CN114907120A - Ultrafine-grained titanium-based high-plasticity ceramic material and preparation method thereof - Google Patents

Ultrafine-grained titanium-based high-plasticity ceramic material and preparation method thereof Download PDF

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CN114907120A
CN114907120A CN202210408338.5A CN202210408338A CN114907120A CN 114907120 A CN114907120 A CN 114907120A CN 202210408338 A CN202210408338 A CN 202210408338A CN 114907120 A CN114907120 A CN 114907120A
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ceramic
based high
ceramic material
plasticity
titanium
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项忠楠
李友军
叶鑫
徐金海
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Chuzhou Yongpu New Material Technology Co ltd
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Chuzhou Yongpu New Material Technology Co ltd
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Abstract

The invention discloses an ultra-fine grain titanium-based high-plasticity ceramic material and a preparation method thereof, and relates to the technical field of ceramic materials. When the ultrafine-grained titanium-based high-plasticity ceramic material is prepared, firstly, tetraethoxysilane and metaaluminate solution are mixed to wrap zirconia particles, and the mixture is sintered by using supercritical ammonia-assisted oscillation pressure to form a silicon nitride-alumina layer with refined grains and zirconium oxide as a support body, so as to prepare a ceramic blank; mixing the ceramic blank, water, ethanol and carbon black to obtain a ceramic premix; finally, titanium tetrachloride is used for carrying out secondary oscillation pressure sintering on the ceramic premix to generate ultrafine-grained titanium carbide grains, and the ultrafine-grained titanium-based high-plasticity ceramic material is prepared; the ultra-fine grain titanium-based high-plasticity ceramic material prepared by the invention has high bending strength and compressive strength and good wear resistance and fracture toughness.

Description

Ultrafine-grained titanium-based high-plasticity ceramic material and preparation method thereof
Technical Field
The invention relates to the technical field of ceramic materials, in particular to an ultra-fine grain titanium-based high-plasticity ceramic material and a preparation method thereof.
Background
With the rapid development of aerospace, automobile and other manufacturing industries in China, the use amount of difficult-to-cut materials such as cast iron, high-temperature alloy and the like is increased rapidly. In addition, due to the requirements on the size, the machining precision, the surface integrity and the like of key parts are continuously improved, and the requirements on the cutting efficiency and the cutting speed are continuously improved, more and more machining processes use numerical control high-speed and high-efficiency machining equipment, and therefore the requirements on the cutter are continuously improved.
Due to the excellent high-temperature stability and chemical stability of the silicon nitride ceramic material, the ceramic knife prepared by the silicon nitride ceramic material is favored by technical personnel in the fields of high-speed and high-efficiency cutting and cutting of difficult-to-process materials. However, the ceramic is brittle and the ceramic blade is often easily broken by abrasion during the cutting process, which greatly increases the cutting cost. Therefore, the preparation of the wear-resistant ceramic with stronger fracture toughness becomes a great technical problem in the current field.
The invention discovers the phenomenon and solves the problem by preparing the ultra-fine grained titanium-based high-plasticity ceramic material.
Disclosure of Invention
The invention aims to provide an ultra-fine grain titanium-based high-plasticity ceramic material and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of an ultra-fine grain titanium-based high-plasticity ceramic material is provided, wherein the ultra-fine grain titanium-based high-plasticity ceramic material is prepared by carrying out secondary oscillation pressure sintering on a ceramic premix by using titanium tetrachloride; the ceramic premix is obtained by mixing ceramic blank, water, ethanol and carbon black; the ceramic blank is prepared by mixing tetraethoxysilane and metaaluminate solution and sintering by using supercritical ammonia to assist primary oscillation pressure.
Further, the preparation method of the ultra-fine grain titanium-based high-plasticity ceramic material comprises the following steps: putting the ceramic premix into a reaction kettle at the temperature of 80-90 ℃ under the protection of argon, and then adding the ceramic premix into the reaction kettle at the speed of 5-7 m 3 Introducing titanium tetrachloride which is 0.3-0.5 times of the ceramic premix into the reactor per minute, continuously stirring the mixture for 2-4 hours, drying the mixture for 46-50 hours at the temperature of 8-12 ℃ under the pressure of 10-20 Pa, and then drying the dried mixture at the speed of 9-11 ℃/mAnd (3) in heating to 1500-1600 ℃, preserving the heat for 3-5 h, and then carrying out oscillating pressure sintering for 3-5 min to prepare the ultrafine-grained titanium-based high-plasticity ceramic material.
