CN113968725A - Al-Zr complex phase oxide continuous ceramic fiber and preparation method thereof - Google Patents

Al-Zr complex phase oxide continuous ceramic fiber and preparation method thereof Download PDF

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CN113968725A
CN113968725A CN202010709621.2A CN202010709621A CN113968725A CN 113968725 A CN113968725 A CN 113968725A CN 202010709621 A CN202010709621 A CN 202010709621A CN 113968725 A CN113968725 A CN 113968725A
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fiber
temperature
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CN113968725B (en
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赵彤
李敬毓
王倩
盖珂
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Institute of Chemistry CAS
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Abstract

The invention discloses an Al-Zr complex phase oxide continuous ceramic fiber and a preparation method thereof. The softening point of the Al-Zr copolymerized oxide ceramic precursor is between 80 and 180 ℃; the continuous ceramic fiber is added with a crystal form stabilizer, Al2O3:ZrO2The mass fraction ratio of the crystal form stabilizer is 50-95: 4-47: 1-3; the technical key point of the invention is that the Al-Zr copolymer oxide ceramic precursor has certain molecular weight, and the composition proportion and the softening point are adjustable; ZrO (ZrO)2Is added to increase Al2O3The room temperature strength and high temperature creep resistance of the fibers; adding crystal form stabilizer to stabilize ZrO2Crystal transformation during cooling. The fiberThe average diameter of the composite material is 5-30 mu m, the tensile strength is not less than 2.0GPa, the tensile elastic modulus is not less than 200GPa, and the strength retention rate after heat treatment for 0.5h at 1400 ℃ is not less than 70%.

Description

Al-Zr complex phase oxide continuous ceramic fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of composite fiber materials, and relates to an Al-Zr complex phase oxide continuous ceramic fiber and a preparation method thereof.
Background
The alumina ceramic fiber has high strength and high strengthThe high-temperature-resistant composite material has the outstanding advantages of high modulus, high surface activity, low thermal conductivity, good insulating property, high-temperature oxidation resistance and the like, is an engineering material with excellent comprehensive performance, and plays an important role in reinforcing high-temperature heat-insulating materials, catalysts and ceramic matrix composite materials. With the technical development in the fields of industry and aerospace in recent years, the practical application requirements have higher requirements on the high-temperature performance of the alumina fiber, and the research focus at home and abroad is also changed from a process production route to the addition of various oxides and heteroatoms. The zirconia has the characteristics of wear resistance, thermal shock resistance, high refractive index, small hot melting and the like, the melting point is 2715 ℃, the zirconia is an excellent high-temperature-resistant heat-insulating material, and the strength and the high-temperature creep resistance of the zirconia can be greatly improved by adding the zirconia into alumina fibers. Zirconia has three crystal forms: monoclinic phase at low temperature, tetragonal phase above 1170 ℃ and cubic phase above 2370 ℃. In the production process of zirconia fiber, along with the process of cooling to room temperature after heat treatment, zirconia can be converted from tetragonal phase to monoclinic phase, along with 5% volume expansion, the appearance of the fiber is seriously damaged, and the mechanical property is further reduced, so that a proper amount of crystal form stabilizer (MgO, CaO, CeO) needs to be added2、Y2O3Etc.), inhibit crystal form transformation during temperature reduction.
Du Pont company prepares alumina-zirconia complex phase oxide ceramic fiber with trade mark PRD-166 by slurry method, and alpha-Al with grain size less than 500nm2O3The powder is used as main raw material, alkali aluminium chloride is used as binder, and is made into slurry together with zirconium salt, and then the slurry is undergone the processes of dry spinning, fibre-forming, low-temp. cracking and high-temp. firing in the air, so that the strength of the obtained fibre can be up to 2.1 GPa. However, the fiber diameter is about 20 μm due to the preparation method, and the flexibility is poor (Ceram. Eng. Sci. Proc.1987(8): 755-.
The alumina-zirconia complex phase oxide ceramic fiber with the trade name of Nextel 650 is prepared by a 3M company by adopting a sol-gel method, crystalline aluminum chloride, acetic acid, aluminum powder and deionized water are used as main raw materials, zirconium salt and a small amount of yttrium oxide are added, after mixing reaction, sol aqueous solution is formed by concentration, and the oxide ceramic fiber is obtained by dry spinning, drying and segmented heat treatment. The diameter of the fiber is about 11 μm, but the preparation method is sensitive to the ambient temperature, and toxic substances are generated in the production process, thereby having serious influence on equipment and environment (Central. Eng. Sci. Proc.21(4): 363-373).
