CN104628391A - Method for preparing zirconium diboride nanopowder by virtue of organic-inorganic complex sol-gel technology - Google Patents

Method for preparing zirconium diboride nanopowder by virtue of organic-inorganic complex sol-gel technology Download PDF

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CN104628391A
CN104628391A CN201510060806.4A CN201510060806A CN104628391A CN 104628391 A CN104628391 A CN 104628391A CN 201510060806 A CN201510060806 A CN 201510060806A CN 104628391 A CN104628391 A CN 104628391A
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powder
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zrb
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glucose
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季惠明
王永超
杨铭
赵晓东
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Tianjin University
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Abstract

The invention relates to a method for preparing ZrB2 nanopowder by virtue of an organic-inorganic complex sol-gel technology. The method comprises the following steps: by taking zirconium chloride oxide as an inorganic zirconium source and boric acid as a boron source and selecting polyhydric organic glucose as a complexing agent, carrying out complexing reaction on the complexing agent and boric acid to improve the solubility of boric acid; adding epoxy propane as a polymerizer to form a stable ZrB2 precusor sol; carrying out carbon thermal reduction reaction on glucose as a carbon source without introducing other carbon sources; finally preparing the ZrB2 nanopowder through links such as gelatinization, drying, calcination of carbon thermal reduction reaction and the like on the prepared sol. The purity of the obtained powder can reach over 95%. The synthesized particles are relatively small in size, near-spherical and relatively uniform in distribution, and the grain sizes are distributed between 50nm and 300nm. The high-temperature calcining synthetic temperature is reduced and the yield of the ZrB2 powder is remarkably improved by virtue of the organic-inorganic complex method.

Description

The sol-gel technique of organic and inorganic complexing prepares the method for zirconium diboride nano-powder
Technical field
The invention belongs to ceramic powder material field, namely one prepares ZrB 2the method of nano-powder material.Relate to a kind of organic and inorganic complexing, namely adopt glucose complexing boric acid, then add propylene oxide and be polymerized with zirconates, improve sol system stability, thus prepare nanometer ZrB by sol-gel technique 2the method of powder.
Background technology
The development of aerospace science and technology, requires more and more higher to material antioxidant property in high temperature environments.Boride, as one of hyperthermal material, owing to having excellent physicochemical property, makes the research interest of researchist to it grow with each passing day.Binary borides is made up of covalent linkage and metallic bond, has higher fusing point, higher hardness, higher thermal conductivity, and density ratio is lower simultaneously, is applicable to heat-resistant light material, so become the study hotspot in superhigh temperature ceramic material field.ZrB 2it is material more common in boride, there is high-melting-point (3250 DEG C), there is covalent linkage (B-B) and metallic bond (Zr-B) simultaneously, so have the double properties of pottery and metal, thus there is the characteristics such as high rigidity, high thermal shock stability, high heat conductance and high conductivity, and when contacting with molten iron, have good unreactiveness, and there are the overall characteristics such as low high-temperature heat expansion coefficient and low saturated vapor pressure.Therefore the candidate material of component under the extreme ultrahigh-temperature service condition such as rocket engine, supersonic plane, refractory materials and nuclear control is become.
Current preparation ZrB 2the method of powder mainly contains solid phase method and the large class of liquid phase method two.Traditional preparation methods is solid phase method, and solid phase method mainly comprises element direct synthesis technique, self-propagating high-temperature method, mechanochemical reaction etc.Adopt solid phase method to prepare the calcining temperature of powder needs is higher, synthetic powder particle size comparatively greatly, purity is lower, thus causes powder sintering poor activity.Liquid phase method mainly comprises hydrothermal method, sol-gel method and chemical coprecipitation etc.Mixed by the raw material in molecular/ionic level, make that the ceramic powder chemical uniformity of synthesis is high, particle diameter is little, specific surface area is large, thus be conducive to the sintering temperature reducing powder.Wherein sol-gel method prepares ZrB at present 2the study hotspot of powder, the advantage of this method is that technique is comparatively simple, and powder synthesis temperature is relatively low, and the purity obtaining powder is high, and particle size is little, thus improves the sintering characteristic of pottery.
