CN114230348A - High-compactness ZrB2High-pressure preparation method of ultrahigh-temperature-based ceramic - Google Patents
High-compactness ZrB2High-pressure preparation method of ultrahigh-temperature-based ceramic Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000919 ceramic Substances 0.000 title claims abstract description 19
- 238000002679 ablation Methods 0.000 claims abstract description 66
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 39
- 229910007948 ZrB2 Inorganic materials 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000011215 ultra-high-temperature ceramic Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
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- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
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- 238000000034 method Methods 0.000 abstract description 8
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- 238000001238 wet grinding Methods 0.000 abstract 2
- 238000002441 X-ray diffraction Methods 0.000 description 9
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
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Abstract
High-compactness ZrB2A high-pressure preparation method of ultrahigh-temperature ceramic belongs to the field of ultrahigh-temperature ceramic materials. In particular to the structure and the ablation resistance of the ultrahigh-temperature ceramic material. In the invention, ZrB2Weighing and mixing the powder and the metal carbide powder according to a molar ratio of 1: 1-20: 1; carrying out particle refinement on the raw material by a wet grinding method, centrifuging, drying and compression molding the slurry subjected to wet grinding, and carrying out sintering densification under the high-pressure condition, wherein the sintering pressure is 2-4 GPa, the sintering temperature is 750-950 ℃, and finally the high-density ZrB is prepared2-ZrC ultra high temperature ceramic material. ZrB provided by the invention2The high-pressure preparation method of the ultrahigh-temperature-based ceramic has the advantages of simple and efficient process, can obviously reduce the sintering temperature of the material, and reduces the high temperature place in the preparation processThe time required. Effectively improves the density of the ceramic material and improves the thermal ablation resistance of the ultrahigh-temperature ceramic.
Description
Technical Field
The invention belongs to the field of ultra-high temperature ceramic materials, and particularly relates to high-density ZrB2A high-pressure preparation method of ultrahigh-temperature-based ceramic.
Background
The ultra-high temperature ceramic refers to a ceramic material with a melting point of more than 3000 ℃ and physical and chemical properties of which are stable at the ultra-high temperature. Ultra-high temperature ceramic materials are generally composed of borides, carbides and nitrides of transition group metals (e.g., Zr, Hf, Ta, etc.). ZrB2The ultrahigh-temperature ceramic has the excellent characteristics of high melting point, high strength, high thermal conductivity, high electrical conductivity, excellent chemical stability, high-temperature ablation resistance and the like. The ceramic material is considered to be one of ultra-high temperature ceramic materials with the most application prospect, and can be used for a heat protection system of an ultra-high speed aircraft and a carrier thereof, a key material of a strategic missile, a thermal protection structural material of a modern airship, a nose cone of a reentry airship, a material of a wing leading edge component and the like. Currently ZrB2The basic ultrahigh temperature ceramic becomes one of the hot spots of basic research and application research at home and abroad.
Single phase ZrB2The sintering property of the ceramic is poor, so that the mechanical property, the oxidation resistance and the burning resistance of the ceramic can not meet the application requirements of the ultra-high temperature environment, and the application of the ceramic is limited to a great extent. In ZrB2The second phase such as SiC, HfC, ZrC and other sintering aids are introduced, so that the compactness and the high-temperature ablation resistance of the material can be effectively improved. But due to ZrB2The self-diffusion coefficient of (a) is low, and high densification is often achieved by long-time sintering at temperatures above 2000 ℃ by conventional methods such as pressureless sintering, hot-pressing sintering, spark plasma sintering, and the like. In view of the limitations of the above preparation method, it is necessary to develop a method for preparing high-density ZrB with high efficiency and lower sintering temperature2A method for preparing a superhigh temperature ceramic material.
Background art patent numbers of the present invention: CN 102167592A
The patent name: ZrB2A preparation method of-ZrC-based ultrahigh temperature resistant ceramic.