CN103408292A Shandong university has invented a preparation method of alumina-zirconia multiphase ceramic fiber, the method utilizes aluminum isopropoxide, formic acid, zirconium acetate and additives to prepare a spinnable sol precursor, a centrifugal fiber forming process is adopted to prepare gel fiber, and then the gel fiber is calcined to obtain the alumina-zirconia multiphase ceramic fiber with the diameter of 1-8 μm. The fiber obtained by the preparation route is short fiber, and the fiber protofilament is easy to dissolve and merge in the air.
CN102465357A provides a preparation method of an alumina-zirconia complex phase ceramic fiber, which adopts zirconium carbonate and hydrochloric acid as raw materials, water or a mixture of water and alcohol as a solvent, and prepares uniform and transparent polyhydroxyzirconium chloride sol by refluxing at 80-95 ℃; adding aluminum sol, phase stabilizer, grain growth inhibitor and water-soluble polymer spinning aid into the sol, distilling under reduced pressure to obtain zirconium-aluminum composite spinning solution, centrifugally spinning or blowing spinning to obtain gel fiber, and performing heat treatment to obtain the alumina-zirconia composite ceramic fiber. Although the high molecular auxiliary agent added in the method is beneficial to fiber formation, in the heat treatment process, too much organic matter is decomposed to form larger pores, so that the prepared ceramic fiber has poor compactness.
Disclosure of Invention
The invention aims to provide an Al-Zr complex phase oxide continuous ceramic fiber and a preparation method thereof. The softening point of the Al-Zr copolymerized oxide ceramic precursor is 98-145 ℃, and the composition proportion and the softening point are adjustable; with addition of ZrO2And a third phase crystal form stabilizer, on the one hand, stabilizing ZrO2Crystal transformation during cooling process, and on the other hand, Al is improved2O3The room temperature strength and high temperature creep resistance of the fibers.
The invention provides a method for preparing Al-Zr complex phase oxide continuous ceramic fiber, which comprises the following steps:
1) carrying out melt spinning on the Al-Zr copolymerized oxide ceramic precursor to obtain a fiber precursor;
2) carrying out non-melting treatment on the fiber protofilament to obtain non-melting fiber;
3) and sequentially carrying out inorganic sintering and high-temperature sintering on the infusible fiber to obtain the Al-Zr complex phase oxide continuous ceramic fiber.
The method for preparing the Al-Zr co-polymer oxide ceramic precursor in the step 1) of the method comprises the following steps:
dissolving an aluminum source in an aluminum source solvent (heating to 60-90 ℃ for dissolution), adding a complexing agent, and refluxing for 0.5-1.5 h (specifically 1 h);
dripping any one of the mixed solutions a-c for refluxing for 0.5-2h (specifically 1 h);
then adding a zirconium source stabilized by a metal stabilizer containing an acetylacetone ligand to perform reduced pressure distillation;
continuously heating to 160-200 ℃ (specifically 170 ℃ and 190 ℃), preserving heat for 1-5h (specifically 2h and 3h), and cooling to room temperature to obtain the Al-Zr co-polymer oxide ceramic precursor;
the mixed solution a consists of water and ethylene glycol monomethyl ether;
the mixed solution b consists of water and ethylene glycol monoethyl ether;
the mixed solution c consists of water and n-propanol.
Specifically, the aluminum source is selected from at least one of aluminum isopropoxide, aluminum n-propoxide and aluminum ethoxide;
the aluminum source solvent is selected from at least one of n-propanol, methanol and isopropanol;
the complexing agent is selected from at least one of acetylacetone, monoethanolamine, diethanolamine and diacetyl;
the crystal form stabilizer is selected from MgO, CaO and CeO2And Y2O3At least one of;
the zirconium source is selected from at least one of a poly-zirconium-siloxane, zirconium chloride and zirconium nitrate; the polymerization degree of the poly-zirconium siloxane is 3-3000 specifically; specifically 100-;
the dosage of the aluminum source, the zirconium source and the crystal form stabilizer is converted into Al2O3:ZrO2:MgO/CaO/CeO2/Y2O3The mass fraction ratio of (A) is 50-95: 4-47: 1-3; specifically 95:4:1, 80:18:2, 50:47:3, 68:30: 2;