Further, the preparation method of the ceramic premix comprises the following steps: mixing ceramic blank, water, ethanol and carbon black according to a mass ratio of 1: 1: 5: 2-1: 3: 7: 4, mixing, and stirring for 10-20 min at a speed of 400-600 r/min to prepare the ceramic premix.
Further, the preparation method of the ceramic blank comprises the following steps: under the protection condition of argon, mixing the composite aerogel, carbon black, nickel and yttrium oxide according to the mass ratio of 1: 3: 0.07: 0.3-1: 5: 0.08: 0.5 percent of the mixture is put into a reaction kettle with 0.7 to 0.9MPa, the temperature is increased to 690 to 710 ℃ at the speed of 4 to 6 ℃/min, and the temperature is increased to 5 to 6m 3 Introducing supercritical ammonia gas 7-8 times the mass of the composite aerogel per hour, stirring for 1-3 hours at 400-600 r/min, heating to 1300-1500 ℃ at 9-11 ℃/min, preserving heat for 1-3 hours, sintering under oscillating pressure for 3-5 minutes, naturally cooling to normal temperature at 5-6 m 3 Introducing supercritical ammonia for 10-20 min, washing with absolute ethyl alcohol for 3-5 times, and putting into an oven at 30-40 ℃ for drying for 1-3 h to prepare the ceramic blank.
Further, the preparation method of the supercritical ammonia gas comprises the following steps: and (3) introducing ammonia gas into a reaction kettle with the pressure of 12-13 MPa, heating to 133-135 ℃ at the speed of 9-11 ℃/min, and preserving heat for 1-3 h to prepare supercritical ammonia gas.
Further, the preparation method of the composite aerogel comprises the following steps: and (3) freezing the composite sol in a refrigerator at a temperature of-4 to-2 ℃ for 47-49 h, drying at a temperature of-10 to 20Pa and-50 to-40 ℃ for 47-49 h, washing with absolute ethyl alcohol for 2-4 times, and drying in a drying oven at a temperature of 10 to 20Pa and 19 to 21 ℃ for 1-3 h to prepare the composite aerogel.
Further, the preparation method of the composite sol comprises the following steps: at the temperature of 24-26 ℃, ethyl orthosilicate and ethanol are mixed according to the mass ratio of 1: 3-1: 5, stirring for 20-30 min at 1200-1300 r/min, then dropwise adding a meta-aluminate solution of which the weight is 5-7 times that of ethyl orthosilicate at 60-80 ℃ for 2-4 h, dropwise adding a sodium hydroxide solution of which the weight is 20% at 60-80 r/min for adjusting the pH value to 8-10, continuously stirring for 2-4 h, adding zirconium oxide particles of which the weight is 0.05-0.07 time that of ethyl orthosilicate, continuously stirring for 3-4 h, and naturally cooling to room temperature to prepare the composite sol.
Further, the zirconia fine particles have a particle diameter of 10 to 12 μm.
Further, the preparation method of the aluminum acid solution comprises the following steps: at the temperature of 24-26 ℃, mixing metaaluminic acid, deionized water and a nitric acid solution with the mass fraction of 30% according to the mass ratio of 1: 29: 2-1: 31: 4, mixing and stirring at 300-400 r/min for 20-30 min to prepare the metaaluminate solution.
Further, the oscillating pressure sintering comprises the following specific steps: heating to 1700-1750 ℃ at a speed of 9-10 ℃/min, boosting to 29-31 MPa at a speed of 1-3 MPa/min, and then superposing an oscillating pressure with a frequency of 2-4 Hz and a pressure of 4-6 MPa.
Compared with the prior art, the invention has the following beneficial effects:
when the ultrafine-grained titanium-based high-plasticity ceramic material is prepared, firstly, tetraethoxysilane and metaaluminic acid solution are mixed and coated with zirconia particles, and supercritical ammonia gas is used for assisting in oscillating pressure sintering to prepare a ceramic blank; mixing the ceramic blank, water, ethanol and carbon black to obtain a ceramic premix; and finally, carrying out secondary oscillation pressure sintering on the ceramic premix by using titanium tetrachloride to prepare the ultrafine-grained titanium-based high-plasticity ceramic material.
