CN114874026B - Preparation method of high-strength fiber composite zirconia foam ceramic - Google Patents
Preparation method of high-strength fiber composite zirconia foam ceramic Download PDFInfo
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Abstract
A preparation method of high-strength fiber composite zirconia foam ceramic relates to a preparation method of zirconia foam ceramic. The invention aims to solve the problems that the prior zirconia aerogel has high porosity and is open inside and poor in thermal stability, and the prior zirconia foam ceramic has high strength and high porosity and is difficult to be compatible. 1. Preparing yttria-stabilized zirconia aerogel powder; 2. preparing a suspension; 3. preparing a green body; 4. sintering at high temperature to obtain the high-strength fiber composite zirconia foam ceramic. The zirconia fiber is added in the preparation process, and the finally prepared zirconia foam ceramic has the advantages of low density, high porosity, high compressive strength and high thermal stability. The invention can obtain the high-strength fiber composite zirconia foam ceramic.
Description
Technical Field
The invention relates to a preparation method of zirconia foam ceramic.
Background
Various aerospace aircrafts often work under extreme conditions such as high temperature, high pressure, and the like, and development of novel aviation composite materials with light weight, high strength and excellent thermal stability is an important research content of scientific researchers. The zirconia foam ceramic has the advantages of high strength, low density, stable chemical property, high thermal stability and the like, and is widely applied to the fields of molten metal filters, silencing materials, high-temperature heat insulation materials and the like. The zirconia foam ceramic is prepared by combining a high-temperature sintering process in a foaming method, freeze drying, gel casting and other modes, the prepared zirconia foam ceramic is difficult to control performance depending on the properties of the zirconia powder, the defects of low strength and poor thermal stability are overcome, and the zirconia foam ceramic prepared by the traditional method is difficult to be compatible with high strength and high porosity, so that the practical application of the zirconia foam ceramic is limited.
The zirconia aerogel has the characteristics of high specific surface area, strong adsorption performance, low heat conduction coefficient and the like, and can be applied to the fields of catalyst carriers, gas filtering materials, high-efficiency heat insulation materials and the like. However, zirconia aerogel has two difficulties in practical application, namely, the open internal structure of high porosity of the aerogel leads to quite different mechanical properties from those of the traditional oxide, and the collapse of the framework structure is easy to occur in the use process; secondly, the mutual transformation of the zirconia crystal forms at high temperature can damage the pore structure of the aerogel, which leads to poor thermal stability.
Disclosure of Invention
The invention aims to solve the problems that the prior zirconia aerogel has high porosity and is open in the interior and poor in thermal stability, and the prior zirconia foam ceramic has high strength and high porosity and is difficult to be compatible, and provides a preparation method of the high-strength fiber composite zirconia foam ceramic.
The preparation method of the high-strength fiber composite zirconia foam ceramic is completed according to the following steps:
1. preparing yttria-stabilized zirconia aerogel powder:
(1) firstly, dissolving zirconium oxychloride octahydrate in a mixed solution of absolute ethyl alcohol and deionized water, then adding a stabilizer and a catalyst, stirring, then adding a drying control agent and a dispersing agent, continuously stirring to obtain zirconia sol, and then dropwise adding a gel accelerator to obtain alcogel;
(2) firstly, aging the alcogel in a mould, and then carrying out alcohol-water exchange to obtain wet gel with the redundant moisture and impurity ions removed from the interior;
(3) aging the wet gel with the moisture and impurity ions removed in a mixed solution of absolute ethyl alcohol and ethyl orthosilicate, and soaking the wet gel with the absolute ethyl alcohol to obtain the wet gel with the redundant ethyl orthosilicate removed inside;
(4) drying the wet gel with the redundant ethyl orthosilicate removed inside, and grinding to obtain yttria-stabilized zirconia aerogel powder;
2. preparing a suspension:
uniformly mixing yttria-stabilized zirconia aerogel powder, deionized water and zirconium oxychloride octahydrate to obtain a raw material; adding a binder solution and a foaming agent solution into the raw materials, and stirring to obtain slurry; sequentially adding zirconia fiber and starch into the slurry, and fully stirring to obtain uniformly dispersed zirconia suspension;
3. preparing a green body:
transferring the uniformly dispersed zirconia suspension into a corundum crucible, air-drying at room temperature, and drying in an oven to obtain a green body;
4. high-temperature sintering:
transferring the green body into a muffle furnace, heating to 1200-1400 ℃, preserving heat at 1200-1400 ℃, heating to 1400-1600 ℃, preserving heat at 1400-1600 ℃, and finally cooling to room temperature to obtain the high-strength fiber composite zirconia foam ceramic.