The specific steps of the background technology are as follows:
(1) preparing a green body: weighing B with the mass ratio of 19:14Mixing the weighed raw materials by ball milling, placing the mixed powder in a mould, keeping the temperature at 120 ℃ for 6 hours, and forming by a mould pressing or crosslinking mode to obtain a green body;
(2) firing of the porous rigid preform: cracking the green body at 900 ℃ under a vacuum condition, and preserving heat for 1h to obtain a porous rigid prefabricated body;
(3) preparing zirconium-containing alloy, taking metal zirconium and metal copper with the mass ratio of 1:1 as main materials, and preparing the zirconium-containing alloy through vacuum induction melting.
(4) Infiltration reaction: taking the prepared porous rigid preform as a base material, taking zirconium-containing alloy as an infiltration agent, embedding the base material in the zirconium-containing alloy, heating to 1100 ℃ under a vacuum condition, preserving heat for 5 hours, separating the obtained composite material from molten metal, and preparing ZrB2-a ZrC-based ultra-high temperature resistant ceramic semi-finished product;
(5) high-temperature treatment: with B4C powder embedding the ZrB2Heating the-ZrC-based ultrahigh temperature resistant ceramic semi-finished product to 1400 ℃ under vacuum condition, and preserving heat for 2 hours to obtain ZrB2-ZrC based ultra high temperature resistant ceramics.
ZrB prepared by the process2The bending strength of the-ZrC-based ultrahigh temperature resistant ceramic is 574MPaFracture toughness of 7.1MPa m1/2The material was ablated in an oxyacetylene flame for 30 seconds with a line ablation rate of 0.45 μm/s.
Summary of the background art:
the advantages are that: ZrB with excellent mechanical property and high-temperature ablation resistance is prepared through infiltration reaction and high-temperature treatment2-ZrC based ultra high temperature resistant ceramics.
The disadvantages are as follows:
(1) when the porous prefabricated body is fired by the green body, the porous prefabricated body is required to be in a vacuum environment, and the porosity and the pore size of the obtained porous rigid prefabricated body are difficult to realize accurate control after the porous rigid prefabricated body is fired at higher temperature for longer time.
(2) ZrB is obtained by carrying out infiltration reaction on zirconium-copper alloy in porous rigid prefabricated part2-ZrC-based ultra high temperature resistant ceramic semi-finished product, wherein metallic copper impurities are difficult to completely remove.
(3) By means of B4ZrB embedded by C powder or SiC powder2The ZrC-based ultrahigh temperature resistant ceramic semi-finished product is subjected to high temperature treatment to obtain ZrB2-ZrC based ultra high temperature resistant ceramics. Wherein ZrB2And ZrC crystal grains can grow abnormally at high temperature, the compactness of the ceramic material is influenced,
(4) the preparation period is long: the long-time heat preservation is performed for many times in the preparation steps, namely the first step is 6 h; the second step is 1 h; fourthly, 5 h; and a fifth step of 2 h. The holding time is 14h in total.
(5) The preparation energy consumption is high: the preparation process is carried out at high temperature under vacuum condition for most of time, namely, the temperature is kept at 120 ℃ for 6 hours; preserving heat for 1h at 900 ℃; keeping the temperature at 1100 ℃ for 5 h; keeping the temperature at 1400 ℃ for 2 h.
(6) The material has a high rate of line ablation: after 30s of ablation in an oxyacetylene flame at 1600 ℃, the respective line ablation rates are 0.45 μm/s; 0.37 μm/s; 0.32 μm/s.
Disclosure of Invention
The invention aims to overcome the technical defects of the preparation method. For preparing high-density ZrB2Ultra high temperature ceramic material requiring ZrB2The sintering aid is added into the base material. The method aims to solve the problems that the optimal doping concentration, the optimal sintering temperature and the optimal pressure condition of a sintering aid are determined, the density of a ceramic material is increased, and the ablation resistance of the ceramic material is improved; the sintering temperature of the ceramic material is reduced, the sintering time and the preparation period are shortened, the production efficiency is improved, and the production cost is saved.