But, although the higher ZrB of purity successfully can be prepared at present 2powder, but in the preparation process of powder, also there are some problems, the stability of colloidal sol in preparation process, the concrete steps such as sol-gel control process also do not have systematize, the temperature drift (mostly at about 1500 DEG C) of sintering, powder skewness, the problems such as agglomeration is obvious still exist.In addition, the zirconium source that current sol-gel method adopts is divided into organic zirconium source and inorganic zirconium source, and organic zirconium source price is high, and toxicity is large; The boron source adopted is generally boric acid (H 3bO 3), and H 3bO 3just simple dissolving in the solution, does not participate in the structure of colloidal sol network, thus has influence on the homogeneity of colloidal sol distribution, affects the microstructure of powder further, thus produces certain impact to the performance of powder.
Summary of the invention
The present invention adopts a kind of sol-gel technique of organic and inorganic complexing to prepare ZrB 2nano-powder, first select chlorine oxygen zirconium as inorganic zirconium source, cost is low, and toxicity is little; Boric acid as boron source, and selects polyhydric Organic grape sugar as complexing agent, by the complex reaction of it and boric acid, improves the solubleness of boric acid.Add propylene oxide afterwards as polymerizing agent, boric acid is polymerized further with chlorine oxygen zirconium, forms stable ZrB 2precursor sol.Glucose also can participate in the carrying out of carbothermic reduction reaction as carbon source simultaneously, does not need to introduce other carbon source.The colloidal sol of preparation, finally by the link such as calcining of gelation, drying, carbothermic reduction reaction, prepares ZrB 2nano-powder.
The present invention is realized by following concrete technical scheme:
The sol-gel technique of organic and inorganic complexing of the present invention prepares the method for zirconium diboride nano-powder, and its step is as follows:
(1) zirconium source solution is prepared: by ZrOCl 28H 2o adds in alcohol solvent and dissolves, heating in water bath at 60-80 DEG C, and then solution is cooled to room temperature, obtains zirconium source solution;
(2) prepare boron source colloidal sol: be dissolved in ethanol by boric acid and glucose, heating in water bath at 80-90 DEG C, is cooled to room temperature, obtains boron source colloidal sol;
(3) prepare Zr-B mixed sols: measure zirconium solution according to mol ratio B:Zr=3.0-4.0:1, zirconium solution is joined in boron colloidal sol, after mixing, add complexing agent propylene oxide, obtain stable Zr-B mixed sols;
(4) ZrB is prepared 2presoma: Zr-B mixed sols is first dried at 60-120 DEG C, obtains transparent wet gel; Then temperature is elevated to 200-300 DEG C, obtains ZrB 2presoma;
(5) ZrB is synthesized 2nano-powder: by ZrB 2presoma grinds, and carries out high-temperature calcination process under an argon atmosphere, obtains grey black ZrB 2powder.
Described step 1) middle ethanol: ZrOCl 28H 2o quality=0.6-0.9.
Described step 1) middle heating in water bath 0.5-1h.
Described step 2) middle H 3bO 3: glucose mol ratio=3.5-5.3:1.
Described step 2) in, ethanol: glucose quality ratio=1.4-2.5:1.
Described step 2) middle heating in water bath 0.5-1h.
Described step 3) oxypropylene: ZrOCl 28H 2o mol ratio=(0.5-3.5): 1.
Described step 4) at 60-120 DEG C, dry 1-3h; At 200-300 DEG C of insulation 1-3h.
Described step 5) calcining temperature 1430-1550 DEG C, insulation 1-3h.
Described step 5) temperature rise rate is 3-5 DEG C/min.
By ZrB 2nano-powder carries out corresponding thing phase and pattern test analysis.
According to technique described in this patent, synthesize high-purity ZrB at a lower temperature 2nano-powder, the purity of the powder obtained can reach more than 95%.The particle size of synthesis is less, becomes near-spherical, and distribution is comparatively even, and size distribution is between 50-300nm.In addition, compared to the sol-gel method of document, the method for this organic and inorganic complexing reduces high-temperature calcination synthesis temperature, and significantly improves ZrB 2the productive rate of powder.