The invention has the beneficial effects that:
1. the preparation method of the fiber composite zirconia foam ceramic provided by the invention is simple, the process is safe and controllable, and the cheap zirconia chloride is adopted as a raw material, so that the fiber composite zirconia foam ceramic is suitable for large-scale production;
2. the invention adopts a great amount of improved methods for preparing the zirconia aerogel powder, so that the zirconia aerogel powder has high thermal stability, and the zirconia aerogel foamed ceramic prepared by taking the zirconia aerogel powder as a raw material has extremely high thermal stability and keeps a stable tetragonal crystal phase after heat treatment at room temperature and 1400 ℃;
3. the zirconia fiber is added in the preparation process, and the finally prepared zirconia foam ceramic has the advantages of low density, high porosity, high compressive strength and high thermal stability.
Drawings
FIG. 1 is a physical diagram of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1;
FIG. 2 is N of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1 2 -an adsorption-desorption curve;
FIG. 3 is a graph showing the pore size distribution of the yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1;
FIG. 4 is a scanning electron microscope image of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1 after heat treatment for 2 hours at (a) 25 ℃, (b) 500 ℃, (c) 700 ℃ and (d) 1100 ℃;
FIG. 5 is a thermogravimetric-differential thermogravimetric curve of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1, wherein 1 is TG and 2 is DTG;
FIG. 6 is an X-ray diffraction pattern of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1 at various temperatures;
FIG. 7 is an X-ray diffraction pattern of the high strength fiber composite zirconia foam ceramic prepared in the fourth step of example 2 at room temperature;
FIG. 8 is an X-ray diffraction pattern of the high strength fiber composite zirconia foam ceramic prepared in the fourth step of example 2 after heat treatment at 1400 ℃;
FIG. 9 is a stress-strain curve of the high strength fiber composite zirconia foam ceramic prepared in step four of example 2;
FIG. 10 is a physical diagram of the high strength fiber composite zirconia foam ceramic prepared in the fourth step of example 2.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
The first embodiment is as follows: the preparation method of the high-strength fiber composite zirconia foam ceramic is completed according to the following steps:
1. preparing yttria-stabilized zirconia aerogel powder:
(1) firstly, dissolving zirconium oxychloride octahydrate in a mixed solution of absolute ethyl alcohol and deionized water, then adding a stabilizer and a catalyst, stirring, then adding a drying control agent and a dispersing agent, continuously stirring to obtain zirconia sol, and then dropwise adding a gel accelerator to obtain alcogel;
(2) firstly, aging the alcogel in a mould, and then carrying out alcohol-water exchange to obtain wet gel with the redundant moisture and impurity ions removed from the interior;
(3) aging the wet gel with the moisture and impurity ions removed in a mixed solution of absolute ethyl alcohol and ethyl orthosilicate, and soaking the wet gel with the absolute ethyl alcohol to obtain the wet gel with the redundant ethyl orthosilicate removed inside;
(4) drying the wet gel with the redundant ethyl orthosilicate removed inside, and grinding to obtain yttria-stabilized zirconia aerogel powder;
2. preparing a suspension:
uniformly mixing yttria-stabilized zirconia aerogel powder, deionized water and zirconium oxychloride octahydrate to obtain a raw material; adding a binder solution and a foaming agent solution into the raw materials, and stirring to obtain slurry; sequentially adding zirconia fiber and starch into the slurry, and fully stirring to obtain uniformly dispersed zirconia suspension;
3. preparing a green body:
transferring the uniformly dispersed zirconia suspension into a corundum crucible, air-drying at room temperature, and drying in an oven to obtain a green body;
4. high-temperature sintering:
