CN111099909A - High-performance ceramic with surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate and preparation method thereof - Google Patents
High-performance ceramic with surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance ceramic of surface-modified polycrystalline mullite fiber composite rare earth lanthanum zirconate and a preparation method thereof. The surface of the polycrystalline mullite fiber is treated, and then the surface of the polycrystalline mullite fiber is coated with alumina to prepare the polycrystalline mullite fiber coated with the alumina on the surface; preparing a large amount of nanometer level high-activity polycrystalline rare earth lanthanum zirconate powder by using a self-propagating combustion method; the aim of improving the mechanical property is achieved by adding the surface modified polycrystalline mullite fiber into the lanthanum zirconate ceramic powder. The preparation method disclosed by the invention comprises the steps of preparing the surface modified polycrystalline mullite fiber, preparing the polycrystalline rare earth lanthanum zirconate and sintering the ceramic biscuit at high temperature and high pressure. The preparation method has stable and reliable process and simple operation, obviously improves the mechanical strength of the rare earth lanthanum zirconate ceramic, and can effectively reduce the thermal conductivity within a certain doping range, so that the rare earth lanthanum zirconate ceramic becomes a high-temperature heat-insulating material with reliable mechanical bearing performance.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a preparation method of a high-performance ceramic with surface modified polycrystalline mullite fiber and rare earth lanthanum zirconate.
Background
The high-temperature heat-insulating material has good thermal stability and low heat conductivity coefficient under the high-temperature condition of higher than 650 ℃ and has certain mechanical strength. The special structure of the material endows the material with the unique heat preservation, heat insulation, sound insulation and fire resistance, so the material is widely applied to the fields of aerospace, national defense and military industry, metallurgy, chemical industry, energy and the like.
The ceramic material has the advantages of high melting point, low thermal conductivity, heat corrosion resistance and the like, and is a preferred material for high-temperature heat insulation. 8 wt% of Y2O3Stabilized ZrO2Ceramics have the excellent properties of high melting point, low thermal conductivity, high thermal expansion coefficient and the like, and are the most commonly used materials at present. However, the upper limit of the working temperature and the higher high-temperature thermal conductivity of the material gradually fail to meet the requirements of practical application. A great deal of research shows that the rare earth zirconate material has wide attention due to special crystal structure and performance, wherein La2Zr2O7The ceramic has high melting point and strong oxidation resistance, has two structures of ordered pyrochlore and disordered fluorite, but is La3+With Zr4+Has a larger radius ratio of La2Zr2O7The energy required for the ordered-disordered phase transformation is large, the phase transformation can not occur before 1600 ℃, the pyrochlore structure is a single pyrochlore structure, and the thermal stability of the structure is very excellent. In addition, the crystal structure of the lanthanum zirconate can effectively enhance phonon scattering, so that the material also has lower thermal conductivity and good heat insulation performance. In terms of mechanics, the lanthanum zirconate ceramic material has high hardnessHigh strength, high elastic modulus, wear resistance and other excellent mechanical performance. Therefore, the lanthanum zirconate is likely to become the best high-temperature heat-insulating material of the new generation.
In order to further improve the performance of the lanthanum zirconate material and enable the lanthanum zirconate material to become a safe and reliable high-temperature heat-insulating material with long service life, besides the improvement of a preparation process, the optimization design of a material formula and a structure is also a very important method.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-performance ceramic of surface-modified polycrystalline mullite fiber and composite rare earth lanthanum zirconate and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-performance ceramic of surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate, wherein the chemical formula of the rare earth lanthanum zirconate is La2Zr2O7The ceramic material is doped with surface-modified polycrystalline mullite fibers with the mass percentage of 2-17%, the compression strength of the ceramic material is 400-650 MPa, and the room-temperature thermal conductivity is 1.70-2.35W/(m.K).