The invention solves the technical problems as follows:
(1) the density of the ceramic material is effectively reduced by changing the doping concentration of the sintering aid; and the dispersion strengthening mechanism of the sintering aid nano particles is utilized to effectively promote the ZrB prepared2Mechanical property of the superhigh temperature ceramic.
(2) The method applies GPa-level high pressure to the material in the high-temperature sintering process, realizes the inhibition of abnormal growth of crystal grains at high temperature by inhibiting atomic diffusion, and obtains ZrB consisting of nano crystal grains2High density ceramic material.
(3) The invention adopts the high-pressure technology, provides additional driving force for densification sintering, obviously reduces the synthesis temperature of the ceramic material, greatly shortens the synthesis time, and effectively reduces ZrB2Production cost of the ultrahigh temperature ceramic material.
(4) The invention realizes the preparation of ZrB2The ultrahigh temperature ceramic material can still maintain excellent thermal ablation resistance in an extreme environment of more than 2000 ℃.
The implementation steps of the invention are as follows:
step one, batching: reacting ZrB2Weighing and mixing the powder and transition metal carbide (ZrC, HfC, TaC and SiC) powder according to a molar ratio of 1: 1-20: 1;
step two, mixing materials: reacting ZrB2Mixing the metal carbide mixed material with absolute ethyl alcohol to prepare slurry, wherein the mass ratio of the mixed material to the ethyl alcohol is 1: 10-1: 20; pouring the slurry into a stainless steel ball milling tank for ball milling, wherein the rotating speed of a planetary ball mill is 200-450 rpm, and the ball milling time is 2-4 h to obtain uniformly mixed slurry;
step three, centrifugal drying: and placing the ball-milled slurry in a centrifuge, centrifuging at the rotating speed of 11000rpm for 5min, removing supernatant after centrifugation, and drying in a constant-temperature air blast drying box at the temperature of 100-120 ℃ for 15-25min to obtain dried powder.
Step four, compression molding: molding the dried powder into a cylinder (with the diameter of 6-10 mm and the height of 4-6 mm) at the molding pressure of 4-6 MPa for 1-3 min;
fifthly, high-pressure sintering: placing the compression-molded cylinder into a double-top high-pressure press for sintering, and increasing the pressure to 2-4 GPa at the pressure increasing rate of 0.2-0.4 GPa per minute; then raising the temperature to 750-950 ℃ at a heating rate of 150-200 ℃ per minute; keeping the temperature and the pressure for 10-20 min; after the heat preservation and pressure maintaining are finished, unloading the pressure and taking out a sample for later use;
sixthly, density and ablation performance: testing the density of the sample prepared by the steps by using an Archimedes method, wherein the density P of the sample is determined by a formula: p ═ P/P0X 100% calculated, where ρ0Is ZrB2-theoretical density of ZrC composite, ρ being measured density of high pressure prepared sample; and (3) ablating the sample prepared in the step by using oxyacetylene flame with the high temperature of 1600-2000 ℃, wherein the ablation time is 60 s. Mass burning of samplesEtching rate RmAccording to the formula Rm＝(m2-m1) V (t.S) is calculated, where m1Is the sample mass before ablation; m is2Mass after ablation; t is the time of ablation; s is the surface area of the sample; line ablation Rate R of the sampleLAccording to the formula RL＝(L2-L1) Calculated as,/t, where L1Is the sample thickness before ablation; l is2Is the thickness after ablation; and t is the ablation time.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample prepared according to an embodiment of the present invention:
(a) x-ray diffraction pattern of the sample of example 1; (b) x-ray diffraction pattern of the sample of example 2;
(c) x-ray diffraction pattern of the sample of example 3; (d) example 4X-ray diffraction pattern of the sample.
