by biomass carbon source is soluble in water, is the ratio of (1:1)～(1:6) in the mol ratio of the carbon in biomass carbon source and boron, in solution A, adds B 4c powder, stirs, and obtains suspension;
2) ratio that is 2:1 in the mol ratio of zirconium and boron, adds the inorganic salt containing zirconium in suspension, stirs, and obtains solution B;
3) by solution B at 170～220 ℃, in microwave source frequency, be 2450MHz, under the condition that power is 1600W, hydro-thermal reaction 20～70min, reaction is centrifugal by reactant after finishing, and gets precipitation, then by washing of precipitate, oven dry, obtains brownish black solid;
4) brownish black solid is calcined to 1～3.5h in argon gas atmosphere at 1200～1500 ℃, naturally cool to room temperature, obtain nanometer ZrB 2powder.
Described biomass carbon source is glucose, sucrose or starch.
The described inorganic salt containing zirconium are ZrCl 4, ZrOCl 2or Zr (NO 3) 4.
Described B 4c powder is through ball-milling processing before adding solution A, and Ball-milling Time is 2～7h.
Step 3) described washing is that the centrifugal precipitation obtaining is first washed through deionization, and then uses absolute ethanol washing.
The nanometer ZrB making 2the particle diameter of powder is 50～200nm.
Compared with prior art, the present invention has following useful technique effect:
The present invention is usingd biomass carbon as carbon source, and the inorganic salt of usining containing Zr, as zirconium source, utilize microwave-hydrothermal method to synthesize ZrO 2, C, B 4the composite granule of C, then by the ZrB of the pyrocarbon thermal reduction reaction synthesis of nano size of calcining under argon atmosphere 2.The biomass carbon of usining has the feature of environmental protection, ZrO as raw material as carbon source 2, C grain graininess is little, efficiency is high, reproducible, be synthesis of nano ZrB 2provide the foundation.The present invention has efficiently, advantage cheaply, is suitable for industrialized production, the nanometer ZrB preparing through the present invention 2it is high that powder has purity, granularity little (particle diameter is 50～200nm), the uniform feature of size distribution, this nanometer ZrB 2powder can be as the starting material of the high temperature resistant products such as development or production superhigh temperature ceramics and high-temperaure coating.
Accompanying drawing explanation
Fig. 1 is ZrB prepared by the present invention 2the X-ray diffraction of nano-powder (XRD) collection of illustrative plates;
Fig. 2 is ZrB prepared by the present invention 2the scanning electron microscope of nano-powder (SEM) photo.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
Embodiment 1
The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, comprises the following steps:
Step 1: glucose is dissolved in water, obtains the solution A that concentration is 10g/L, the ratio that is 1:1 in the mol ratio of carbon in glucose and boron adds the B after ball milling 7h in solution A 4c, stirs and obtains suspension;
Step 2: the ratio that is 2:1 in the mol ratio of zirconium and boron, by ZrCl 4add in suspension, stir, obtain solution B;
Step 3: solution B is carried out at 170 ℃ to microwave hydrothermal reaction 70min, the intermediate product obtaining after reacting completely is got precipitation through centrifugation, and precipitate with deionized water and absolute ethanol washing post-drying are obtained to brownish black product;
Step 4: brownish black product is calcined to 3.5h in argon gas atmosphere at 1200 ℃, be then naturally down to room temperature, obtain nanometer ZrB 2powder.
The present embodiment gained nanometer ZrB 2the particle diameter of powder is in 40nm left and right.
Embodiment 2
The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, comprises the following steps:
Step 1: glucose is dissolved in water, obtains the solution A that concentration is 30g/L, the ratio that is 1:2 in the mol ratio of carbon in glucose and boron adds the B after ball milling 6h in solution A 4c, stirs and obtains suspension;
Step 2: the ratio that is 2:1 in the mol ratio of zirconium and boron, by ZrCl 4add in suspension, stir, obtain solution B;
Step 3: solution B is carried out at 180 ℃ to microwave hydrothermal reaction 60min, the intermediate product obtaining after reacting completely is got precipitation through centrifugation, and precipitate with deionized water and absolute ethanol washing post-drying are obtained to brownish black product;
Step 4: brownish black product is calcined to 3h in argon gas atmosphere at 1300 ℃, be then naturally down to room temperature, obtain ZrB 2nano-powder.
The present embodiment gained ZrB 2the particle diameter of nano-powder is in 60nm left and right.
Embodiment 3
The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, comprises the following steps:
Step 1: sucrose dissolved, in water, is obtained to the solution A that concentration is 50g/L, is that 1:3 adds the B after ball milling 5h in solution A by the mol ratio of carbon in sucrose and boron 4c, stirs and obtains suspension;
Step 2: the ratio that is 2:1 in the mol ratio of zirconium and boron, by ZrOCl 2add in suspension, stir, obtain solution B;
Step 3: solution B is carried out at 190 ℃ to microwave hydrothermal reaction 50min, the intermediate product obtaining after reacting completely is got precipitation through centrifugation, and precipitate with deionized water and absolute ethanol washing post-drying are obtained to brownish black product;
Step 4: brownish black product is calcined to 2.5h in argon gas atmosphere at 1350 ℃, be then naturally down to room temperature, obtain ZrB 2nano-powder.