transferring the green body into a muffle furnace, heating to 1200-1400 ℃, preserving heat at 1200-1400 ℃, heating to 1400-1600 ℃, preserving heat at 1400-1600 ℃, and finally cooling to room temperature to obtain the high-strength fiber composite zirconia foam ceramic.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the stabilizer in the step one (1) is yttrium nitrate; the catalyst is 65wt% nitric acid; the drying control agent is formamide; the dispersing agent is polyethylene glycol; the gel accelerator is propylene oxide. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the mole ratio of the stabilizer to the zirconium oxychloride octahydrate in the step one (1) is (5-12) 100; the molar ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water in the step one (1) is 1 (0.5-1); the volume ratio of the amount of the zirconium oxychloride octahydrate material in the step one (1) to the mixed solution of the absolute ethyl alcohol and the deionized water is (0.04 mol-0.06 mol) (25 mL-30 mL). The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the molar ratio of the drying control agent to the zirconium oxychloride octahydrate in the step one (1) is 1 (0.6-1); the mol ratio of the catalyst to the zirconium oxychloride octahydrate in the step one (1) is (0.06-1) (0.04-0.06); the mole ratio of the dispersant to the zirconium oxychloride octahydrate in the step one (1) is (0.004-0.006): 0.04-0.06. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the mol ratio of the gel accelerator to the zirconium oxychloride in the step one (1) is (0.1-0.2) (0.04-0.06); stirring in the first step (1) for 15-25 min, and continuing stirring for 2-3 h; the aging treatment time in the step one (2) is 3-4 hours, and the aging treatment temperature is 45-70 ℃; in the first step (2), the gel after aging treatment is soaked in absolute ethyl alcohol for 3-4 times within 24 hours, and the soaking time is 360-480 min. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the volume fraction of the absolute ethyl alcohol in the mixed solution of the absolute ethyl alcohol and the tetraethoxysilane in the step one (3) is 20% -40%; the aging time in the step one (3) is 2 to 5 days; soaking the aged wet gel in the absolute ethyl alcohol for 3 to 4 times within 24 hours, wherein the soaking time is 360 to 480 minutes; the drying time in the step one (4) is 24-36 h, and the drying temperature is 45-60 ℃; the particle size of the yttria-stabilized zirconia aerogel powder in the step one (4) is 10 nm-30 nm. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: in the second step, the mass fraction of yttria-stabilized zirconia aerogel powder in the raw materials is 35-45%, the mass fraction of deionized water is 55-65%, and the mass fraction of zirconium oxychloride octahydrate is 1-2%; the binder solution in the second step is a polyvinyl alcohol solution with the mass fraction of 2.5% -3.5%; the foaming agent solution is a hydrogen peroxide solution with the mass fraction of 35% -40%. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the mass ratio of the yttria-stabilized zirconia aerogel powder to the binder in the second step is 1 (0.002-0.003); the mass ratio of the yttria-stabilized zirconia aerogel powder to the foaming agent in the second step is 1 (0.15-0.2); and step two, the crystal form of the zirconia fiber is a stable tetragonal crystal form. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the mass ratio of the yttria-stabilized zirconia aerogel powder to the zirconia fiber in the second step is 1 (0.2-0.4); the mass ratio of the yttria-stabilized zirconia aerogel powder to the starch in the second step is 1 (0.04-0.06); the stirring speed in the second step is 80-100 r/min, and the stirring time is 20-40 min; the speed of the full stirring in the second step is 80 r/min-100 r/min, and the time of the full stirring is 5 h-9 h. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the air drying time in the third step is 3-5 days; the temperature rising rate in the fourth step is 3 ℃/min-5 ℃/min; in the fourth step, the heat preservation time is 1 h-2 h at 1200-1400 ℃; the heat preservation time is 2-3 h at 1400-1600 ℃. The other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the high-strength fiber composite zirconia foam ceramic is completed according to the following steps:
1. preparing yttria-stabilized zirconia aerogel powder:
(1) firstly, dissolving zirconium oxychloride octahydrate in a mixed solution of absolute ethyl alcohol and deionized water, then adding a stabilizer and a catalyst, stirring, then adding a drying control agent and a dispersing agent, continuously stirring to obtain zirconia sol, and then dropwise adding a gel accelerator to obtain alcogel;
the stabilizer in the step one (1) is yttrium nitrate; the catalyst is 65wt% nitric acid; the drying control agent is formamide; the dispersing agent is polyethylene glycol; the gel accelerator is propylene oxide;
the mole ratio of the stabilizer to the zirconium oxychloride octahydrate in the step one (1) is 8:100;
the molar ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water in the step one (1) is 1:0.75;