A preparation method of the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate comprises the following steps:
1) heating and stirring the polycrystalline mullite fiber in hydrochloric acid, cleaning and modifying the surface of the polycrystalline mullite fiber, taking out the polycrystalline mullite fiber, washing and drying to obtain a surface-modified polycrystalline mullite fiber;
2) taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyethylene oxide as a surfactant, fully stirring and mixing surface-modified polycrystalline mullite fiber with polyethylene oxide and ethanol, then gradually dropwise adding deionized water, slowly adding crystalline aluminum chloride to fully dissolve the crystalline aluminum chloride, finally adding 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing and aging the gel; removing the aging liquid, washing with ethanol, and drying; putting the dried aged gel into a muffle furnace for heat treatment to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina;
3) mixing a mixture of 1:1, putting lanthanum acetate and zirconyl nitrate as precursor raw materials into a ball milling device; then, fully ball-milling by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue fully ball-milling; evaporating the solvent after the ball milling is finished to obtain loose and porous xerogel; placing the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, carrying out self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain a nano-sized polycrystalline rare earth lanthanum zirconate powder raw material;
4) putting the surface modified polycrystalline mullite fiber and the polycrystalline rare earth lanthanum zirconate powder raw materials into a ball milling device, and carrying out dry ball milling for 2 hours, wherein the mass percent of the surface modified polycrystalline mullite fiber is 2-17%; then adding alcohol into the mixed powder raw materials subjected to ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is raised to 1500 ℃ of the maximum sintering temperature, and the pressure is raised to 200MPa of the maximum pressure; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate.
Preferably, in the step 1), the polycrystalline mullite fiber with the diameter of 6-8 μm and the length of 60-90 μm is put into 0.6mol/L hydrochloric acid and is heated and stirred for 2 hours at 50 ℃; then filtering, washing the filtered fiber with distilled water for 3 times, and then putting the fiber into a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface.
Preferably, in the step 1), the mixing mass ratio of the polycrystalline mullite fiber and 0.6mol/L hydrochloric acid is 1: 20.
preferably, in the step 2), the mass ratio of the added crystalline aluminum chloride, ethanol, deionized water, 1, 2-propylene oxide and polyethylene oxide in the process of preparing the gel is 1:1.5:1.5:2: 0.03; the mass ratio of the mullite fiber to the crystalline aluminum chloride is 1: 5.
Preferably, in the step 2), the aging time of the gel is 10 hours, the aging solution is removed after aging, the aged gel is washed 3 times with ethanol, and then is put into a vacuum drying oven at 80 ℃ for drying treatment for 1 hour, the dried aged gel is put into a muffle furnace and is subjected to heat treatment at 300 ℃ for 2 hours, and the modified polycrystalline mullite fiber with the surface coated with alumina is prepared.
Preferably, in the step 3), the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1.
Preferably, in the step 3), the ball milling time of lanthanum acetate and zirconyl nitrate is 2 hours, and the ball milling time after adding alanine and polyethylene glycol is 1 hour; after the ball milling is finished, the solvent is evaporated in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel.
Preferably, in the step 4), alcohol is added to the mixed powder raw material at a mass ratio of 5% during granulation.
Preferably, in the step 4), the temperature rise rate is 10 ℃/min during the process of raising the temperature to the maximum sintering temperature.
The preparation method of the invention takes the design of the high-temperature heat-insulating ceramic with stable and reliable process, simple operation, and good mechanical property and thermal property as a research target, firstly, the surface of the polycrystalline mullite fiber is treated, and then the surface of the polycrystalline mullite fiber is coated with alumina to prepare the polycrystalline mullite fiber coated with the alumina; preparing a large amount of nanometer level high-activity polycrystalline rare earth lanthanum zirconate powder by using a self-propagating combustion method; the high-performance ceramic material of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate is prepared by high-temperature hot-pressing sintering. The material has the compression strength of 400-650 MPa and the room-temperature thermal conductivity of 1.70-2.35W/(m.K), and is an excellent high-temperature heat-insulating material.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following will clearly and completely describe the technical solutions of the present invention 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 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.