Firstly, the metaaluminate and the tetraethoxysilane react and crosslink to form the silicon dioxide-aluminum oxide composite aerogel with an interpenetrating network structure, so that aluminum oxide crystal grains are uniformly dispersed in the ceramic blank, and the reduction of the bending strength of the silicon nitride ceramic blank caused by the agglomeration of the aluminum oxide is avoided; the silicon dioxide-aluminum oxide composite aerogel takes zirconium oxide particles as a support body and is sintered and formed with ammonia gas to form a silicon nitride-aluminum oxide layer, a large number of free radicals such as amino groups and the like are formed in silicon nitride pore channels, and meanwhile, a plurality of new surfaces with small curvature radius are formed with the zirconium oxide in the growth process of silicon nitride and aluminum oxide crystal grains, the increase of the new surfaces increases the free energy of a system, prevents the growth of the silicon nitride and aluminum oxide crystal grains, so that the silicon nitride and aluminum oxide crystal grains are refined, and the compressive strength of a ceramic blank is increased.
Secondly, titanium tetrachloride is rapidly adsorbed by the ceramic blank, chlorine atoms of the titanium tetrachloride react with amino groups in the pore channels of the ceramic blank for crosslinking, hydrolysis and polycondensation to form a titanium dioxide crosslinking network, and the titanium dioxide is carbonized and reduced to form a large amount of ultrafine-grained titanium carbide, so that the density of the ceramic material is enhanced, and the wear resistance of the ceramic material is further enhanced; meanwhile, the ultrafine crystal titanium carbide is uniformly dispersed in the silicon carbide ceramic matrix, and when microcracks and residual stress are generated around the ultrafine crystal titanium carbide, pinning effects on the microcracks can be generated, fracture energy is consumed, and therefore the toughness of the ceramic material is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided to illustrate the method for testing each index of the ultra-fine grained titanium-based high-plasticity ceramic material prepared in the following examples as follows:
wear resistance: the wear resistance of the ultra-fine grained titanium-based high-plastic ceramic materials prepared in the same mass of the examples and comparative examples was tested by measuring the density according to the standard ASTMC 20.
Bending strength: the ultra-fine grained titanium-based high-plastic ceramic material prepared by the embodiment and the comparative example with the same length and width is measured for bending strength according to the standard of ASTMC 1161.
Compressive strength: the compression strength of the ultra-fine grained titanium-based high-plasticity ceramic material ASTMC773 prepared by the same mass of the embodiment and the comparative example is tested.
Fracture toughness: the fracture toughness of the ultra-fine grained titanium-based high-plastic ceramic material prepared by the embodiment and the comparative example with the same length and width is tested according to ASTMC 1421.
Example 1
A preparation method of an ultra-fine grain titanium-based high-plasticity ceramic material comprises the following preparation steps:
(1) at the temperature of 24 ℃, mixing metaaluminic acid, deionized water and a nitric acid solution with the mass fraction of 30% according to the mass ratio of 1: 29: 2, mixing, and stirring at 300r/min for 20min to prepare a metaaluminate solution; at the temperature of 24 ℃, ethyl orthosilicate and ethanol are mixed according to the mass ratio of 1: 3, mixing, stirring for 20min at 1200r/min, then dropwise adding an aluminum acid solution which is 5 times that of ethyl orthosilicate at 60 drops/min, continuously stirring for 2h at 60 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 20% at 60 drops/min to adjust the pH value to 8, continuously stirring for 2h, adding zirconium oxide particles with the particle size of 10 mu m and the mass of 0.05 time that of the ethyl orthosilicate, continuously stirring for 3h, and naturally cooling to room temperature to prepare composite sol; freezing the composite sol in a refrigerator at-4 ℃ for 47h, then drying at 10Pa and-50 ℃ for 47h, washing with absolute ethyl alcohol for 2 times, and drying in an oven at 10Pa and 19 ℃ for 1h to prepare the composite aerogel;
(2) introducing ammonia gas into a 12MPa reaction kettle, heating to 133 ℃ at the speed of 9 ℃/min, and preserving heat for 1h to prepare supercritical ammonia gas; under the protection condition of argon, mixing the composite aerogel, carbon black, nickel and yttrium oxide according to the mass ratio of 1: 3: 0.07: 0.3 mixing, putting into a 0.7MPa reaction kettle, heating to 690 ℃ at a rate of 4 ℃/min, and heating to 5m 3 Introducing supercritical ammonia gas 7 times the mass of the composite aerogel, stirring at 400r/min for 1h, heating to 1300 ℃ at 9 ℃/min, keeping the temperature for 1h, heating to 1700 ℃ at 9 ℃/min, boosting to 29MPa at 1MPa/min, then superposing an oscillation pressure with the frequency of 2Hz and 4MPa, keeping the oscillation pressure for 3min, naturally cooling to normal temperature, and cooling at 5m 3 Introducing supercritical ammonia for 10min, washing with anhydrous ethanol for 3 times, and oven drying at 30 deg.C for 1h to obtain ceramic blank;
(3) ceramic blank, water, ethanol and carbon black are mixed according to the mass ratio of 1: 1: 5: 2, mixing and stirring for 10min at the speed of 400r/min to prepare a ceramic premix; the ceramic premix was placed in a reaction kettle at 80 ℃ under argon protection and subsequently at 5m 3 Permin four times of ceramic premix is addedAnd (3) continuously stirring the titanium chloride for 2h, drying the titanium chloride for 46h at 10Pa and 8 ℃, then heating the titanium chloride to 1500 ℃ at the speed of 9 ℃/min, preserving the heat for 3h, then heating the titanium chloride to 1700 ℃ at the speed of 9 ℃/min, boosting the titanium chloride to 29MPa at the speed of 1MPa/min, and then superposing an oscillating pressure with the frequency of 2Hz and the pressure of 4MPa to keep the oscillating pressure for 3min to prepare the ultrafine-crystal titanium-based high-plasticity ceramic material.