FIG. 2 is a scanning electron micrograph of a cross section of a sample prepared according to an embodiment of the present invention after ablation at 1600 deg.C:
(a) scanning electron micrographs of sample sections of example 1; (b) example 2 scanning electron micrographs of sample sections;
(c) example 3 scanning electron micrographs of sample sections; (d) example 4 scanning electron micrographs of a cross section of a sample.
Detailed Description
The core idea of the invention will be explained in detail below with reference to the accompanying drawings and specific embodiments:
example one
High-compactness ZrB2The preparation method of the basic ultra-high temperature ceramic material comprises the following specific implementation steps:
step one, batching and compounding: reacting ZrB2Weighing and mixing powder (with the particle size of 45-150 mu m and the purity of 99.5%) and ZrC powder (with the particle size of 1 mu m and the purity of 99.5%) according to a molar ratio of 2: 1; putting the mixed material into a ball milling tank, adding absolute ethyl alcohol, wherein the mass ratio of the mixed material to the ethyl alcohol is 1:15, and carrying out ball milling for 3h at the rotating speed of 300 rpm.
Step two, drying and forming: and placing the ball-milled slurry in a centrifuge, centrifuging at the rotation speed of 11000rpm for 5min, and drying the slurry after centrifuging and removing the supernatant in a constant-temperature air blast drying box at the temperature of 120 ℃ for 20min to obtain a dried powder mixed material. And (3) molding the dried mixed material into a cylinder shape (phi 6mm multiplied by 4.5mm), wherein the molding pressure is 4MPa, and the molding time is 1 min.
Thirdly, high-pressure sintering: putting the cylindrical mixed material into a press for high-pressure sintering, and keeping the temperature and the pressure for 10min under the conditions that the pressure is 2.9GPa and the temperature is 950 ℃; the synthesized cylindrical sample was taken out by reducing the temperature and the pressure, and the XRD pattern thereof was as shown in FIG. 1 (a). After comparing the XRD pattern of the sample with PDFs (#34-0423) and (#35-0784), it was confirmed that the sample was ZrB2-a ZrC composite ceramic material;
fourthly, density and ablation performance: and (2) ablating the sample synthesized in the step in oxyacetylene flame at the temperature of 1600-2000 ℃, wherein the flow rate of oxygen is 25L/min, the flow rate of acetylene is 50L/min, the inner diameter of a nozzle of a spray gun is 2mm, the surface of the sample vertically faces to the nozzle at a distance of 30-50 mm from the nozzle, and the ablation time is 60 s. The density of the sample prepared by the embodiment is 95.4%, and the mass ablation rate after the sample is ablated for 60s at 1600 ℃ is 0.19 mg/(s-cm)2) The linear ablation rate is 0.15 μm/s; the mass ablation rate after ablation for 60s at 2000 ℃ is 0.92 mg/(s-cm)2) The linear ablation rate was 4.6 μm/s. FIG. 2(a) is a cross-sectional profile of a sample prepared according to the present embodiment after ablation at 1600 ℃. The average thickness of the oxide layer after ablation was 238 μm.
Example two
High-compactness ZrB2The preparation method of the basic ultra-high temperature ceramic material comprises the following specific implementation steps:
in contrast to the first example, this comparative example follows ZrB2ZrC is weighed according to the molar ratio of 4:1, the mixture is mixed, the ablation temperature is 1600 ℃, and other implementation steps are the same as those in the first embodiment.
The X-ray diffraction pattern of the sample prepared in this example is shown in FIG. 1 (b). The density of the sample is 93.8 percent, and the mass ablation rate is 0.15 mg/(s-cm)2) The linear ablation rate was 0.19 μm/s. FIG. 2(b) is a scanning electron microscope image of the ablated profile of the sample prepared in this example, wherein the average thickness of the oxide layer after ablation is 140 μm.