Example 1
(1) Polycrystalline mullite fiber with the diameter of 6-8 mu m and the length of 60-90 mu m is put into hydrochloric acid (0.6mol/L) and is heated and stirred for 2 hours at the temperature of 50 ℃; then filtering, washing with distilled water for 3 times, and then placing in a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface, wherein the mass ratio of the polycrystalline mullite fiber to hydrochloric acid (0.6mol/L) is 1: 20.
(2) putting the polycrystalline mullite fiber with a clean surface into a beaker, taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyoxyethylene as a surfactant, and measuring the crystalline aluminum chloride, the ethanol, the deionized water, the 1, 2-propylene oxide and the polyoxyethylene according to a mass ratio of 1:1.5:1.5:2: 0.03. Under the condition of a constant-temperature water bath at 25 ℃, adding weighed polyoxyethylene and ethanol into a beaker, fully stirring and mixing for 1 hour, then gradually dropwise adding weighed deionized water, slowly adding weighed crystalline aluminum chloride (the mass ratio of mullite fiber to crystalline aluminum chloride is 1:5) to fully dissolve the crystalline aluminum chloride, finally adding weighed 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing for 10 hours to age the gel; removing the aging solution, washing the aged gel with ethanol for 3 times, and drying in a vacuum drying oven at 80 deg.C for 1 hr; and (3) putting the dried aged gel into a muffle furnace, and carrying out heat treatment for 2 hours at the temperature of 300 ℃ to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina.
(3) Preparing a rare earth lanthanum zirconate powder raw material: lanthanum acetate and zirconyl nitrate are used as precursor raw materials, and the molar ratio is 1:1 weighing corresponding powder, and then putting the powder into a ball milling device; then, fully ball-milling for 2 hours by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue ball-milling for 1 hour; wherein the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1. Then evaporating the solvent in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel; and putting the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, performing self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain the nano-sized high-activity polycrystalline rare earth lanthanum zirconate powder raw material.
(4) The method comprises the following steps of (1) mixing surface-modified polycrystalline mullite fiber and polycrystalline rare earth lanthanum zirconate powder according to a mass ratio of 2: 98, then putting the mixture into a ball milling device for dry ball milling for 2 hours (the mass percentage of the surface modified polycrystalline mullite fiber is 2%), and then adding 5% alcohol by mass into the mixed powder raw materials after ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is increased to the maximum sintering temperature of 1500 ℃ at the heating rate of 10 ℃/min, and the pressure is increased to the maximum pressure of 200 MPa; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate. The material has the compression strength of 430MPa and the room-temperature thermal conductivity of 2.15W/(m.K), and is an excellent high-temperature heat-insulating material.
Example 2
(1) Polycrystalline mullite fiber with the diameter of 6-8 mu m and the length of 60-90 mu m is put into hydrochloric acid (0.6mol/L) and is heated and stirred for 2 hours at the temperature of 50 ℃; then filtering, washing with distilled water for 3 times, and then placing in a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface, wherein the mass ratio of the polycrystalline mullite fiber to hydrochloric acid (0.6mol/L) is 1: 20.
(2) putting the polycrystalline mullite fiber with a clean surface into a beaker, taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyoxyethylene as a surfactant, and measuring the crystalline aluminum chloride, the ethanol, the deionized water, the 1, 2-propylene oxide and the polyoxyethylene according to a mass ratio of 1:1.5:1.5:2: 0.03; under the condition of a constant-temperature water bath at 25 ℃, adding weighed polyoxyethylene and ethanol into a beaker, fully stirring and mixing for 1 hour, then gradually dropwise adding weighed deionized water, slowly adding weighed crystalline aluminum chloride (the mass ratio of mullite fiber to crystalline aluminum chloride is 1:5) to fully dissolve the crystalline aluminum chloride, finally adding weighed 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing for 10 hours to age the gel; removing the aging solution, washing the aged gel with ethanol for 3 times, and drying in a vacuum drying oven at 80 deg.C for 1 hr; and (3) putting the dried aged gel into a muffle furnace, and carrying out heat treatment for 2 hours at the temperature of 300 ℃ to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina.