Example 2
A preparation method of an ultra-fine grain titanium-based high-plasticity ceramic material comprises the following preparation steps:
(1) at the temperature of 25 ℃, mixing metaaluminic acid, deionized water and a nitric acid solution with the mass fraction of 30% according to the mass ratio of 1: 30: 3, mixing, and stirring at 350r/min for 25min to prepare a metaaluminate solution; at the temperature of 25 ℃, ethyl orthosilicate and ethanol are mixed according to the mass ratio of 1: 4, mixing, stirring for 25min at 1250r/min, then dropwise adding a meta-aluminum acid solution 6 times of ethyl orthosilicate at 70 drops/min, continuously stirring for 3h at 70 ℃, dropwise adding a sodium hydroxide solution with the mass fraction of 20% at 70 drops/min to adjust the pH to 9, continuously stirring for 3h, adding zirconium oxide particles with the particle size of 11 mu m and the mass of 0.06 time of the ethyl orthosilicate, continuously stirring for 3.5h, and naturally cooling to room temperature to prepare composite sol; putting the composite sol into a refrigerator at the temperature of-3 ℃ for freezing for 48h, then drying for 48h at the temperature of 15Pa and-45 ℃, washing for 3 times by using absolute ethyl alcohol, putting into an oven at the temperature of 15Pa and 20 ℃ for drying for 2h, grinding, and sieving by using a 900-mesh sieve to prepare the composite aerogel;
(2) introducing ammonia gas into a reaction kettle with the pressure of 12.5MPa, heating to 134 ℃ at the speed of 10 ℃/min, and preserving heat for 2h to prepare supercritical ammonia gas; under the protection condition of argon, mixing the composite aerogel, carbon black, nickel and yttrium oxide according to the mass ratio of 1: 4: 0.075: 0.4, placing the mixture into a reaction kettle with the pressure of 0.8MPa, heating the mixture to 700 ℃ at the speed of 5 ℃/min and heating the mixture to 5.5m 3 Introducing supercritical ammonia gas with the mass 7.5 times of that of the composite aerogel per hour, stirring at 500r/min for 2 hours, heating to 1400 ℃ at 10 ℃/min, preserving heat for 2 hours, heating to 1725 ℃ at 9 ℃/min, boosting to 30MPa at 2MPa/min, then superposing an oscillation pressure with the frequency of 3Hz and 5MPa, keeping the oscillation pressure for 4 minutes, naturally cooling to normal temperature, and cooling at 5.5m 3 Introducing supercritical ammonia gas for 15min, and washing with anhydrous ethanol for 4 timesPutting the ceramic blank into a 35 ℃ oven to be dried for 2 hours to prepare a ceramic blank;
(3) ceramic blank, water, ethanol and carbon black are mixed according to the mass ratio of 1: 2: 6: 3, mixing, and stirring for 15min at the speed of 500r/min to prepare a ceramic premix; the ceramic premix was placed in a reaction kettle at 85 ℃ under argon protection and subsequently at 6m 3 Introducing titanium tetrachloride of 0.4 time of the ceramic premix into the mixture per minute, continuously stirring the mixture for 3 hours, drying the mixture for 48 hours at 15Pa and 10 ℃, then heating the mixture to 1550 ℃ at 10 ℃/min, keeping the temperature for 4 hours, heating the mixture to 1725 ℃ at 9.5 ℃/min, boosting the temperature to 30MPa at 2MPa/min, and then superposing an oscillation pressure with the frequency of 3Hz and the pressure of 5MPa to keep the oscillation pressure for 4 minutes to prepare the ultrafine grained titanium-based high-plasticity ceramic material.