the volume ratio of the amount of the material of the zirconium oxychloride octahydrate to the mixed solution of the absolute ethyl alcohol and the deionized water in the step one (1) is 0.05mol:30mL;
the molar ratio of the drying control agent to the zirconium oxychloride octahydrate in the step one (1) is 1:0.65;
the molar ratio of the catalyst to the zirconium oxychloride octahydrate in the step one (1) is 1:0.625;
the mole ratio of the dispersant to the zirconium oxychloride octahydrate in the step one (1) is 1:10;
the molar ratio of the gel accelerator to the zirconium oxychloride in the step one (1) is 1:0.35;
stirring in the first step (1) for 20min, and continuing stirring for 3h;
(2) firstly, aging the alcogel in a mould, and then carrying out alcohol-water exchange to obtain wet gel with the redundant moisture and impurity ions removed from the interior;
the aging treatment time in the step one (2) is 3-4 hours, and the aging treatment temperature is 60 ℃;
in the first step (2), the gel after aging treatment is soaked in absolute ethyl alcohol for 3 times within 24 hours, and the soaking time is 480 minutes each time;
(3) aging the wet gel with the moisture and impurity ions removed in a mixed solution of absolute ethyl alcohol and ethyl orthosilicate, and soaking the wet gel with the absolute ethyl alcohol to obtain the wet gel with the redundant ethyl orthosilicate removed inside;
the volume fraction of the absolute ethyl alcohol in the mixed solution of the absolute ethyl alcohol and the tetraethoxysilane in the step one (3) is 25vol%;
the aging time in the step one (3) is 5 days;
the step one (3) of soaking by using absolute ethyl alcohol is to soak the aged wet gel in the absolute ethyl alcohol for 3 times within 24 hours, wherein the soaking time is 480 minutes each time;
(4) drying the wet gel with the redundant ethyl orthosilicate removed inside, and grinding to obtain yttria-stabilized zirconia aerogel powder;
the drying time in the step one (4) is 24 hours, and the drying temperature is 60 ℃;
the particle size of the yttria-stabilized zirconia aerogel powder in the step one (4) is 10-30nm.
FIG. 1 is a physical diagram of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1;
as can be seen from FIG. 1, the yttria-stabilized zirconia aerogel prepared in the step one (4) of example 1 is a macroscopically white powdery sample with uniform particle distribution.
FIG. 2 is step one (4) of example 1N of the prepared yttria-stabilized zirconia aerogel powder 2 -an adsorption-desorption curve;
as can be seen from FIG. 2, the curve is a typical class IV isothermal curve, and the zirconia aerogel powder has a mesoporous structure with a specific surface area of about 276m 2 /g。
FIG. 3 is a graph showing the pore size distribution of the yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1;
as can be seen from FIG. 3, the pore volume of the yttria-stabilized zirconia aerogel powder was about 0.73cm 3 And/g, pore size distribution is between 10 and 20 nm.
FIG. 4 is a scanning electron microscope image of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1 after heat treatment for 2 hours at (a) 25 ℃, (b) 500 ℃, (c) 700 ℃ and (d) 1100 ℃;
as can be seen from fig. 4: the particle sizes of the yttrium oxide stabilized zirconia aerogel subjected to heat treatment at different temperatures are uniform, the three-dimensional network structure is obvious, and the yttrium oxide stabilized zirconia aerogel still maintains a relatively complete porous network structure along with the increase of the heat treatment temperature, so that the yttrium oxide stabilized zirconia aerogel synthesized by the method has relatively high heat stability.
FIG. 5 is a thermogravimetric-differential thermogravimetric plot of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1, wherein 1 is TG and 2 is DTG;
three weight loss stages are shown in FIG. 5, the first stage being about 8.0% thermal weight loss below 120℃, caused by volatilization of the solvent remaining in the aerogel powder; the second stage is about 6.0% of thermal weight loss at 120-200deg.C, which is caused by volatilization of residual water or crystal water in aerogel powder; the third stage is about 20.5% thermal weight loss at 200-600deg.C, which is caused by decomposition of residual organic substances in the aerogel powder; the bulk thermal weight loss was about 34.5%, and the aerogel powder remained stable in weight after 600 ℃, indicating that sintering temperatures above 600 ℃ removed various impurities from the yttria-stabilized zirconia aerogel powder.