EXAMPLE III
High-compactness ZrB2The preparation method of the basic ultra-high temperature ceramic material comprises the following specific implementation steps:
in contrast to the first example, this comparative example follows ZrB2ZrC is weighed according to the molar ratio of 8:1, the mixture is mixed, the ablation temperature is 1600 ℃, and other implementation steps are the same as those in the first embodiment.
The X-ray diffraction pattern of the sample prepared in this example is shown in FIG. 1 (c). The density of the sample is 95.4 percent, and the mass ablation rate is 0.12 mg/(s-cm)2) The linear ablation rate was 0.19 μm/s. FIG. 2(c) is a scanning electron microscope image of the ablated profile of the sample prepared in this example, wherein the average thickness of the oxide layer after ablation is 80 μm.
Example four
High-compactness ZrB2The preparation method of the basic ultra-high temperature ceramic material comprises the following specific implementation steps:
in contrast to the first example, this comparative example follows ZrB2ZrC is weighed according to the molar ratio of 16:1, the ablation temperature is 1600 ℃, and other implementation steps are the same as those in the first embodiment.
The X-ray diffraction pattern of the sample prepared in this example is shown in FIG. 1 (d). The density of the sample is 95.5 percent, and the mass ablation rate is 0.28 mg/(s-cm)2) The linear ablation rate was 0.20 μm/s. FIG. 2(d) is a scanning electron microscope image of the ablated profile of the sample prepared in this example, wherein the average thickness of the oxide layer after ablation is 112 μm.
And (4) analyzing results: in conclusion, ZrB is improved by adding the metal carbide sintering aid2The sintering capability of the ultrahigh-temperature ceramic promotes the densification of the sample; the high-pressure synthesis technology is utilized to realize the rapid preparation of the high-density ZrB at a lower sintering temperature2The ultrahigh-temperature ceramic material is based, and the abnormal growth of crystal grains at high temperature is inhibited, so that the ultrahigh-temperature ceramic material can keep excellent mechanical property and excellent high-temperature ablation resistance.
Claims (3)
1. AHigh-density ZrB2The high-pressure preparation method of the ultrahigh-temperature-based ceramic is characterized by comprising the following steps of: the preparation method comprises the following specific steps:
step one, batching: reacting ZrB2Weighing and mixing the powder and transition metal carbide (ZrC, HfC, TaC and SiC) powder according to a molar ratio of 1: 1-20: 1;
step two, mixing and ball milling: ZrB2Respectively mixing the metal carbide (ZrC, SiC, HfC and TaC) and the metal carbide (ZrC, SiC, HfC and TaC) to obtain a mixed material, and mixing the mixed material and absolute ethyl alcohol to prepare slurry, wherein the mass ratio of the mixed material to the ethyl alcohol is 1: 10-1: 20; pouring the slurry into a stainless steel ball milling tank for ball milling, wherein the rotating speed of a planetary ball mill is 200-400 rpm, and the ball milling time is 2-4 h to obtain uniformly mixed slurry;
step three, centrifugal drying: placing the ball-milled slurry in a centrifuge, centrifuging at the rotation speed of 11000rpm for 5min, removing supernatant after centrifugation, and drying in a constant-temperature air blast drying oven at the temperature of 100-120 ℃ for 15-25min to obtain a dried powder mixed material;
step four, compression molding: molding the dried powder mixture into a cylinder (the diameter is 6-10 mm, the height is 4-6 mm), the molding pressure is 4-6 MPa, and the molding time is 1-3 min;
fifthly, high-pressure sintering: placing the compression-molded cylinder into a press for high-pressure sintering, and increasing the pressure to 2-4 GPa at the pressure increasing rate of 0.2-0.4 GPa per minute; then raising the temperature to 750-950 ℃ at a heating rate of 150-200 ℃ per minute; keeping the temperature and the pressure for 10-20 min; after the heat preservation and pressure maintaining are finished, unloading the pressure and taking out a sample for later use;
sixthly, density and ablation performance: testing the density of the sample prepared by the steps by using an Archimedes method, wherein the density P of the sample is determined by a formula: p ═ P/P0X 100% calculated, where ρ0Is ZrB2-theoretical density of ZrC composite, ρ being measured density of high pressure prepared sample; burning the sample prepared in the step by using oxygen-acetylene flame at 1600-2000 ℃, wherein the burning time is 60 s; mass ablation rate R of samplemAccording to the formula Rm＝(m2-m1)/(t.S) is calculated, wherein m1Mass of sample before ablation, m2The mass after ablation, t the time of ablation and S the surface area of the sample; line ablation Rate R of the sampleLAccording to the formula RL＝(L2-L1) Calculated as,/t, where L1Thickness of the sample before ablation, L2For thickness after ablation, t is the ablation time of the sample.