Example 3
A preparation method of an ultra-fine grain titanium-based high-plasticity ceramic material comprises the following preparation steps:
(1) at the temperature of 26 ℃, mixing metaaluminic acid, deionized water and a nitric acid solution with the mass fraction of 30% according to the mass ratio of 1: 31: 4, mixing, and stirring at 400r/min for 30min to prepare a metaaluminate solution; at 26 ℃, ethyl orthosilicate and ethanol are mixed according to a mass ratio of 1: 5, mixing, stirring for 30min at 1300r/min, then dropwise adding a 7-time metaaluminate solution of ethyl orthosilicate at 80 drops/min, continuously stirring for 4h at 80 ℃, dropwise adding a 20% sodium hydroxide solution at 80 drops/min to adjust the pH to 10, continuously stirring for 4h, adding zirconium oxide particles with the particle size of 12 mu m, the mass of which is 0.07 time that of the ethyl orthosilicate, continuously stirring for 4h, and naturally cooling to room temperature to prepare composite sol; freezing the composite sol in a refrigerator at-2 ℃ for 49h, drying at 20Pa and-40 ℃ for 49h, washing with absolute ethyl alcohol for 4 times, drying in a drying oven at 20Pa and 21 ℃ for 3h, grinding, and sieving with a 1000-mesh sieve to obtain the composite aerogel;
(2) introducing ammonia gas into a 13MPa reaction kettle, heating to 135 ℃ at the speed of 11 ℃/min, and preserving heat for 3h to prepare supercritical ammonia gas; under the protection condition of argon, mixing the composite aerogel, carbon black, nickel and yttrium oxide according to the mass ratio of 1: 5: 0.08: 0.5 mixing, putting into a 0.9MPa reaction kettle, heating to 710 deg.C at 6 deg.C/min, and heating to 6m 3 Introducing supercritical ammonia gas 8 times the mass of the composite aerogel, stirring at 600r/min for 3h, heating to 1500 deg.C at 11 deg.C/min, maintaining for 3h, heating to 1750 deg.C at 10 deg.C/min, boosting to 31MPa at 3MPa/min, adding an oscillation pressure with frequency of 4Hz and 6MPa, maintaining the oscillation pressure for 5min, naturally cooling to room temperature at 6m 3 Introducing supercritical ammonia for 20min, washing with anhydrous ethanol for 5 times, and oven drying at 40 deg.C for 3 hr to obtain ceramic blank;
(3) ceramic blank, water, ethanol and carbon black are mixed according to the mass ratio of 1: 3: 7: 4, mixing, and stirring at 600r/min for 20min to prepare a ceramic premix; the ceramic premix was placed in a reaction kettle at 90 ℃ under argon protection and subsequently at 7m 3 Introducing titanium tetrachloride of 0.5 time of the ceramic premix into the mixture/min, continuously stirring the mixture for 4h, drying the mixture for 50h at 20Pa and 12 ℃, heating the mixture to 1600 ℃ at the speed of 11 ℃/min, preserving the heat for 5h, heating the mixture to 1750 ℃ at the speed of 10 ℃/min, boosting the mixture to 31MPa at the speed of 3MPa/min, and then superposing an oscillating pressure of 4Hz and 6MPa to keep the oscillating pressure for 5min to prepare the ultrafine-crystal titanium-based high-plasticity ceramic material.
