CN111848178A - Method for microwave synthesis of hafnium diboride nano powder by complex sol-gel technology - Google Patents

Method for microwave synthesis of hafnium diboride nano powder by complex sol-gel technology Download PDF

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CN111848178A
CN111848178A CN202010778256.0A CN202010778256A CN111848178A CN 111848178 A CN111848178 A CN 111848178A CN 202010778256 A CN202010778256 A CN 202010778256A CN 111848178 A CN111848178 A CN 111848178A
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彭志明
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Hunan Huawei Jingcheng Material Technology Co ltd
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Abstract

The invention provides a method for microwave synthesis of hafnium diboride nano-powder by a complex sol-gel technology. Preparing hafnium source solution and boron source sol, complexing boric acid with glucose as complexing agent, adding epoxypropane to complex with hafnium salt, and preparing nano HfB at lower synthesis temperature by sol-gel technology2And (3) powder. The invention selects the hafnium oxychloride as the inorganic hafnium source, and has low cost and low toxicity; boric acid is used as a boron source, and polyhydroxy organic glucose is selected as a complexing agent to form stable HfB2And (5) precursor sol. Meanwhile, glucose can also be used as a carbon source to participate in the carbothermic reduction reaction, and other carbon sources are not required to be introduced. Powder particle ruler prepared by the processSmall size, sphere-like shape, uniform dispersion, low synthesis temperature, and obtaining high-purity HfB under low B/Hf2And (3) nano powder.

Description

Method for microwave synthesis of hafnium diboride nano powder by complex sol-gel technology
Technical Field
The invention relates to the field of ceramic powder materials, in particular to a method for microwave synthesis of hafnium diboride nano powder by a complex sol-gel technology.
Background
Hafnium diboride (HfB)2) Is one of the materials with the best high-temperature performance in ultra-high-temperature ceramic materials (UHTCS), has high melting point (3380 ℃) and simultaneously has covalent bonds (B-B) and metal bonds (H)f-B), thereby having the dual properties of ceramics and metals, thereby having the characteristics of high hardness, high thermal shock resistance, high thermal conductivity, high electrical conductivity and the like, having good chemical inertness when contacting molten iron, and having the comprehensive characteristics of low high-temperature thermal expansion coefficient, low saturated vapor pressure and the like. Therefore, the material is the preferable material for parts under extreme ultra-high temperature service conditions such as rocket engines, supersonic aircrafts, refractory materials and nuclear control, but the problem of difficult sintering and the like still restricts the application development of the material. The nanometer hafnium diboride (HfB) prepared by the invention2) The powder can improve the sintering driving force, reduce the sintering temperature and improve the structural strength and the ablation resistance of parts.
Preparation of HfB2The powder method mainly includes two main types, namely a solid phase method and a liquid phase method. The traditional preparation method is a solid phase method which mainly comprises an element direct synthesis method, a high-temperature self-propagating method, a carbon reduction method and the like. The solid phase method for preparing the powder has the disadvantages of high preparation temperature, large particle size of the synthesized powder and uneven particle size distribution, so that the powder has poor sintering activity and poor sintering quality. The liquid phase method mainly comprises a hydrothermal method, a sol-gel method, a vapor deposition method and the like. Through the mixing of the raw materials at the molecular/ionic level, the synthesized ceramic powder has high chemical uniformity, small particle size and large specific surface area, thereby being beneficial to reducing the sintering temperature of the powder. Wherein the sol-gel method is currently used for preparing HfB2The method has the advantages of simple process, relatively low powder synthesis temperature, high purity of the obtained powder and small particle size, thereby improving the sintering characteristic of the ceramic.
At present, HfB with higher purity can be successfully prepared2The powder has some problems in the preparation process of the powder, and the problems of stability of sol, sol-gel control process and other specific steps in the preparation process are not systematized, the sintering temperature is relatively high (mostly about 1500-1800 ℃), the powder is not uniformly distributed, the agglomeration phenomenon is obvious and the like still exist. In addition, the hafnium source adopted by the current sol-gel method is divided into an organic hafnium source and an inorganic hafnium source, and the organic hafnium source has high price and high toxicity; the boron source employed is typically boric acid (H)3BO3) And H is3BO3The sol is simply dissolved in the solution and does not participate in the construction of the sol network, so that the distribution uniformity of the sol is influenced, the microstructure of the powder is further influenced, and the performance of the powder is greatly influenced.