(3) Preparing a rare earth lanthanum zirconate powder raw material: lanthanum acetate and zirconyl nitrate are used as precursor raw materials, and the molar ratio is 1:1 weighing corresponding powder, and then putting the powder into a ball milling device; then, fully ball-milling for 2 hours by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue ball-milling for 1 hour; wherein the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1. Then evaporating the solvent in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel; and putting the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, performing self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain the nano-sized high-activity polycrystalline rare earth lanthanum zirconate powder raw material.
(4) The method comprises the following steps of mixing surface-modified polycrystalline mullite fiber and polycrystalline rare earth lanthanum zirconate powder according to the mass ratio of 5: 95, then putting the mixture into a ball milling device for dry ball milling for 2 hours (the mass percentage of the surface modified polycrystalline mullite fiber is 5%), and then adding 5% alcohol by mass into the mixed powder raw materials after ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is increased to the maximum sintering temperature of 1500 ℃ at the heating rate of 10 ℃/min, and the pressure is increased to the maximum pressure of 200 MPa; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate. The material has the compression strength of 480MPa and the room-temperature thermal conductivity of 2.02W/(m.K), and is an excellent high-temperature heat-insulating material.
Example 3
(1) Polycrystalline mullite fiber with the diameter of 6-8 mu m and the length of 60-90 mu m is put into hydrochloric acid (0.6mol/L) and is heated and stirred for 2 hours at the temperature of 50 ℃; then filtering, washing with distilled water for 3 times, and then placing in a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface, wherein the mass ratio of the polycrystalline mullite fiber to hydrochloric acid (0.6mol/L) is 1: 20.
(2) putting the polycrystalline mullite fiber with a clean surface into a beaker, taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyoxyethylene as a surfactant, and measuring the crystalline aluminum chloride, the ethanol, the deionized water, the 1, 2-propylene oxide and the polyoxyethylene according to a mass ratio of 1:1.5:1.5:2: 0.03; under the condition of a constant-temperature water bath at 25 ℃, adding weighed polyoxyethylene and ethanol into a beaker, fully stirring and mixing for 1 hour, then gradually dropwise adding weighed deionized water, slowly adding weighed crystalline aluminum chloride (the mass ratio of mullite fiber to crystalline aluminum chloride is 1:5) to fully dissolve the crystalline aluminum chloride, finally adding weighed 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing for 10 hours to age the gel; removing the aging liquid, washing the aged gel with ethanol for 3 times, and drying in a vacuum drying oven at 80 deg.C for 1 hr; and (3) putting the dried gel into a muffle furnace, and carrying out heat treatment for 2 hours at the temperature of 300 ℃ to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina.
(3) Preparing a rare earth lanthanum zirconate powder raw material: lanthanum acetate and zirconyl nitrate are used as precursor raw materials, and the molar ratio is 1:1 weighing corresponding powder, and then putting the powder into a ball milling device; then, fully ball-milling for 2 hours by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue ball-milling for 1 hour; wherein the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1. Then evaporating the solvent in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel; and putting the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, performing self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain the nano-sized high-activity polycrystalline rare earth lanthanum zirconate powder raw material.
(4) The surface modified polycrystalline mullite fiber and the rare earth lanthanum zirconate powder are mixed according to the mass ratio of 8: 92, then putting the mixture into a ball milling device for dry ball milling for 2 hours (the mass percentage of the surface modified polycrystalline mullite fiber is 2%), and then adding 5% alcohol by mass into the mixed powder raw materials after ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is increased to the maximum sintering temperature of 1500 ℃ at the heating rate of 10 ℃/min, and the pressure is increased to the maximum pressure of 200 MPa; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate. The material has the compression strength of 550MPa and the room-temperature thermal conductivity of 1.81W/(m.K), and is an excellent high-temperature heat-insulating material.
Example 4
(1) Polycrystalline mullite fiber with the diameter of 6-8 mu m and the length of 60-90 mu m is put into hydrochloric acid (0.6mol/L) and is heated and stirred for 2 hours at the temperature of 50 ℃; then filtering, washing with distilled water for 3 times, and then placing in a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface, wherein the mass ratio of the polycrystalline mullite fiber to hydrochloric acid (0.6mol/L) is 1: 20.