The sol-gel technique utilizing organic and inorganic complexing of the present invention to the effect that by glucose as complexing agent and boric acid complexing, propylene oxide is as polymerizing agent, make boric acid complex and the chlorine oxygen zirconium polymerization reaction take place of formation, form the macromolecular network structure of Zr-O-C-O-B, prepare ZrB in conjunction with carbothermic reduction reaction 2nano-powder.The powder granule size of preparation is little, and become near-spherical, be uniformly dispersed, synthesis temperature is lower, and obtains high-purity ZrB under lower B/Zr 2nano-powder.
Accompanying drawing explanation
Fig. 1: in the embodiment of the present invention 1, B/Zr are than being 3.0:1, the powder material phase analysis figure that 1430 DEG C of sintering soak 1h obtain.
Fig. 2: in the embodiment of the present invention 1, B/Zr are than being 3.0:1, the powder scintigram that 1430 DEG C of sintering soak 1h obtain.
Fig. 3: in the embodiment of the present invention 2, B/Zr are than being 3.5:1, the powder material phase analysis figure that 1490 DEG C of sintering soak 2h obtain.
Fig. 4: in the embodiment of the present invention 2, B/Zr are than being 3.5:1, the powder scintigram that 1490 DEG C of sintering soak 2h obtain.
Fig. 5: in the embodiment of the present invention 3, B/Zr are than being 4.0:1, the powder material phase analysis figure that 1550 DEG C of sintering soak 3h obtain.
Fig. 6: in the embodiment of the present invention 3, B/Zr are than being 4.0:1, the powder scintigram that 1550 DEG C of sintering soak 3h obtain.
Embodiment
Embodiments of the invention adopt following optimal technical scheme, and be illustrated by reference to the accompanying drawings, but be not limited to this, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Be preferably as follows step:
(1) zirconium source colloidal sol is prepared: take ZrOCl 28H 2o, by ethanol: ZrOCl 28H 2o=(0.6-0.9): 1 mass ratio adds ethanol as solvent, by ZrOCl 28H 2o dissolves, and at 60-80 DEG C, heating in water bath 0.5-1h, is cooled to room temperature by solution, obtains zirconium source colloidal sol;
(2) boron source colloidal sol is prepared: take H 3bO 3, by H 3bO 3: glucose=(3.5-5.3): 1 (mol ratio) takes glucose, by ethanol: glucose=(1.4-2.5): 1 (mass ratio) takes ethanol, boric acid and glucose are dissolved in ethanol, heating in water bath 0.5-1h at 80-90 DEG C, be cooled to room temperature, obtain boron source colloidal sol.
(3) Zr-B mixed sols is prepared: get boron source colloidal sol, according to B:Zr=(3.0-4.0): 1 (mol ratio) measures zirconium colloidal sol, under induction stirring, zirconium source colloidal sol is joined gradually in the colloidal sol of boron source, after mixing, by propylene oxide: ZrOCl 28H 2o=(0.5-3.5): 1 (mol ratio) adds complexing agent propylene oxide gradually, Keep agitation 0.5-1h, obtains stable Zr-B mixed sols.
(4) ZrB is prepared 2presoma: transfer in baking oven by Zr-B mixed sols, first dries 1-3h at 60-120 DEG C, obtains transparent wet gel; Afterwards temperature is elevated to 200-300 DEG C, insulation 1-3h, obtains ZrB 2presoma;
(5) ZrB is synthesized 2nano-powder: by ZrB 2presoma grinds, and is placed in saggar, is placed in by saggar in tube-type atmosphere furnace, carries out high-temperature calcination process under an argon atmosphere, and temperature increasing schedule is, rises to synthesis temperature 1430-1550 DEG C with the speed of 3-5 DEG C/min from room temperature, at this synthesis temperature insulation 1-3h; Then be down to room temperature with stove, stop passing into argon gas, obtain grey black powder, the powder obtained is ground, finally obtains ZrB 2nano-powder.
Embodiment 1:
(1) zirconium source solution is prepared: weigh in the balance and get 3.2225g ZrOCl 28H 2o, by ethanol: ZrOCl 28H 2o=0.6:1 (mass ratio) adds 1.9335g ethanol as solvent by ZrOCl 28H 2o dissolves, and at 60 DEG C, heating in water bath 0.5h, is cooled to room temperature by solution, obtains zirconium source solution.