The present embodiment gained ZrB 2the particle diameter of nano-powder is in 90nm left and right.
Embodiment 4
The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, comprises the following steps:
Step 1: sucrose dissolved, in water, is obtained to the solution A that concentration is 30g/L, and the ratio that is 1:4 in the mol ratio of carbon in sucrose and boron adds the B after ball milling 4h in solution A 4c, stirs and obtains suspension;
Step 2: the ratio that is 2:1 in the mol ratio of zirconium and boron, by ZrOCl 2add in suspension, stir, obtain solution B;
Step 3: solution B is carried out at 200 ℃ to microwave hydrothermal reaction 40min, the intermediate product obtaining after reacting completely is got precipitation through centrifugation, and precipitate with deionized water and absolute ethanol washing post-drying are obtained to brownish black product;
Step 4: brownish black product is calcined to 2h in argon gas atmosphere at 1400 ℃, be then naturally down to room temperature, obtain ZrB 2nano-powder.
The present embodiment gained ZrB 2the particle diameter of nano-powder is in 70nm left and right.
Embodiment 5
The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, comprises the following steps:
Step 1: starch dissolution, in water, is obtained to the solution A that concentration is 40g/L, and the ratio that is 1:5 in the mol ratio of carbon in starch and boron adds the B after ball milling 3h in solution A 4c, stirs and obtains suspension;
Step 2: the ratio that is 2:1 in the mol ratio of zirconium and boron, by Zr (NO 3) 4add in suspension, stir, obtain solution B;
Step 3: solution B is carried out at 210 ℃ to microwave hydrothermal reaction 30min, the intermediate product obtaining after reacting completely is got precipitation through centrifugation, and precipitate with deionized water and absolute ethanol washing post-drying are obtained to brownish black product;
Step 4: brownish black product is calcined to 1.5h in argon gas atmosphere at 1450 ℃, be then naturally down to room temperature, obtain ZrB 2nano-powder.
The present embodiment gained ZrB 2the particle diameter of nano-powder is in 100nm left and right.
Embodiment 6
The auxiliary preparation of a kind of microwave hydrothermal nanometer ZrB 2the method of powder, comprises the following steps:
Step 1: starch dissolution, in water, is obtained to the solution A that concentration is 60g/L, and the ratio that is 1:6 in the mol ratio of carbon in starch and boron adds the B after ball milling 2h in solution A 4c, stirs and obtains suspension;
Step 2: the ratio that is 2:1 in the mol ratio of zirconium and boron, by Zr (NO 3) 4add in suspension, stir, obtain solution B;
Step 3: solution B is carried out at 220 ℃ to microwave hydrothermal reaction 20min, the intermediate product obtaining after reacting completely is got precipitation through centrifugation, and precipitate with deionized water and absolute ethanol washing post-drying are obtained to brownish black product;
Step 4: brownish black product is calcined to 1h in argon gas atmosphere at 1500 ℃, be then naturally down to room temperature, obtain ZrB 2nano-powder.
The present embodiment gained ZrB 2the particle diameter of nano-powder is in 150nm left and right.
Refer to shown in Fig. 1, it is the nanometer ZrB being prepared by the inventive method 2the XRD figure spectrum of powder.As seen from Figure 1: the ZrB that powder prepared by the present invention is pure phase 2.
Refer to shown in Fig. 2, it is ZrB prepared by the present invention 2the SEM pattern of nano-powder.As seen from Figure 2: ZrB prepared by the present invention 2the size of nano-powder is at 50～200nm.
In sum, the present invention prepares nanometer ZrB 2the method of powder at least has the following advantages: the present invention is usingd reproducible biomass carbon and had the cost-saving feature of environmental protection as raw material, utilizes microwave hydrothermal technology to synthesize ZrO 2, C, B 4the composite granule of C, ZrO 2, C grain graininess is little, efficiency is high, reproducible, be synthesis of nano ZrB 2provide the foundation.The nanometer ZrB that the present invention obtains 2powder has that purity is high, granularity is little and the uniform feature of size distribution, and this preparation method has efficiently, advantage cheaply, is suitable for industrialized production.The nanometer ZrB making 2powder can be as the starting material of the high temperature resistant products such as development or production superhigh temperature ceramics and high-temperaure coating.