(2) putting the polycrystalline mullite fiber with a clean surface into a beaker, taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyoxyethylene as a surfactant, and measuring the crystalline aluminum chloride, the ethanol, the deionized water, the 1, 2-propylene oxide and the polyoxyethylene according to a mass ratio of 1:1.5:1.5:2: 0.03; under the condition of a constant-temperature water bath at 25 ℃, adding weighed polyoxyethylene and ethanol into a beaker, fully stirring and mixing for 1 hour, then gradually dropwise adding weighed deionized water, slowly adding weighed crystalline aluminum chloride (the mass ratio of mullite fiber to crystalline aluminum chloride is 1:5) to fully dissolve the crystalline aluminum chloride, finally adding weighed 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing for 10 hours to age the gel; removing the aging solution, washing the aged gel with ethanol for 3 times, and drying in a vacuum drying oven at 80 deg.C for 1 hr; and (3) putting the dried aged gel into a muffle furnace, and carrying out heat treatment for 2 hours at the temperature of 300 ℃ to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina.
(3) Preparing a rare earth lanthanum zirconate powder raw material: lanthanum acetate and zirconyl nitrate are used as precursor raw materials, and the molar ratio is 1:1 weighing corresponding powder, and then putting the powder into a ball milling device; then, fully ball-milling for 2 hours by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue ball-milling for 1 hour; wherein the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1. Then evaporating the solvent in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel; and putting the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, performing self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain the nano-sized high-activity polycrystalline rare earth lanthanum zirconate powder raw material.
(4) The surface modified polycrystalline mullite fiber and the rare earth lanthanum zirconate powder are mixed according to the mass ratio of 11: 89, then putting the mixture into a ball milling device for dry ball milling for 2 hours (the mass percentage of the surface modified polycrystalline mullite fiber is 11%), and then adding 5% alcohol by mass into the mixed powder raw materials after ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is increased to the maximum sintering temperature of 1500 ℃ at the heating rate of 10 ℃/min, and the pressure is increased to the maximum pressure of 200 MPa; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate. The material has the compression strength of 650MPa and the room-temperature thermal conductivity of 1.70W/(m.K), and is an excellent high-temperature heat-insulating material.
Example 5
(1) Polycrystalline mullite fiber with the diameter of 6-8 mu m and the length of 60-90 mu m is put into hydrochloric acid (0.6mol/L) and is heated and stirred for 2 hours at the temperature of 50 ℃; then filtering, washing with distilled water for 3 times, and then placing in a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface, wherein the mass ratio of the polycrystalline mullite fiber to hydrochloric acid (0.6mol/L) is 1: 20.
(2) putting the polycrystalline mullite fiber with a clean surface into a beaker, taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyoxyethylene as a surfactant, and measuring the crystalline aluminum chloride, the ethanol, the deionized water, the 1, 2-propylene oxide and the polyoxyethylene according to a mass ratio of 1:1.5:1.5:2: 0.03; under the condition of a constant-temperature water bath at 25 ℃, adding weighed polyoxyethylene and ethanol into a beaker, fully stirring and mixing for 1 hour, then gradually dropwise adding weighed deionized water, slowly adding weighed crystalline aluminum chloride (the mass ratio of mullite fiber to crystalline aluminum chloride is 1:5) to fully dissolve the crystalline aluminum chloride, finally adding weighed 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing for 10 hours to age the gel; removing the aging solution, washing the aged gel with ethanol for 3 times, and drying in a vacuum drying oven at 80 deg.C for 1 hr; and (3) putting the dried aged gel into a muffle furnace, and carrying out heat treatment for 2 hours at the temperature of 300 ℃ to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina.
(3) Preparing a rare earth lanthanum zirconate powder raw material: lanthanum acetate and zirconyl nitrate are used as precursor raw materials, and the molar ratio is 1:1 weighing corresponding powder, and then putting the powder into a ball milling device; then, fully ball-milling for 2 hours by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue ball-milling for 1 hour; wherein the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1. Then evaporating the solvent in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel; and putting the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, performing self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain the nano-sized high-activity polycrystalline rare earth lanthanum zirconate powder raw material.