(2) boron source colloidal sol is prepared: weigh in the balance and get 1.8549g H 3bO 3, by H 3bO 3: glucose=3.5:1 (mol ratio) takes glucose 1.5442g, by ethanol: glucose=1.4:1 (mass ratio) takes ethanol 2.1619g, is dissolved in ethanol by boric acid and glucose, heating in water bath 0.5h at 80 DEG C, be cooled to room temperature, obtain boron source colloidal sol.
(3) Zr-B mixed sols is prepared: get 5.5610g boron source colloidal sol, measure zirconium solution 5.1560g according to B:Zr=3.0:1 (mol ratio), under induction stirring, zirconium solution is dropwise added drop-wise in boron colloidal sol, after mixing, by propylene oxide: ZrOCl 28H 2o=0.5:1 (mol ratio) dropwise adds complexing agent propylene oxide 0.2904g, Keep agitation 0.5h, obtains stable Zr-B mixed sols.
(4) ZrB is prepared 2presoma: transfer in baking oven by Zr-B mixed sols, first dries 1h at 60 DEG C, obtains transparent wet gel.Afterwards temperature is elevated to 200 DEG C, insulation 1h, obtains ZrB 2presoma.
(5) ZrB is synthesized 2nano-powder: by ZrB 2presoma grinds, and is placed in saggar, is placed in by saggar in tube-type atmosphere furnace, carries out high-temperature calcination process under an argon atmosphere, and temperature increasing schedule is, rises to synthesis temperature 1430 DEG C with the speed of 3 DEG C/min from room temperature, at this synthesis temperature insulation 1h.Then be down to room temperature with stove, stop passing into argon gas, obtain greyish black toner originally, the powder obtained is ground, finally obtains ZrB 2nano-powder.
In the powder that embodiment 1 is obtained, granule-morphology is nearly ball-like structure, and granular size is between 50-100nm, is evenly distributed, ZrB 2phase reaches 95%.
Embodiment 2:
Detailed process is as embodiment 1, and difference is
(1) by ethanol: ZrOCl 28H 2o=0.75:1 (mass ratio), adds 2.4169g ethanol as solvent by ZrOCl 28H 2o dissolves, heating in water bath 0.75h at 70 DEG C.
(2) 2.1641g H is taken 3bO 3, by H 3bO 3: glucose=4.4:1 (mol ratio) takes glucose 1.4331g, by ethanol: glucose=2.0:1 (mass ratio) takes ethanol 2.8662g, is dissolved in ethanol by boric acid and glucose, heating in water bath 0.75h at 85 DEG C.
(3) get 6.4634g boron source colloidal sol, measure zirconium solution 5.6394g according to B:Zr=3.5:1 (mol ratio).By propylene oxide: ZrOCl 28H 2o=2:1 (mol ratio) dropwise adds propylene oxide 1.1616g, Keep agitation 0.75h.
(4) first Zr-B mixed sols dries 2h at 90 DEG C, obtains transparent wet gel.Afterwards temperature is elevated to 250 DEG C, insulation 2h.
(5) temperature increasing schedule is, rises to synthesis temperature 1490 DEG C with the speed of 4 DEG C/min from room temperature, at this synthesis temperature insulation 2h.
In the powder that embodiment 2 is obtained, granule-morphology is nearly ball-like structure, and granular size is about 100nm, is evenly distributed, and there is slight agglomeration, ZrB 2phase reaches 98%.
Embodiment 3:
Detailed process as embodiment 1, difference is,
(1) by ethanol: ZrOCl 28H 2o=0.9:1 (mass ratio), adds 2.9003g ethanol as solvent by ZrOCl 28H 2o dissolves, heating in water bath 1h at 80 DEG C.
(2) 2.4732g H is taken 3bO 3, by H 3bO 3: glucose=5.3:1 (mol ratio) takes glucose 1.3597g, by ethanol: glucose=2.5:1 (mass ratio) takes ethanol 3.3993g, is dissolved in ethanol by boric acid and glucose, heating in water bath 1h at 90 DEG C.
(3) get 7.2322g boron source colloidal sol, measure zirconium solution 6.1228g according to B:Zr=4.0:1 (mol ratio).By propylene oxide: ZrOCl 28H 2o=3.5:1 (mol ratio) dropwise adds propylene oxide 2.0328g, Keep agitation 1h.