the molar amount of the complexing agent is 0.3-0.9 times of that of the aluminum source; specifically 0.5, 0.6, 0.7 times;
in the mixed solution a, the mass ratio of the water to the ethylene glycol monomethyl ether is 1: 1 to 7; specifically 1:2.5, 1: 4;
in the mixed solution b, the mass ratio of the water to the ethylene glycol ethyl ether is 1: 1-10;
in the mixed solution c, the mass ratio of the water to the n-propanol is 1: 1 to 7; specifically, 1: 2;
the adding mode of the mixed solution a-c is dropwise adding; the dropping speed is 0.5-5 drops/s; specifically 1-2 drops/s or 4 drops/s;
in the step of reduced pressure distillation, the temperature is 115-135 ℃; in particular 130 ℃;
the time is 0.5-6 h; in particular 1-3 h; more specifically 2h, 3.5h or 5.5 h;
in the step 1) of melt spinning, the softening point of the Al-Zr complex phase oxide ceramic precursor is 80-180 ℃; in particular to 120-140 ℃; more specifically, the temperature can be 110 ℃, 126 ℃, 145 ℃, 163 ℃ and 180 ℃;
the temperature of the melt spinning is higher than the softening point of the fiber; specifically, the temperature can be 124 deg.C, 145 deg.C, 170 deg.C, 185 deg.C, 190 deg.C, 200 deg.C, 230 deg.C;
the aperture of the filament outlet hole is 0.1-1 mm; specifically 0.25mm, 0.5mm, 0.7 mm;
the extrusion force of the screw is 5-30 MPa; specifically 15MPa, 20MPa, 25 MPa;
the spinning speed is 1000-8000 r/min; specifically 2000, 3000r/min and 4000 r/min;
the step 2) non-melting treatment comprises the following steps: placing the fiber precursor in a constant temperature and humidity box, firstly heating to 40-55 ℃ (such as 45 ℃ and 50 ℃), preserving heat for 10-50min (such as 20min, 30min and 40min) at 40-60% (such as 50% and 55%) relative humidity, then heating to 70-90 ℃ (such as 75 ℃, 80 ℃ and 85 ℃), preserving heat for 10-50min (such as 20min, 30min and 40min) at 75-95% (such as 80%, 85% and 90%) relative humidity, and cooling to room temperature.
In the step 3) of inorganic treatment, the rate of raising the temperature from room temperature to the inorganic treatment temperature is 0.5-3 ℃/min; specifically 1 ℃/min and 2 ℃/min;
the inorganic temperature is 400-800 ℃; specifically, the temperature can be 500 ℃, 600 ℃ and 700 ℃;
the inorganic time is 30min-4 h; specifically 1h, 1.5h and 2 h;
the inorganic atmosphere is selected from at least one of air, oxygen and water vapor;
the cooling to room temperature is carried out naturally;
in the ceramic step, the speed of raising the temperature from room temperature to the ceramic temperature is 10-30 ℃/min; specifically 15, 20 and 25 ℃/min;
the ceramic temperature is 1100-1500 ℃; specifically 1200 deg.C, 1300 deg.C, 1400 deg.C;
the ceramic time is 30 min-2 h; specifically 50min, 1h and 1.5 h;
the atmosphere for ceramization is air.
In addition, the Al-Zr complex phase oxide continuous ceramic fiber prepared by the method and the application of the Al-Zr complex phase oxide continuous ceramic fiber in preparing materials with at least one of the properties of structural reinforcement and high-temperature heat insulation also belong to the protection scope of the invention.
Specifically, the Al-Zr complex phase oxide continuous ceramic fiber is made of Al2O3、ZrO2And a crystal form stabilizer;
the crystal form stabilizer is specifically selected from MgO, CaO and CeO2And Y2O3At least one of;
the Al is2O3、ZrO2And the weight ratio of the crystal form stabilizer is 50-95: 4-47: 1-3; specifically 95:4:1, 80:18:2, 50:47:3, 68:30: 2;
the tensile strength of the Al-Zr complex phase oxide continuous ceramic fiber is not less than 2.0 Gpa; specifically, the air pressure can be 2.0GPa, 2.1GPa, 2.2GPa or 2.3 GPa;
the tensile elastic modulus of the Al-Zr complex phase oxide continuous ceramic fiber is not less than 200 GPa; specifically, 218GPa, 248GPa, 274GPa, 275GPa, 300GPa, 307GPa or 308 GPa;
the crystalline phase of the Al-Zr complex phase oxide continuous ceramic fiber is selected from alpha-Al2O3Phase, gamma-Al2O3Phase and ZrO2At least two of the phases.
The average diameter of the Al-Zr complex phase oxide continuous ceramic fiber is 5-30 mu m; specifically 8 μm, 12 μm, 18 μm or 24 μm;
the retention rate of the tensile strength of the Al-Zr complex phase oxide continuous ceramic fiber is not lower than 70 percent after the Al-Zr complex phase oxide continuous ceramic fiber is treated for 30min at the temperature of 1400 ℃ in the air.