Disclosure of Invention
The invention provides a method for microwave synthesis of hafnium diboride nano powder by a complex sol-gel technology, and aims to provide a preparation method which has the advantages of low cost, simple process, low synthesis temperature, small synthesis particle size and uniform dispersion of high-purity HfB2The nano-powder is prepared by mixing the following raw materials,
in order to achieve the aim, the invention provides a method for microwave synthesis of hafnium diboride nano powder by a complex sol-gel technology, which comprises the following steps:
step 1, preparing a hafnium source solution:
mixing HfOCl2·8H 20, adding the mixture into an ethanol solvent for dissolving, heating in a water bath, and then cooling to room temperature to obtain a hafnium source solution;
step 2, preparing boron source sol:
dissolving boric acid and glucose in ethanol, heating in water bath, and cooling to room temperature to obtain boron source sol;
step 3, preparing Hf-B mixed sol:
adding the hafnium solution obtained in the step 1 into the boron source sol obtained in the step 2, uniformly mixing, and adding a complexing agent propylene oxide to obtain stable Hf-B mixed sol, wherein the molar ratio of B to Hf is 2.5-3.2: 1;
step 4, preparing HfB2Precursor:
drying the Hf-B mixed sol to obtain transparent wet gel; then raising the temperature to the heat preservation temperature for heat preservation to obtain HfB2A precursor;
step 5, synthesizing HfB2Nano powder:
to HfB2Grinding and crushing the precursor, and performing high-temperature calcination treatment by using a microwave vacuum furnace at 1250-1450 ℃ for 2-3 h to obtain grayish black HfB2And (3) powder.
Preferably, in step 1, HfOCl2·8H2The mass ratio of 0 to ethanol is 1: 0.7 to 0.9.
Preferably, in the step 1, the water bath heating temperature is: 50-80 ℃ for the following time: 1-1.5 h.
Preferably, in said step 2, H3B03The molar ratio of the glucose to the glucose is 3.2-5.5: 1.
Preferably, in the step 2, the mass ratio of the ethanol to the glucose is 1.8-2.5: 1.
Preferably, in the step 2, the water bath heating temperature is as follows: 50-100 ℃, and the time is as follows: 1-2.5 h.
Preferably, in the step 3, the propylene oxide and the HfOCl are reacted2·8H2The molar ratio of 0 is 0.5-3.2: 1.
Preferably, in the step 4, the drying temperature is; drying for 1-3 h at 80-150 ℃; the heat preservation temperature is as follows: 220-350 ℃, and the heat preservation time is as follows: 2-3 h.
Preferably, in the step 5, the temperature rise rate is 3-5 ℃/min.
The scheme of the invention has the following beneficial effects:
according to the invention, by utilizing the organic-inorganic complexing sol-gel technology, glucose is used as a complexing agent to be complexed with boric acid to improve the solubility of the boric acid, and propylene oxide is used as a polymerizing agent to enable the formed boric acid complex to be subjected to polymerization reaction with hafnium oxychloride to form a macromolecular network structure of Hf-0-C-O-B, and glucose can also be used as a carbon source, other carbon sources are not required to be introduced, and HfB is prepared through carbothermic reduction reaction2And (3) nano powder. The prepared powder has small particle size, is spherical, is uniformly dispersed, has lower synthesis temperature, and can obtain high-purity HfB under lower B/Hf2And (3) nano powder.
According to the process of the invention, high-purity HfB is synthesized at lower temperature2The purity of the obtained nano powder can reach more than 95 percent. The synthesized particles have small size, are shaped like spheres or rods, are distributed uniformly, and have the particle size distribution of 80-150 nm. In addition, organic-inorganic complexingThe method reduces the high-temperature calcination synthesis temperature and obviously improves HfB2Yield of powder.
Drawings
FIG. 1 shows HfB obtained in example 1 of the present invention2XRD pattern of nano powder.
FIG. 2 shows HfB obtained in example 1 of the present invention2TEM image of nanopowder.
FIG. 3 shows HfB obtained in example 2 of the present invention2XRD pattern of nano powder.
FIG. 4 shows HfB obtained in example 2 of the present invention2TEM image of nanopowder.
FIG. 5 shows HfB obtained in example 3 of the present invention2XRD pattern of nano powder.
FIG. 6 shows HfB obtained in example 3 of the present invention2TEM image of nanopowder.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Step 1, preparing a hafnium source solution: by ethanol with HfOCl2·8H 20 mass ratio of 0.7-0.9: 1, and taking HfOCl by balance2·8H 20, adding the hafnium-containing raw material into ethanol for dissolving, heating in water bath for 1.0-2.5 hours at the temperature of 60-80 ℃, and then cooling the solution to room temperature to obtain the hafnium source solution.