Comparative example 1
Comparative example 1 differs from example 2 only in the steps (1), (2), step (1) being modified: at 25 ℃, deionized water and a nitric acid solution with the mass fraction of 30% are mixed according to the mass ratio of 30: 3, mixing, stirring at 350r/min for 25min to prepare a mixed solution; at the temperature of 25 ℃, ethyl orthosilicate and ethanol are mixed according to the mass ratio of 1: 4, stirring for 25min at 1250r/min, then dropwise adding mixed solution 6 times of tetraethoxysilane at 70 drops/min, continuously stirring for 3h at 70 ℃, adding zirconia particles with the particle size of 11 mu m, the mass of which is 0.06 time of that of the tetraethoxysilane, continuously stirring for 3.5h, and naturally cooling to room temperature to prepare composite sol; and (3) putting the composite sol into a refrigerator with the temperature of-3 ℃ for freezing for 48h, then drying for 48h at the temperature of 15Pa and-45 ℃, washing for 3 times by using absolute ethyl alcohol, putting into an oven with the temperature of 15Pa and 20 ℃ for drying for 2h, grinding, and sieving by using a 900-mesh sieve to prepare the composite aerogel. Modifying the step (2) as follows: introducing ammonia gas into a reaction kettle with the pressure of 12.5MPa, heating to 134 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to prepare supercritical ammonia gas; under the protection of argon, the composite aerogel is mixed,Carbon black, nickel and yttrium oxide in a mass ratio of 1: 4: 0.075: 0.4 is mixed and put into a reaction kettle with 0.8MPa, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, and the temperature is raised to 5.5m 3 Introducing supercritical ammonia gas with the mass 7.5 times of that of the composite aerogel per hour, stirring at 500r/min for 2 hours, heating to 1400 ℃ at 10 ℃/min, preserving heat for 2 hours, heating to 1725 ℃ at 9 ℃/min, boosting to 30MPa at 2MPa/min, then superposing an oscillation pressure with the frequency of 3Hz and 5MPa, keeping the oscillation pressure for 4 minutes, naturally cooling to normal temperature, and cooling at 5.5m 3 Introducing supercritical ammonia gas for 15min, washing with anhydrous ethanol for 4 times, and drying in a 35 ℃ oven for 2h to obtain the ceramic blank. The rest of the preparation steps are the same as example 2.
Comparative example 2
Comparative example 2 differs from example 2 only in step (1), step (1) being modified: at the temperature of 25 ℃, mixing metaaluminic acid, deionized water and a nitric acid solution with the mass fraction of 30% according to the mass ratio of 1: 30: 3, mixing, and stirring at 350r/min for 25min to prepare a metaaluminate solution; at the temperature of 25 ℃, ethyl orthosilicate and ethanol are mixed according to the mass ratio of 1: 4, stirring at 1250r/min for 25min, then dropwise adding a meta-aluminum acid solution 6 times of ethyl orthosilicate at 70 drops/min, continuously stirring at 70 ℃ for 3h, dropwise adding a sodium hydroxide solution with the mass fraction of 20% at 70 drops/min to adjust the pH value to 9, continuously stirring for 3h, and naturally cooling to room temperature to prepare a composite sol; and (3) putting the composite sol into a refrigerator with the temperature of-3 ℃ for freezing for 48h, then drying for 48h at the temperature of 15Pa and-45 ℃, washing for 3 times by using absolute ethyl alcohol, putting into an oven with the temperature of 15Pa and 20 ℃ for drying for 2h, grinding, and sieving by using a 900-mesh sieve to prepare the composite aerogel. The rest of the preparation steps are the same as example 2.
Comparative example 3
Comparative example 3 differs from example 2 only in step (2), step (2) being modified: under the protection condition of argon, mixing the composite aerogel, the carbon black, the nickel and the yttrium oxide according to the mass ratio of 1: 4: 0.075: 0.4, adding the mixture into a 0.8MPa reaction kettle, heating to 700 ℃ at a speed of 5 ℃/min, stirring for 2h at a speed of 500r/min, heating to 1400 ℃ at a speed of 10 ℃/min, preserving heat for 2h, heating to 1725 ℃ at a speed of 9 ℃/min, boosting to 30MPa at a speed of 2MPa/min, then superposing an oscillating pressure with a frequency of 3Hz and 5MPa, keeping the oscillating pressure for 4min, adding zirconium oxide particles with a particle size of 11 mu m and a mass of 0.06 time of the ethyl orthosilicate, continuously stirring for 3.5h, naturally cooling to normal temperature, washing for 4 times by using absolute ethyl alcohol, and drying in a 35 ℃ oven for 2h to prepare the ceramic blank. The rest of the preparation steps are the same as example 2.
Comparative example 4
Comparative example 4 differs from example 2 only in step (3), step (3) being modified: ceramic blank, water, ethanol and carbon black are mixed according to the mass ratio of 1: 2: 6: 3, mixing, and stirring for 15min at the speed of 500r/min to prepare a ceramic premix; putting the ceramic premix into a reaction kettle under the conditions of 85 ℃ and argon protection, heating to 1550 ℃ at a speed of 10 ℃/min, preserving heat for 4h, then heating to 1725 ℃ at a speed of 9.5 ℃/min, boosting to 30MPa at a speed of 2MPa/min, and then superposing an oscillation pressure with a frequency of 3Hz and 5MPa to keep the oscillation pressure for 4min to prepare the ultrafine-grained titanium-based high-plasticity ceramic material. The rest of the preparation steps are the same as example 2.