2. High-density ZrB according to claim 12The high-pressure preparation method of the ultrahigh-temperature ceramic material is characterized by comprising the following steps of: ball milling time is 2-4 h; centrifuging the slurry for 5 min; drying the slurry for 15-25 min; forming time is 1-3 min; boosting time is 10 min; heating for 5-7 min; and keeping the temperature and the pressure for 10-20 min.
3. High-compactness ZrB2The ultrahigh-temperature ceramic material is characterized in that: said ZrB2The ultrahigh-temperature-based ceramic material is the high-density ZrB as claimed in claim 12The high-pressure preparation method of the ultrahigh-temperature-based ceramic comprises the following steps:
(1) the initial raw material is ZrB2Weighing and mixing the powder (with the purity of 99.5%) and ZrC powder (with the purity of 99.5%) according to the molar ratio of 2: 1-16: 1;
(2) after drying and compression molding, the ball-milled mixed material is put into a double-top high-pressure press, and is kept for 10min under the conditions of 2.9GPa of pressure and 950 ℃ of temperature, and the sample is taken out for standby after temperature reduction and pressure relief;
(3)ZrB2ZrB prepared by mixing ZrC with ZrC in a molar ratio of 2:12The density of the-ZrC ceramic material is 5.97g/cm3The density is 95.4%; ablating the obtained ZrB in oxyacetylene flame at 1600 ℃ for 60s2The mass ablation rate of the-ZrC ceramic material is 0.19 mg/(s-cm)2) The linear ablation rate is 0.15 μm/s; after ablation in oxyacetylene flame at 2000 ℃ for 60s, ZrB was obtained2The mass ablation rate of the-ZrC ceramic material is 0.92 mg/(s-cm)2) The linear ablation rate is 4.6 μm/s;
(4)ZrB2is prepared by mixing ZrC with the raw materials according to the molar ratio of 4:1ZrB of2The density of the-ZrC ceramic material is 5.82g/cm3The density is 93.8%; ZrB obtained after ablation in oxyacetylene flame at 1600 DEG C2The mass ablation rate of the-ZrC ceramic material is 0.15 mg/(s-cm)2) The linear ablation rate is 0.19 μm/s;
(5)ZrB2ZrB prepared by mixing ZrC with a molar ratio of 8:12The density of the-ZrC ceramic material is 5.87g/cm3The density is 95.4%; ZrB obtained after ablation in oxyacetylene flame at 1600 DEG C2The mass ablation rate of the-ZrC ceramic material is 0.12 mg/(s-cm)2) The linear ablation rate is 0.19 μm/s;
(6)ZrB2ZrB prepared by mixing ZrC with a molar ratio of 16:12The density of the-ZrC ceramic material is 5.85g/cm3The density is 95.5%; ZrB obtained after ablation in oxyacetylene flame at 1600 DEG C2The mass ablation rate of the-ZrC ceramic material is 0.28 mg/(s-cm)2) The linear ablation rate was 0.20 μm/s.
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