Step 2, preparing boron source sol: according to H3B03The molar ratio of the glucose to the glucose is 3.2-5.5: 1, and H is weighed by using balance3B03And glucose, weighing the ethanol according to the mass ratio of the ethanol to the glucose of 1.8-2.5: 1, dissolving boric acid and the glucose in the ethanol, heating the solution in water bath at the temperature of 80-100 ℃ for 1-2.5h, and then cooling the solution to the room temperature to obtain the boron source sol.
Step 3, preparing Hf-B mixed sol: according to the molar ratio of B to Hf of 2.5-3.2: 1, taking a boron source sol and a hafnium source solution, dropwise adding the hafnium solution into the boron source sol under electromagnetic stirring, uniformly mixing, and then mixing epoxypropane and HfOCl2·8H 20 mol ratio of 0.5-3.2: 1, and dropwise adding a complexing agentAnd continuously stirring the epoxypropane for 0.5-1 h to obtain the stable Hf-B mixed sol.
Step 4, preparing HfB2Precursor: transferring the Hf-B mixed sol into a drying oven, and drying for 1-3 h at 80-150 ℃ to obtain transparent wet gel. Then raising the temperature to 220-350 ℃, and preserving the heat for 2-3 h to obtain HfB2And (3) precursor.
Step 5, synthesizing HfB2Nano powder: to HfB2Grinding and crushing the precursor, placing the precursor into a tungsten carbide crucible, placing the tungsten carbide crucible into a microwave vacuum furnace, and carrying out high-temperature calcination treatment in a high vacuum environment, wherein the temperature rise system is that the temperature is increased from room temperature to the synthesis temperature of 1250-1450 ℃ at the speed of 3-5 ℃/min, the vacuum degree is less than 5Pa, and the temperature is kept at the synthesis temperature for 1-3 h. Then cooling to room temperature along with the furnace to obtain a gray black powder, grinding the obtained powder to obtain HfB2And (3) nano powder.
Example 1
Step 1, preparing a hafnium source solution: by ethanol with HfOCl2·8H 20 mass ratio of 0.7:1, weighing 15.12g HfOCl by balance2·8H 20, adding 21.6g of ethanol to dissolve, heating in a water bath at 60 ℃ for 1.0h, and then cooling the solution to room temperature to obtain a hafnium source solution.
Step 2, preparing boron source sol: according to H3B03The molar ratio of the glucose to the glucose is 3.5:1, and 5.46gH is weighed by using a scale3B03And 41.92 of glucose, wherein 58.67g of ethanol is weighed according to the mass ratio of the ethanol to the glucose of 1.4:1, boric acid and the glucose are dissolved in the ethanol, the mixture is heated in a water bath at 100 ℃ for 1.5h, and then the mixture is cooled to room temperature, so that the boron source sol is obtained.
Step 3, preparing Hf-B mixed sol: according to the molar ratio of B to Hf of 2.5:1, 16.35g of boron source sol and 25.78g of hafnium source solution are taken, the hafnium solution is dropwise added into the boron source sol under electromagnetic stirring, and after uniform mixing, propylene oxide and HfOCl are added2·8H 20 mol ratio of 0.5:1, 1.793g of complexing agent propylene oxide is added dropwise, and the mixture is continuously stirred for 0.8h to obtain the stable Hf-B mixed sol.
Step 4, preparing HfB2Precursor: transferring the Hf-B mixed sol into a drying oven, and firstly drying the Hf-B mixed sol for 1h at 80 ℃ to obtain transparent wet gel. Then raising the temperature to 250 ℃, and preserving the temperature for 1h to obtain HfB2And (3) precursor.
Step 5, synthesizing HfB2Nano powder: to HfB2Grinding and crushing the precursor, placing the precursor into a tungsten carbide crucible, placing the tungsten carbide crucible into a microwave vacuum furnace, and carrying out high-temperature calcination treatment in a high vacuum environment, wherein the temperature rise system is that the temperature is raised from room temperature to a synthesis temperature 1480 ℃ at the speed of 3 ℃/min, the vacuum degree is less than 5Pa, and the temperature is kept for 2h at the synthesis temperature. Then cooling to room temperature along with the furnace to obtain a gray black powder, grinding the obtained powder to obtain HfB2And (3) nano powder.