FIG. 6 is an X-ray diffraction pattern of yttria-stabilized zirconia aerogel powder prepared in step one (4) of example 1 at various temperatures,
as can be seen from fig. 6: the sample remained amorphous after heat treatment at 700 c, and tetragonal diffraction peaks began to appear when the heat treatment temperature reached 1000 c, and slightly increased when the heat treatment temperature reached 1100 c. In addition, no monoclinic phase diffraction peak appears in the whole heat treatment temperature range, which indicates that the zirconia aerogel powder synthesized under the condition can be well stabilized in tetragonal phase, and the material has extremely high heat stability.
Example 2: the preparation method of the high-strength fiber composite zirconia foam ceramic comprises the following steps:
1. preparing a suspension:
uniformly mixing 8.0g of the yttria-stabilized zirconia aerogel powder prepared in example 1, 12g of deionized water and 0.32g of zirconium oxychloride octahydrate to obtain a raw material; adding 0.8g of polyvinyl alcohol solution with mass fraction of 2.5% and 4.0g of hydrogen peroxide solution with mass fraction of 35% into the raw materials, and stirring for 20min at stirring speed of 100r/min to obtain slurry; sequentially adding 2.4g of tetragonal zirconia fiber and 0.4g of starch into the slurry, and stirring for 7 hours at the stirring speed of 100r/min to obtain uniformly dispersed zirconia suspension;
2. preparing a green body:
transferring the uniformly dispersed zirconia suspension into a corundum crucible, sealing with filter paper, naturally air-drying at room temperature for 48h, and drying in an oven at 60 ℃ for 24h to obtain a green body;
3. high-temperature sintering:
transferring the green body into a muffle furnace, heating to 1200 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h at 1200 ℃, heating to 1400 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h at 1400 ℃, cooling to room temperature, taking out a sample, and polishing to a regular shape to obtain the high-strength fiber composite zirconia foam ceramic.
The high-strength fiber composite zirconia foam ceramic prepared in example 2 had a compressive strength of 17.0MPa and a permanent linear shrinkage under heating of 0.53%, and its density was measured by the Archimedes drainage methodDegree of 1.10cm 3 And/g, a porosity of about 81.6%, and X-ray diffraction analysis was conducted to obtain a stable tetragonal phase.
FIG. 7 is an X-ray diffraction pattern of the high strength fiber composite zirconia foam ceramic prepared in the fourth step of example 2 at room temperature;
as can be seen from fig. 7: the high strength fiber composite zirconia foam ceramic prepared in the step four of example 2 is a stable tetragonal phase.
FIG. 8 is an X-ray diffraction pattern of the high strength fiber composite zirconia foam ceramic prepared in the fourth step of example 2 after heat treatment at 1400 ℃;
as can be seen from fig. 8: example 2 step four the high strength fiber composite zirconia foam ceramic prepared at 1400
A stable tetragonal phase after heat treatment at a temperature of about DEG C; both fig. 4 and 5 show diffraction peaks of tetragonal phase silica because tetraethyl orthosilicate hydrolyzes to form silica covering the zirconia surface during wet gel aging, and the silica layer crystallizes after high temperature heat treatment, further stabilizing the crystalline form of the zirconia foam at high temperature.
FIG. 9 is a stress-strain curve of the high strength fiber composite zirconia foam ceramic prepared in step four of example 2;
as is clear from FIG. 9, the high-strength fiber composite zirconia foam ceramic prepared in the fourth step of example 2 was subjected to a pressure of about 17.0MPa at a peak value when the strain was about 1.6%, and thereafter the material was broken due to overload, and the pressure was drastically decreased.
FIG. 10 is a physical diagram of the high strength fiber composite zirconia foam ceramic prepared in the fourth step of example 2.
From fig. 10, it can be seen that the high-strength fiber composite zirconia foam ceramic prepared in the step four of example 2 has a macroscopic morphology of a porous foam ceramic material.
Example 3: the preparation method of the high-strength fiber composite zirconia foam ceramic comprises the following steps:
1. preparing a suspension:
uniformly mixing 8.0g of the yttria-stabilized zirconia aerogel powder prepared in example 1, 12g of deionized water and 0.32g of zirconium oxychloride octahydrate to obtain a raw material; adding 0.8g of polyvinyl alcohol solution with mass fraction of 2.5% and 4.0g of hydrogen peroxide solution with mass fraction of 35% into the raw materials, and stirring for 20min at stirring speed of 100r/min to obtain slurry; sequentially adding 2.8g of tetragonal zirconia fiber and 0.4g of starch into the slurry, and stirring for 7 hours at the stirring speed of 100r/min to obtain uniformly dispersed zirconia suspension;
2. preparing a green body:
transferring the uniformly dispersed zirconia suspension into a corundum crucible, sealing with filter paper, naturally air-drying at room temperature for 48h, and drying in an oven at 60 ℃ for 24h to obtain a green body;
3. high-temperature sintering:
transferring the green body into a muffle furnace, heating to 1200 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h at 1200 ℃, heating to 1400 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h at 1400 ℃, cooling to room temperature, taking out a sample, and polishing to a regular shape to obtain the high-strength fiber composite zirconia foam ceramic.