(4) first Zr-B mixed sols dries 3h at 120 DEG C, obtains transparent wet gel.Afterwards temperature is elevated to 300 DEG C, insulation 3h.
(5) temperature increasing schedule is, rises to synthesis temperature 1550 DEG C with the speed of 5 DEG C/min from room temperature, at this synthesis temperature insulation 3h.
In the powder that embodiment 3 is obtained, granule-morphology is nearly ball-like structure, and granular size is between 100-200nm, is evenly distributed, and there is slight agglomeration, ZrB 2phase reaches 95%.
Open and all methods that propose of the present invention and technology of preparing, those skilled in the art are by using for reference present disclosure, the links such as appropriate change raw material and operational path realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.

Claims (10)

1. the sol-gel technique of organic and inorganic complexing prepares a method for zirconium diboride nano-powder, it is characterized in that step is as follows:
(1) zirconium source solution is prepared: by ZrOCl 28H 2o adds in alcohol solvent and dissolves, heating in water bath at 60 ~ 80 DEG C, and then solution is cooled to room temperature, obtains zirconium source solution;
(2) prepare boron source colloidal sol: be dissolved in ethanol by boric acid and glucose, heating in water bath at 80 ~ 90 DEG C, is cooled to room temperature, obtains boron source colloidal sol;
(3) prepare Zr ~ B mixed sols: measure zirconium solution according to mol ratio B:Zr=3.0 ~ 4.0:1, zirconium solution is joined in boron colloidal sol, after mixing, add complexing agent propylene oxide, obtain stable Zr ~ B mixed sols;
(4) ZrB is prepared 2presoma: Zr ~ B mixed sols is first dried at 60 ~ 120 DEG C, obtains transparent wet gel; Then temperature is elevated to 200 ~ 300 DEG C, obtains ZrB 2presoma;
(5) ZrB is synthesized 2nano-powder: by ZrB 2presoma grinds, and carries out high-temperature calcination process under an argon atmosphere, obtains grey black ZrB 2powder.
2. the method for claim 1, is characterized in that described step 1) middle ethanol: ZrOCl 28H 2o quality=0.6 ~ 0.9.
3. the method for claim 1, is characterized in that described step 1) middle heating in water bath 0.5 ~ 1h.
4. the method for claim 1, is characterized in that described step 2) middle H 3bO 3: glucose mol ratio=3.5 ~ 5.3:1.
5. the method for claim 1, is characterized in that described step 2) in, ethanol: glucose quality is than=1.4 ~ 2.5:1.
6. the method for claim 1, is characterized in that described step 2) middle heating in water bath 0.5 ~ 1h.
7. the method for claim 1, is characterized in that described step 3) oxypropylene: ZrOCl 28H 2o mol ratio=(0.5 ~ 3.5): 1.
8. the method for claim 1, is characterized in that described step 4) at 60 ~ 120 DEG C, dry 1 ~ 3h; At 200 ~ 300 DEG C of insulation 1 ~ 3h.
9. the method for claim 1, is characterized in that described step 5) calcining temperature 1430 ~ 1550 DEG C, insulation 1 ~ 3h.
10. the method for claim 1, is characterized in that described step 5) temperature rise rate is 3 ~ 5 DEG C/min.
CN201510060806.4A 2015-02-05 2015-02-05 Method for preparing zirconium diboride nanopowder by virtue of organic-inorganic complex sol-gel technology Pending CN104628391A (en)

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CN108975919A (en) * 2018-09-19 2018-12-11 陕西科技大学 A kind of liquid phase method prepares the technique of spherical ultra-fine zirconium boride powder and the zirconium boride powder of preparation
CN111517799A (en) * 2020-04-20 2020-08-11 中国科学院合肥物质科学研究院 Method for preparing zirconium boride powder with assistance of alcohol solvent
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
CN112010617A (en) * 2020-08-31 2020-12-01 常州坚鹏建材有限公司 Durable stable steel slag-mineral powder concrete and preparation method thereof
CN115073183A (en) * 2022-06-27 2022-09-20 山东大学 High-entropy boride nano powder and sol-gel preparation method thereof
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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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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Application publication date: 20150520