Claims (6)

1. a microwave hydrothermal is assisted preparation nanometer ZrB 2the method of powder, is characterized in that, comprises the following steps:
1) making the solution A that concentration is 10～100g/L by biomass carbon source is soluble in water, is the ratio of (1:1)～(1:6) in the mol ratio of the carbon in biomass carbon source and boron, in solution A, adds B 4c powder, stirs, and obtains suspension;
2) ratio that is 2:1 in the mol ratio of zirconium and boron, adds the inorganic salt containing zirconium in suspension, stirs, and obtains solution B;
3) by solution B at 170～220 ℃, in microwave source frequency, be 2450MHz, under the condition that power is 1600W, hydro-thermal reaction 20～70min, reaction is centrifugal by reactant after finishing, and gets precipitation, then by washing of precipitate, oven dry, obtains brownish black solid;
4) brownish black solid is calcined to 1～3.5h in argon gas atmosphere at 1200～1500 ℃, naturally cool to room temperature, obtain nanometer ZrB 2powder.
2. a kind of microwave hydrothermal according to claim 1 is assisted preparation nanometer ZrB 2the method of powder, is characterized in that, described biomass carbon source is glucose, sucrose or starch.
3. a kind of microwave hydrothermal according to claim 1 is assisted preparation nanometer ZrB 2the method of powder, is characterized in that, the described inorganic salt containing zirconium are ZrCl 4, ZrOCl 2or Zr (NO 3) 4.
4. a kind of microwave hydrothermal according to claim 1 is assisted preparation nanometer ZrB 2the method of powder, is characterized in that, described B 4c powder is through ball-milling processing before adding solution A, and Ball-milling Time is 2～7h.
5. a kind of microwave hydrothermal according to claim 1 is assisted preparation nanometer ZrB 2the method of powder, is characterized in that step 3) described washing be by the centrifugal precipitation obtaining first through deionization washing, and then use absolute ethanol washing.
6. a kind of microwave hydrothermal according to claim 1 is assisted preparation nanometer ZrB 2the method of powder, is characterized in that, the nanometer ZrB making 2the particle diameter of powder is 50～200nm.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105239160A (en) * 2015-09-06 2016-01-13 浙江大学 Nano monocrystal zirconium diboride, alloy thereof and application thereof in surface treatment of bearing balls
CN111484028A (en) * 2020-04-20 2020-08-04 浙江工业大学 Porous zirconium boride material, preparation method thereof and application of porous zirconium boride material in preparation of vinyl chloride through hydrochlorination of acetylene
CN111573688A (en) * 2020-04-20 2020-08-25 中国科学院合肥物质科学研究院 Method for preparing superfine zirconium boride powder with assistance of solvent heat treatment
CN111848178A (en) * 2020-08-05 2020-10-30 湖南华威景程材料科技有限公司 Method for microwave synthesis of hafnium diboride nano powder by complex sol-gel technology
CN112062577A (en) * 2020-09-06 2020-12-11 西北工业大学 Method for preparing boride ultrahigh-temperature ceramic powder by hydrothermal method-assisted molten salt growth method

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CN1948152A (en) * 2006-11-10 2007-04-18 清华大学 High purity ultra fine zirconium biboride powder and its preparation method
CN101486577A (en) * 2009-02-24 2009-07-22 武汉理工大学 Preparation of nano zirconium diboride ceramic powder
CN103265048A (en) * 2013-06-14 2013-08-28 兰州理工大学 Preparation method of TiB2 ultrafine powder material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964388A (en) * 1953-07-10 1960-12-13 Nat Lead Co Method for the production of zirconium boride
CN1948152A (en) * 2006-11-10 2007-04-18 清华大学 High purity ultra fine zirconium biboride powder and its preparation method
CN101486577A (en) * 2009-02-24 2009-07-22 武汉理工大学 Preparation of nano zirconium diboride ceramic powder
CN103265048A (en) * 2013-06-14 2013-08-28 兰州理工大学 Preparation method of TiB2 ultrafine powder material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105239160A (en) * 2015-09-06 2016-01-13 浙江大学 Nano monocrystal zirconium diboride, alloy thereof and application thereof in surface treatment of bearing balls
CN105239160B (en) * 2015-09-06 2018-02-27 浙江大学 Nano crystal zirconium diboride and its alloy and the application in bearing ball surface treatment
CN111484028A (en) * 2020-04-20 2020-08-04 浙江工业大学 Porous zirconium boride material, preparation method thereof and application of porous zirconium boride material in preparation of vinyl chloride through hydrochlorination of acetylene
CN111573688A (en) * 2020-04-20 2020-08-25 中国科学院合肥物质科学研究院 Method for preparing superfine zirconium boride powder with assistance of solvent heat treatment
CN111848178A (en) * 2020-08-05 2020-10-30 湖南华威景程材料科技有限公司 Method for microwave synthesis of hafnium diboride nano powder by complex sol-gel technology
CN112062577A (en) * 2020-09-06 2020-12-11 西北工业大学 Method for preparing boride ultrahigh-temperature ceramic powder by hydrothermal method-assisted molten salt growth method

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