The high-strength fiber composite zirconia foam ceramic prepared in example 3 had a compressive strength of 15.3MPa, a permanent linear shrinkage under heating of 0.33%, and a density of 1.71cm as measured by the Archimedes drainage method 3 And/g, a porosity of about 71.5%, and X-ray diffraction analysis was conducted to obtain a stable tetragonal phase.
Example 4: the preparation method of the high-strength fiber composite zirconia foam ceramic comprises the following steps:
1. preparing a suspension:
uniformly mixing 8.0g of the yttria-stabilized zirconia aerogel powder prepared in example 1, 12g of deionized water and 0.32g of zirconium oxychloride octahydrate to obtain a raw material; adding 0.8g of polyvinyl alcohol solution with mass fraction of 2.5% and 4.0g of hydrogen peroxide solution with mass fraction of 35% into the raw materials, and stirring for 20min at stirring speed of 100r/min to obtain slurry; sequentially adding 3.2g of tetragonal zirconia fiber and 0.4g of starch into the slurry, and stirring for 7 hours at a stirring speed of 100r/min to obtain uniformly dispersed zirconia suspension;
2. preparing a green body:
transferring the uniformly dispersed zirconia suspension into a corundum crucible, sealing with filter paper, naturally air-drying at room temperature for 48h, and drying in an oven at 60 ℃ for 24h to obtain a green body;
3. high-temperature sintering:
transferring the green body into a muffle furnace, heating to 1200 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h at 1200 ℃, heating to 1400 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h at 1400 ℃, cooling to room temperature, taking out a sample, and polishing to a regular shape to obtain the high-strength fiber composite zirconia foam ceramic.
The high-strength fiber composite zirconia foam ceramic prepared in example 4 had a compressive strength of 6.7MPa, a permanent linear shrinkage under heating of 0.72% and a density of 1.98cm as measured by the Archimedes drainage method 3 And/g, a porosity of about 66.9%, and X-ray diffraction analysis was conducted to obtain a stable tetragonal phase.
Claims (9)
1. The preparation method of the high-strength fiber composite zirconia foam ceramic is characterized by comprising the following steps of:
1. preparing yttria-stabilized zirconia aerogel powder:
(1) firstly, dissolving zirconium oxychloride octahydrate in a mixed solution of absolute ethyl alcohol and deionized water, then adding a stabilizer and a catalyst, stirring, then adding a drying control agent and a dispersing agent, continuously stirring to obtain zirconia sol, and then dropwise adding a gel accelerator to obtain alcogel;
the stabilizer in the step one (1) is yttrium nitrate; the catalyst is 65wt% nitric acid; the drying control agent is formamide; the dispersing agent is polyethylene glycol; the gel accelerator is propylene oxide;
(2) firstly, aging the alcogel in a mould, and then carrying out alcohol-water exchange to obtain wet gel with the redundant moisture and impurity ions removed from the interior;
(3) aging the wet gel with the moisture and impurity ions removed in a mixed solution of absolute ethyl alcohol and ethyl orthosilicate, and soaking the wet gel with the absolute ethyl alcohol to obtain the wet gel with the redundant ethyl orthosilicate removed inside;
(4) drying the wet gel with the redundant ethyl orthosilicate removed inside, and grinding to obtain yttria-stabilized zirconia aerogel powder;
2. preparing a suspension:
uniformly mixing yttria-stabilized zirconia aerogel powder, deionized water and zirconium oxychloride octahydrate to obtain a raw material; adding a binder solution and a foaming agent solution into the raw materials, and stirring to obtain slurry; sequentially adding zirconia fiber and starch into the slurry, and fully stirring to obtain uniformly dispersed zirconia suspension;
the foaming agent solution in the second step is hydrogen peroxide solution with the mass fraction of 35% -40%;
the mass ratio of the yttria-stabilized zirconia aerogel powder to the foaming agent in the second step is 1 (0.15-0.2);
3. preparing a green body:
transferring the uniformly dispersed zirconia suspension into a corundum crucible, air-drying at room temperature, and drying in an oven to obtain a green body;
4. high-temperature sintering:
transferring the green body into a muffle furnace, heating to 1200-1400 ℃, preserving heat at 1200-1400 ℃, heating to 1400-1600 ℃, preserving heat at 1400-1600 ℃, and finally cooling to room temperature to obtain the high-strength fiber composite zirconia foam ceramic.