(4) The surface modified polycrystalline mullite fiber and the rare earth lanthanum zirconate powder are mixed according to the mass ratio of 14: 86, then putting the mixture into a ball milling device for dry ball milling for 2 hours (the mass percentage of the surface modified polycrystalline mullite fiber is 14%), and then adding 5% alcohol by mass into the mixed powder raw materials after ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is increased to the maximum sintering temperature of 1500 ℃ at the heating rate of 10 ℃/min, and the pressure is increased to the maximum pressure of 200 MPa; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate. The material has the compression strength of 530MPa and the room-temperature thermal conductivity of 1.97W/(m.K), and is an excellent high-temperature heat-insulating material.
Example 6
(1) Polycrystalline mullite fiber with the diameter of 6-8 mu m and the length of 60-90 mu m is put into hydrochloric acid (0.6mol/L) and is heated and stirred for 2 hours at the temperature of 50 ℃; then filtering, washing with distilled water for 3 times, and then placing in a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface, wherein the mass ratio of the polycrystalline mullite fiber to hydrochloric acid (0.6mol/L) is 1: 20.
(2) putting the polycrystalline mullite fiber with a clean surface into a beaker, taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyoxyethylene as a surfactant, and measuring the crystalline aluminum chloride, the ethanol, the deionized water, the 1, 2-propylene oxide and the polyoxyethylene according to a mass ratio of 1:1.5:1.5:2: 0.03; under the condition of a constant-temperature water bath at 25 ℃, adding weighed polyoxyethylene and ethanol into a beaker, fully stirring and mixing for 1 hour, then gradually dropwise adding weighed deionized water, slowly adding weighed crystalline aluminum chloride (the mass ratio of mullite fiber to crystalline aluminum chloride is 1:5) to fully dissolve the crystalline aluminum chloride, finally adding weighed 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing for 10 hours to age the gel; removing the aging solution, washing the aged gel with ethanol for 3 times, and drying in a vacuum drying oven at 80 deg.C for 1 hr; and (3) putting the dried aged gel into a muffle furnace, and carrying out heat treatment for 2 hours at the temperature of 300 ℃ to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina.
(3) Preparing a rare earth lanthanum zirconate powder raw material: lanthanum acetate and zirconyl nitrate are used as precursor raw materials, and the molar ratio is 1:1 weighing corresponding powder, and then putting the powder into a ball milling device; then, fully ball-milling for 2 hours by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue ball-milling for 1 hour; wherein the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1. Then evaporating the solvent in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel; and putting the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, performing self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain the nano-sized high-activity polycrystalline rare earth lanthanum zirconate powder raw material.
(4) Mixing the surface modified polycrystalline mullite fiber and the rare earth lanthanum zirconate powder according to the mass ratio of 17: 83, then putting the mixture into a ball milling device for dry ball milling for 2 hours (the mass percentage of the surface modified polycrystalline mullite fiber is 17%), and then adding 5% alcohol by mass into the mixed powder raw materials after ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is increased to the maximum sintering temperature of 1500 ℃ at the heating rate of 10 ℃/min, and the pressure is increased to the maximum pressure of 200 MPa; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate. The material has the compression strength of 400MPa and the room-temperature thermal conductivity of 2.35W/(m.K), and is an excellent high-temperature heat-insulating material.
Comparative example
(1) Preparing a rare earth lanthanum zirconate powder raw material: lanthanum acetate and zirconyl nitrate are used as precursor raw materials, and the molar ratio is 1:1 weighing corresponding powder, and then putting the powder into a ball milling device; then, fully ball-milling for 2 hours by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue ball-milling for 1 hour; wherein the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1. Then evaporating the solvent in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel; and putting the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, performing self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain the nano-sized high-activity polycrystalline rare earth lanthanum zirconate powder raw material.