In the powder prepared in example 1, the particle morphology is a near-bat-shaped structure, the particle size is 80-150nm, and large particles exceeding 200 nm exist, which may be caused by rapid growth of particles due to high synthesis temperature, XRD diffraction analysis, HfB2The phase composition purity reaches 97%, and the hafnium oxide content is about 3%. Through stoichiometric analysis, because the quality of the boron source is less, the reaction is incomplete, and a hafnium oxide impurity phase exists.
Example 2
Step 1, preparing a hafnium source solution: by ethanol with HfOCl2·8H 20 mass ratio of 0.7:1, weighing 15.12g HfOCl by balance2·8H 20, adding 21.6g of ethanol to dissolve, heating in a water bath at 60 ℃ for 1.0h, and then cooling the solution to room temperature to obtain a hafnium source solution.
Step 2, preparing boron source sol: according to H3B03The molar ratio of the glucose to the glucose is 3.5:1, and 5.46gH is weighed by using a scale3B03And 41.92 of glucose, wherein 58.67g of ethanol is weighed according to the mass ratio of the ethanol to the glucose of 1.4:1, boric acid and the glucose are dissolved in the ethanol, the mixture is heated in a water bath at 100 ℃ for 1.5h, and then the mixture is cooled to room temperature, so that the boron source sol is obtained.
Step 3, preparing Hf-B mixed sol: according to the molar ratio of B to Hf of 3.0:1, 19.62g of boron source sol and 25.78g of hafnium source solution are taken, and the hafnium solution is dropwise added into the mixture under electromagnetic stirringMixing the boron source sol uniformly, and mixing the mixture with the HfOCl2·8H 20 mol ratio of 0.5:1, 1.793g of complexing agent propylene oxide is added dropwise, and the mixture is continuously stirred for 0.8h to obtain the stable Hf-B mixed sol.
Step 4, preparing HfB2Precursor: transferring the Hf-B mixed sol into a drying oven, and firstly drying the Hf-B mixed sol for 1h at 80 ℃ to obtain transparent wet gel. Then raising the temperature to 250 ℃, and preserving the temperature for 1h to obtain HfB2And (3) precursor.
Step 5, synthesizing HfB2Nano powder: to HfB2Grinding and crushing the precursor, placing the precursor into a tungsten carbide crucible, placing the tungsten carbide crucible into a microwave vacuum furnace, and carrying out high-temperature calcination treatment in a high vacuum environment, wherein the temperature rise system is that the temperature is increased from room temperature to the synthesis temperature of 1450 ℃ at the speed of 3 ℃/min, the vacuum degree is less than 5Pa, and the temperature is kept at the synthesis temperature for 2 h. Then cooling to room temperature along with the furnace to obtain a gray black powder, grinding the obtained powder to obtain HfB2And (3) nano powder.
In the powder prepared in example 1, the particle morphology is a near-bat-shaped structure, the particle size is 80-150nm, and large particles exceeding 200 nm exist, which may be caused by rapid growth of particles due to high synthesis temperature, XRD diffraction analysis, HfB2The phase composition purity reaches 98.2%, and the hafnium oxide content is about 1.8%. By adjusting the proportioning weight of the boron source, the impurity phase of hafnium oxide is effectively reduced.
Example 3
Step 1, preparing a hafnium source solution: by ethanol with HfOCl2·8H 20 mass ratio of 0.7:1, weighing 15.12g HfOCl by balance2·8H 20, adding 21.6g of ethanol to dissolve, heating in a water bath at 60 ℃ for 1.0h, and then cooling the solution to room temperature to obtain a hafnium source solution.
Step 2, preparing boron source sol: according to H3B03The molar ratio of the glucose to the glucose is 3.5:1, and 5.46gH is weighed by using a scale3B03And 41.92 of glucose, and the mass ratio of ethanol to glucose is 1.4:1, 58.67g of ethanol is weighed, boric acid and glucose are dissolved in ethanol, water bath heating is carried out for 1.5h at 100 ℃, and then cooling is carried outAnd cooling to room temperature to obtain the boron source sol.
Step 3, preparing Hf-B mixed sol: according to the molar ratio of B to Hf of 3.2:1, 20.93gg boron source sol and 25.78g hafnium source solution are taken, the hafnium solution is dropwise added into the boron source sol under electromagnetic stirring, and after uniform mixing, epoxypropane and HfOCl are added2·8H 20 mol ratio of 0.5:1, 1.793g of complexing agent propylene oxide is added dropwise, and the mixture is continuously stirred for 0.8h to obtain the stable Hf-B mixed sol.