2. The method for preparing a high-strength fiber composite zirconia foam ceramic according to claim 1, wherein the molar ratio of the stabilizer to the zirconium oxychloride octahydrate in the step one (1) is (5-12): 100; the molar ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water in the step one (1) is 1 (0.5-1); the volume ratio of the amount of the zirconium oxychloride octahydrate material in the step one (1) to the mixed solution of the absolute ethyl alcohol and the deionized water is (0.04 mol-0.06 mol) (25 mL-30 mL).
3. The method for preparing a high-strength fiber composite zirconia foam ceramic according to claim 1, wherein the molar ratio of the drying control agent to the zirconium oxychloride octahydrate in the step one (1) is 1 (0.6-1); the mol ratio of the catalyst to the zirconium oxychloride octahydrate in the step one (1) is (0.06-1) (0.04-0.06); the mole ratio of the dispersant to the zirconium oxychloride octahydrate in the step one (1) is (0.004-0.006): 0.04-0.06.
4. The method for preparing high-strength fiber composite zirconia foam ceramic according to claim 1, wherein the molar ratio of the gel accelerator to the zirconium oxychloride octahydrate in the step one (1) is (0.1-0.2) (0.04-0.06); stirring in the first step (1) for 15-25 min, and continuing stirring for 2-3 h; the aging treatment time in the step one (2) is 3-4 hours, and the aging treatment temperature is 45-70 ℃; in the first step (2), the gel after aging treatment is soaked in absolute ethyl alcohol for 3-4 times within 24 hours, and the soaking time is 360-480 min.
5. The method for preparing high-strength fiber composite zirconia foam ceramic according to claim 1, wherein the volume fraction of absolute ethyl alcohol in the mixed solution of absolute ethyl alcohol and tetraethoxysilane in the step one (3) is 20% -40%; the aging time in the step one (3) is 2 to 5 days; soaking the aged wet gel in the absolute ethyl alcohol for 3 to 4 times within 24 hours, wherein the soaking time is 360 to 480 minutes; the drying time in the step one (4) is 24-36 h, and the drying temperature is 45-60 ℃; the particle size of the yttria-stabilized zirconia aerogel powder in the step one (4) is 10 nm-30 nm.
6. The preparation method of the high-strength fiber composite zirconia foam ceramic according to claim 1, wherein the mass fraction of yttria-stabilized zirconia aerogel powder in the raw materials in the second step is 35-45%, the mass fraction of deionized water is 55-65%, and the mass fraction of zirconium oxychloride octahydrate is 1-2%; the binder solution in the second step is a polyvinyl alcohol solution with the mass fraction of 2.5% -3.5%.
7. The preparation method of the high-strength fiber composite zirconia foam ceramic according to claim 1, wherein the mass ratio of the yttria-stabilized zirconia aerogel powder to the binder in the second step is 1 (0.002-0.003); and step two, the crystal form of the zirconia fiber is a stable tetragonal crystal form.
8. The method for preparing the high-strength fiber composite zirconia foam ceramic according to claim 1, wherein the mass ratio of the yttria-stabilized zirconia aerogel powder to the zirconia fiber in the second step is 1 (0.2-0.4); the mass ratio of the yttria-stabilized zirconia aerogel powder to the starch in the second step is 1 (0.04-0.06); the stirring speed in the second step is 80-100 r/min, and the stirring time is 20-40 min; the speed of the full stirring in the second step is 80 r/min-100 r/min, and the time of the full stirring is 5 h-9 h.
9. The method for preparing the high-strength fiber composite zirconia foam ceramic according to claim 1, which is characterized in that
The air drying time in the third step is 3-5 days; the temperature rising rate in the fourth step is 3 ℃/min-5 ℃/min;
in the fourth step, the heat preservation time is 1 h-2 h at 1200-1400 ℃; the heat preservation time is 2-3 h at 1400-1600 ℃.
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