(2) Adding 5% by mass of alcohol into a rare earth lanthanum zirconate powder raw material for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is increased to the maximum sintering temperature of 1500 ℃ at the heating rate of 10 ℃/min, and the pressure is increased to the maximum pressure of 200 MPa; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the rare earth lanthanum zirconate ceramic of the undoped surface modified polycrystalline mullite fiber. The material has the compression strength of 380MPa and the room-temperature thermal conductivity of 2.45W/(m.K).
The following table shows the properties of the ceramics prepared in the above examples 1 to 6 and comparative examples.
TABLE 1 Properties of surface-modified polycrystalline mullite fiber composite rare earth lanthanum zirconate ceramics with different contents
| Mullite fiber content (%) | Compressive Strength (MPa) | Thermal conductivity at room temperature (W/(m.K)) | |
| Example 1 | 2 | 430 | 2.15 |
| Example 2 | 5 | 480 | 2.02 |
| Example 3 | 8 | 550 | 1.81 |
| Example 4 | 11 | 650 | 1.70 |
| Example 5 | 14 | 530 | 1.97 |
| Example 6 | 17 | 400 | 2.35 |
| Comparative example | 0 | 380 | 2.45 |
The results show that the addition of the surface-modified polycrystalline mullite fiber to the ceramic of the present invention can greatly improve the overall compressive strength and room temperature thermal conductivity relative to the ceramic without the addition of the fiber. Therefore, the surface-modified polycrystalline mullite fiber composite rare earth lanthanum zirconate ceramic is selected, one side of the ceramic can be based on a liquid phase sintering principle, and the alumina coated on the surface of the polycrystalline mullite fiber and the polycrystalline rare earth lanthanum zirconate powder have higher reaction activity, so that the densification of the ceramic can be promoted to improve the strength of the material; on the other hand, the surface modified polycrystalline mullite fiber is used as a second phase, so that the purpose of reinforcing the second phase is realized. The preparation method has stable and reliable process and simple operation, obviously improves the mechanical strength of the rare earth lanthanum zirconate ceramic, and can effectively reduce the thermal conductivity within a certain doping range, so that the rare earth lanthanum zirconate ceramic becomes a high-temperature heat-insulating material with reliable mechanical bearing performance.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (10)
1. Surface-modified polycrystalline mullite fiber composite rare earth zirconiumThe high-performance lanthanum zirconate ceramic is characterized in that the chemical formula of rare earth lanthanum zirconate is La2Zr2O7The ceramic material is doped with surface-modified polycrystalline mullite fibers with the mass percentage of 2-17%, the compression strength of the ceramic material is 400-650 MPa, and the room-temperature thermal conductivity is 1.70-2.35W/(m.K).
2. A method for preparing the surface-modified polycrystalline mullite fiber composite rare earth lanthanum zirconate high-performance ceramic as claimed in claim 1, which comprises the following steps:
1) heating and stirring the polycrystalline mullite fiber in hydrochloric acid, cleaning and modifying the surface of the polycrystalline mullite fiber, taking out the polycrystalline mullite fiber, washing and drying to obtain a surface-modified polycrystalline mullite fiber;
2) taking crystalline aluminum chloride as an aluminum source, ethanol and deionized water as solvents, 1, 2-propylene oxide as a gel accelerator and polyethylene oxide as a surfactant, fully stirring and mixing surface-modified polycrystalline mullite fiber with polyethylene oxide and ethanol, then gradually dropwise adding deionized water, slowly adding crystalline aluminum chloride to fully dissolve the crystalline aluminum chloride, finally adding 1, 2-propylene oxide, stopping stirring to form gel, and placing the gel into an isopropanol solution for standing and aging the gel; removing the aging liquid, washing with ethanol, and drying; putting the dried aged gel into a muffle furnace for heat treatment to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina;