Comparative example 5
Silicon nitride with the particle size of 15 microns, alumina with the particle size of 15 microns, water, ethanol and carbon black are mixed according to the mass ratio of 1: 0.3: 2: 6: 3, mixing, and stirring for 15min at the speed of 500r/min to prepare a ceramic premix; the ceramic premix was placed in a reaction kettle at 85 ℃ under argon protection and subsequently at 6m 3 Introducing titanium tetrachloride of 0.4 time of the ceramic premix into the mixture per minute, continuously stirring the mixture for 3 hours, drying the mixture for 48 hours at 15Pa and 10 ℃, then heating the mixture to 1550 ℃ at 10 ℃/min, keeping the temperature for 4 hours, heating the mixture to 1725 ℃ at 9.5 ℃/min, boosting the temperature to 30MPa at 2MPa/min, and then superposing an oscillation pressure with the frequency of 3Hz and the pressure of 5MPa to keep the oscillation pressure for 4 minutes to prepare the ultrafine grained titanium-based high-plasticity ceramic material.
Examples of effects
Table 1 below shows the results of analyzing the wear resistance, bending strength, compressive strength, and fracture toughness of the ultra-fine grained titanium-based high-plastic ceramic materials prepared in examples 1 to 3 of the present invention and comparative examples 1 to 5.
TABLE 1
Figure BDA0003603020460000081
Figure BDA0003603020460000091
From table 1, it can be seen that the ultra-fine grained titanium-based high-plasticity ceramic material prepared in examples 1, 2 and 3 has high bending strength and compressive strength, and good wear resistance and fracture toughness; compared with the experimental data of examples 1, 2 and 3 and comparative example 1, the ceramic blank prepared by using the meta-aluminate solution contains alumina grains, the dispersibility of the alumina grains is good, and the prepared ultra-fine grained titanium-based high-plasticity ceramic material has strong compressive strength and bending strength; from the experimental data of examples 1, 2, 3 and comparative example 3, it can be found that the ceramic blank prepared by using the zirconia particles has fine grains, and the compressive strength of the prepared ultra-fine grained titanium-based high-plasticity ceramic material is high; from the experimental data of the examples 1, 2 and 3 and the comparative example 3, it can be found that the ceramic blank prepared by using supercritical ammonia gas-assisted oscillation pressure sintering has high porosity, titanium tetrachloride can be adsorbed when the titanium tetrachloride is subsequently used for secondary oscillation pressure sintering, a titanium dioxide cross-linked network is generated, and the titanium dioxide is carbonized and reduced to form ultrafine-grained titanium carbide, so that the prepared ultrafine-grained titanium-based high-plasticity ceramic material has high wear resistance and fracture toughness; from the experimental data of examples 1, 2, 3 and comparative example 4, it can be found that the ultrafine grained titanium-based high-plasticity ceramic material prepared by using titanium tetrachloride generates a titanium dioxide cross-linked network, and titanium dioxide is carbonized and reduced to form ultrafine grained titanium carbide, so that the prepared ultrafine grained titanium-based high-plasticity ceramic material has strong wear resistance and fracture toughness; from the experimental data of examples 1, 2, 3 and comparative example 5, it can be seen that the bending strength and compressive strength of the ultra-fine grained titanium-based high-plastic ceramic material prepared by directly adding silicon nitride and alumina are weak.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The preparation method of the ultrafine-grained titanium-based high-plasticity ceramic material is characterized in that the ultrafine-grained titanium-based high-plasticity ceramic material is prepared by carrying out secondary oscillation pressure sintering on a ceramic premix by using titanium tetrachloride; the ceramic premix is obtained by mixing ceramic blank, water, ethanol and carbon black; the ceramic blank is prepared by mixing tetraethoxysilane and a meta-aluminate solution to wrap zirconia particles and sintering by using supercritical ammonia gas to assist oscillation pressure.
2. The method for preparing the ultra-fine grained titanium-based high-plasticity ceramic material according to claim 1, wherein the method for preparing the ultra-fine grained titanium-based high-plasticity ceramic material comprises the following steps: putting the ceramic premix into a reaction kettle at the temperature of 80-90 ℃ under the protection of argon, and then adding the ceramic premix into the reaction kettle at the speed of 5-7 m 3 Introducing titanium tetrachloride which is 0.3-0.5 times of the ceramic premix into the reactor per minute, continuously stirring for 2-4 hours, drying for 46-50 hours at 10-20 Pa and 8-12 ℃, then heating to 1500-1600 ℃ at the speed of 9-11 ℃/min, preserving the heat for 3-5 hours, and then carrying out oscillatory pressure sintering for 3-5 minutes to prepare the ultrafine-grained titanium-based high-plasticity ceramic material.