Step 4, preparing HfB2Precursor: transferring the Hf-B mixed sol into a drying oven, and firstly drying the Hf-B mixed sol for 1h at 80 ℃ to obtain transparent wet gel. Then raising the temperature to 250 ℃, and preserving the temperature for 1h to obtain HfB2And (3) precursor.
Step 5, synthesizing HfB2Nano powder: to HfB2Grinding and crushing the precursor, placing the precursor into a tungsten carbide crucible, placing the tungsten carbide crucible into a microwave vacuum furnace, and carrying out high-temperature calcination treatment in a high vacuum environment, wherein the temperature rise system is that the temperature is raised from room temperature to the synthesis temperature of 1350-1380 ℃ at the speed of 3 ℃/min, the vacuum degree is less than 5Pa, and the temperature is kept for 4 hours at the synthesis temperature. Then cooling to room temperature along with the furnace to obtain a gray black powder, grinding the obtained powder to obtain HfB2And (3) nano powder.
In the powder prepared in the embodiment 1, the particle morphology is a near-bat-shaped structure, the particle size is 80-150nm, the distribution is uniform, no large particles exceeding 200 nm exist, the slight agglomeration phenomenon exists, XRD diffraction analysis shows that HfB (x-ray diffraction) analysis shows that HfB (high-frequency B)2The phase composition purity reaches 100%, and no impurity phase exists.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. A method for microwave synthesis of hafnium diboride nano-powder by a complex sol-gel technology is characterized by comprising the following steps:
step 1, preparing a hafnium source solution:
mixing HfOCl2·8H20, adding the mixture into an ethanol solvent for dissolving, heating in a water bath, and then cooling to room temperature to obtain a hafnium source solution;
step 2, preparing boron source sol:
dissolving boric acid and glucose in ethanol, heating in water bath, and cooling to room temperature to obtain boron source sol;
step 3, preparing Hf-B mixed sol:
adding the hafnium solution obtained in the step 1 into the boron source sol obtained in the step 2, uniformly mixing, and adding a complexing agent propylene oxide to obtain stable Hf-B mixed sol, wherein the molar ratio of B to Hf is 2.5-3.2: 1;
step 4, preparing HfB2Precursor:
drying the Hf-B mixed sol to obtain transparent wet gel; then raising the temperature to the heat preservation temperature for heat preservation to obtain HfB2A precursor;
step 5, synthesizing HfB2Nano powder:
to HfB2Grinding and crushing the precursor, and performing high-temperature calcination treatment by using a microwave vacuum furnace at 1250-1450 ℃ for 2-3 h to obtain HfB2And (3) powder.
2. The method for microwave synthesis of hafnium diboride nanopowder by using the complex sol-gel technique as claimed in claim 1, wherein in the step 1, HfOCl2·8H2The mass ratio of 0 to ethanol is 1: 0.7 to 0.9.
3. The method for microwave synthesis of hafnium diboride nanopowder by using the complex sol-gel technique according to claim 1, wherein in the step 1, the water bath heating temperature is as follows: 50-80 ℃ for the following time: 1-1.5 h.
4. The method for microwave synthesis of hafnium diboride nanopowder by using the complex sol-gel technique according to claim 1, wherein in the step 2, H3B03With grapesThe molar ratio of the sugar is 3.2-5.5: 1.
5. The method for microwave synthesis of the hafnium diboride nanopowder by the complex sol-gel technique according to claim 1, wherein in the step 2, the mass ratio of ethanol to glucose is 1.8-2.5: 1.
6. The method for microwave synthesis of hafnium diboride nanopowder by using the complex sol-gel technique according to claim 1, wherein in the step 2, the water bath heating temperature is as follows: 50-100 ℃, and the time is as follows: 1-2.5 h.
7. The method for microwave synthesis of hafnium diboride nanopowder by using the complex sol-gel technique as claimed in claim 1, wherein in the step 3, propylene oxide and HfOCl are used2·8H2The molar ratio of 0 is 0.5-3.2: 1.
8. The method for microwave synthesis of hafnium diboride nanopowder by using the complex sol-gel technique according to claim 1, wherein in the step 4, the drying temperature is; drying for 1-3 h at 80-150 ℃; the heat preservation temperature is as follows: 220-350 ℃, and the heat preservation time is as follows: 2-3 h.
9. The method for microwave synthesis of hafnium diboride nanopowder by using the complex sol-gel technique as claimed in claim 1, wherein in the step 5, the temperature rise rate is 3-5 ℃/min.
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