3) mixing a mixture of 1:1, putting lanthanum acetate and zirconyl nitrate as precursor raw materials into a ball milling device; then, fully ball-milling by taking alcohol as a medium, and then adding alanine and polyethylene glycol (PEG1200) to continue fully ball-milling; evaporating the solvent after the ball milling is finished to obtain loose and porous xerogel; placing the loose and porous xerogel into a muffle furnace, igniting the xerogel in the air atmosphere, carrying out self-propagating combustion to obtain gray powder, and then heating the gray powder to 900 ℃ for heat preservation for 2 hours to obtain a nano-sized polycrystalline rare earth lanthanum zirconate powder raw material;
4) putting the surface modified polycrystalline mullite fiber and the polycrystalline rare earth lanthanum zirconate powder raw materials into a ball milling device, and carrying out dry ball milling for 2 hours, wherein the mass percent of the surface modified polycrystalline mullite fiber is 2-17%; then adding alcohol into the mixed powder raw materials subjected to ball milling for granulation to obtain granulated powder; prefabricating the granulated powder into a biscuit, putting the biscuit into a graphite sintering mold, and applying initial pressure to the biscuit through a pressure head at normal temperature to prevent material leakage during heating, wherein the initial pressure is 30 MPa; heating and boosting under the condition of keeping the pressure unchanged, wherein the temperature is raised to 1500 ℃ of the maximum sintering temperature, and the pressure is raised to 200MPa of the maximum pressure; and (3) preserving heat and pressure for 20min at the highest sintering temperature and the highest pressure, unloading the pressure to 0MPa at the speed of 10MPa/min, continuously preserving heat for 10min at the highest sintering temperature, and cooling to the normal temperature at the speed of 8 ℃/min after heat preservation is finished, thus preparing the high-performance ceramic of the surface modified polycrystalline mullite fiber composite rare earth lanthanum zirconate.
3. The method for preparing high performance ceramic according to claim 2, wherein in the step 1), the polycrystalline mullite fiber with the diameter of 6-8 μm and the length of 60-90 μm is put into 0.6mol/L hydrochloric acid and is heated and stirred for 2 hours at 50 ℃; then filtering, washing the filtered fiber with distilled water for 3 times, and then putting the fiber into a vacuum drying oven at 80 ℃ for drying treatment for 2 hours to prepare the polycrystalline mullite fiber with clean surface.
4. The method for preparing the high-performance ceramic according to claim 3, wherein in the step 1), the mixing mass ratio of the polycrystalline mullite fiber and the 0.6mol/L hydrochloric acid is 1: 20.
5. the method for preparing high-performance ceramic according to claim 2, wherein in the step 2), crystalline aluminum chloride, ethanol, deionized water, 1, 2-propylene oxide and polyethylene oxide are added in the process of preparing the gel at a mass ratio of 1:1.5:1.5:2: 0.03; the mass ratio of the mullite fiber to the crystalline aluminum chloride is 1: 5.
6. The method for preparing high-performance ceramic according to claim 2, wherein in the step 2), the aging time of the gel is 10 hours, the aging liquid is removed after aging, the aged gel is washed 3 times with ethanol, and then is put into a vacuum drying oven at 80 ℃ for drying treatment for 1 hour, and the dried aged gel is put into a muffle furnace and is subjected to heat treatment at 300 ℃ for 2 hours to obtain the modified polycrystalline mullite fiber with the surface coated with the alumina.
7. The method for preparing high-performance ceramic according to claim 2, wherein in the step 3), the ratio of the total mass of the added alanine and polyethylene glycol to the total mass of the added lanthanum acetate and zirconyl nitrate is 10: 1, and the mass ratio of the alanine to the polyethylene glycol is 5:1.
8. The method for preparing high-performance ceramic according to claim 2, wherein in the step 3), the ball milling time of lanthanum acetate and zirconyl nitrate is 2 hours, and the ball milling time after adding alanine and polyethylene glycol is 1 hour; after the ball milling is finished, the solvent is evaporated in a vacuum drying oven at 80 ℃ for 3 hours to obtain loose and porous xerogel.
9. The method of manufacturing a high-performance ceramic according to claim 2, wherein in the step 4), 5% by mass of alcohol is added to the mixed powder raw material during granulation.
10. The method for preparing high-performance ceramic according to claim 2, wherein the temperature rise rate in the step 4) is 10 ℃/min during the temperature rise to the maximum sintering temperature.
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