3. The method for preparing the ultra-fine grained titanium-based high-plasticity ceramic material as claimed in claim 2, wherein the method for preparing the ceramic premix comprises the following steps: ceramic blank, water, ethanol and carbon black are mixed according to the mass ratio of 1: 1: 5: 2-1: 3: 7: 4, mixing, and stirring for 10-20 min at a speed of 400-600 r/min to prepare the ceramic premix.
4. The method for preparing ultra-fine grained titanium-based high-plasticity ceramic material according to claim 3,the preparation method of the ceramic blank is characterized by comprising the following steps: under the protection condition of argon, mixing the composite aerogel, carbon black, nickel and yttrium oxide according to the mass ratio of 1: 3: 0.07: 0.3-1: 5: 0.08: 0.5 percent of the mixture is put into a reaction kettle with 0.7 to 0.9MPa, the temperature is increased to 690 to 710 ℃ at the speed of 4 to 6 ℃/min, and the temperature is increased to 5 to 6m 3 Introducing supercritical ammonia gas 7-8 times the mass of the composite aerogel per hour, stirring for 1-3 hours at 400-600 r/min, heating to 1300-1500 ℃ at 9-11 ℃/min, preserving heat for 1-3 hours, sintering under oscillating pressure for 3-5 minutes, naturally cooling to normal temperature at 5-6 m 3 Introducing supercritical ammonia for 10-20 min, washing with absolute ethyl alcohol for 3-5 times, and putting into an oven at 30-40 ℃ for drying for 1-3 h to prepare the ceramic blank.
5. The method for preparing the ultra-fine grained titanium-based high-plasticity ceramic material as claimed in claim 4, wherein the supercritical ammonia gas is prepared by the following steps: and (3) introducing ammonia gas into a reaction kettle with the pressure of 12-13 MPa, heating to 133-135 ℃ at the speed of 9-11 ℃/min, and preserving heat for 1-3 h to prepare supercritical ammonia gas.
6. The method for preparing the ultra-fine grained titanium-based high-plasticity ceramic material as claimed in claim 4, wherein the method for preparing the composite aerogel comprises the following steps: and (3) freezing the composite sol in a refrigerator at a temperature of-4 to-2 ℃ for 47-49 h, then drying at a temperature of 10-20 Pa and-50 to-40 ℃ for 47-49 h, washing with absolute ethyl alcohol for 2-4 times, and drying in a drying oven at a temperature of 10-20 Pa and 19-21 ℃ for 1-3 h to prepare the composite aerogel.
7. The method for preparing the ultra-fine grained titanium-based high-plasticity ceramic material according to claim 6, wherein the method for preparing the composite sol comprises the following steps: at the temperature of 24-26 ℃, mixing ethyl orthosilicate and ethanol according to a mass ratio of 1: 3-1: 5, stirring for 20-30 min at 1200-1300 r/min, then dropwise adding a meta-aluminate solution of which the weight is 5-7 times that of ethyl orthosilicate at 60-80 ℃ for 2-4 h, dropwise adding a sodium hydroxide solution of which the weight is 20% at 60-80 r/min for adjusting the pH value to 8-10, continuously stirring for 2-4 h, adding zirconium oxide particles of which the weight is 0.05-0.07 time that of ethyl orthosilicate, continuously stirring for 3-4 h, and naturally cooling to room temperature to prepare the composite sol.
8. The method for preparing the ultra-fine grained titanium-based high-plasticity ceramic material as claimed in claim 7, wherein the particle size of the zirconia particles is 10-12 μm.
9. The method for preparing an ultra-fine grained titanium-based high-plasticity ceramic material according to claim 7, wherein the method for preparing the meta-aluminate solution is as follows: at the temperature of 24-26 ℃, mixing metaaluminic acid, deionized water and a nitric acid solution with the mass fraction of 30% according to the mass ratio of 1: 29: 2-1: 31: 4, mixing and stirring at 300-400 r/min for 20-30 min to prepare the metaaluminate solution.
10. The method for preparing ultra-fine grained titanium-based high-plasticity ceramic material according to claim 2 or 4, wherein the oscillating pressure sintering comprises the following specific steps: heating to 1700-1750 ℃ at a speed of 9-10 ℃/min, boosting to 29-31 MPa at a speed of 1-3 MPa/min, and then superposing an oscillating pressure with a frequency of 2-4 Hz and a pressure of 4-6 MPa.
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