The invention has the following beneficial effects:
1) the Al-Zr co-polymerized oxide ceramic precursor provided by the invention has adjustable composition, certain softening point and adjustable softening point, and can form fiber without adding a spinning auxiliary agent;
2) the Al-Zr multiphase oxide continuous ceramic fiber provided by the invention is added with a third phase of MgO/CaO/CeO2/Y2O3On the one hand, ZrO is stabilized2Crystal transformation during cooling process, and on the other hand, Al is improved2O3High temperature creep resistance of the fiber;
3) in the preparation method of the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention, the fiber is formed by adopting melt spinning, the equipment is simple, the diameter of a fiber outlet hole, the extrusion pressure and the fiber receiving rate are adjustable, and the large-scale production is convenient.
4) The crystal phase composition of the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention is alpha-Al2O3Phase, gamma-Al2O3Phase and ZrO2Mixing of phases, ZrO2Crystal grain is located in Al2O3The grain growth of the fiber at high temperature is effectively inhibited among the grains, and the high-temperature creep resistance of the fiber is improved.
5) The average diameter of the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention is 5-30 μm, the tensile strength is not less than 2.0GPa, the tensile elastic modulus is not less than 200GPa, and the strength retention rate after heat treatment for 0.5h at 1400 ℃ is not less than 70%.
Drawings
Figure 1 is an XRD pattern of the fiber prepared in example 1 at different temperatures.
FIG. 2 is an SEM image of the fiber of example 1.
Figure 3 is an XRD pattern of the fiber prepared in example 2 at different temperatures.
FIG. 4 is a TG plot of the precursors in example 2.
Fig. 5 is a comprehensive analysis chart of SEC refractive index chromatogram, cumulative molar mass distribution, and differential molar mass distribution of the precursor.
FIG. 6 is an SEM image of the fiber of example 3.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified. The degree of polymerization of the zirconoxanes used in the following examples was 100-150. In the following examples, the tensile modulus of elasticity and the tensile strength were measured in accordance with GJB 1871-94.
Example 1
Firstly, preparing Al-Zr copolymerized oxide ceramic precursor
Dissolving aluminum isopropoxide in n-propanol, heating to 75 ℃ under stirring, adding acetylacetone with 0.3 times of mole fraction of aluminum isopropoxide, and heating and refluxing for 1 h; then dropping the mixture into the mixture with the mass ratio of 1: 4, dripping the mixed solution of water and ethylene glycol monomethyl ether, and refluxing for 1 h; adding calcium-stabilized poly-zirconium siloxane (calcium acetylacetonate and poly-zirconium oxygen alkane precursor propyl zirconate for reflux reaction at 120 deg.C, copolymerizing for 2h, and converting into ZrO2The mass ratio of CaO to CaO is 4: 1); distilling at 115 deg.C under vacuum degree of 450mbar for 2h, and simultaneously replacing n-propanol with ethylene glycol methyl ether; continuously heating to 160 ℃, preserving the temperature for 5 hours, and then cooling to room temperature to prepare an Al-Zr copolymerized oxide ceramic precursor with the softening point of 80 ℃; wherein the dosage of aluminum isopropoxide, the zirconium-oxygen alkane and the acetylacetone calcium is converted into Al2O3:ZrO2CaO in a mass fraction ratio of 95:4: 1;
second, preparing Al-Zr complex phase oxide continuous ceramic fiber
1) Melt spinning: heating the Al-Zr copolymerized oxide ceramic precursor prepared in the step to 110 ℃, carrying out melt spinning at the temperature of 124 ℃ after the precursor is melted into a uniform melt and residual bubbles are removed, wherein the aperture of a filament outlet is 1mm, the extrusion force of a screw is 5MPa, and filament winding is carried out at the speed of 1000r/min to prepare fiber precursor;
2) non-melting: placing the obtained fiber precursor in a constant temperature and humidity box, heating to 50 ℃, preserving heat for 20min at 55% relative humidity, heating to 80 ℃, preserving heat for 40min at 80% relative humidity, and cooling to room temperature to obtain infusible fiber;
3) inorganic treatment: placing the obtained infusible fiber in a high temperature furnace, heating to 400 ℃ at the speed of 1 ℃/min, preserving the temperature for 30min, and naturally cooling to room temperature, wherein the atmosphere in the furnace is air;
4) ceramic preparation: and (3) placing the obtained inorganic fiber in a high-temperature furnace, heating to 1200 ℃ at the speed of 10 ℃/min, preserving the temperature for 30min, and taking air as the atmosphere in the furnace to obtain the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention.
The average diameter of the obtained fiber was 30 μm; the crystal phase composition is amorphous, gamma-Al2O3Phase and ZrO2The fiber has the tensile strength of 2.1GPa and the tensile modulus of 218GPa after being mixed, and the strength retention rate of the fiber is 78 percent after the heat treatment for 0.5h at 1400 ℃ in air. XRD patterns of the fibers prepared at different temperatures are shown in figure 1, and SEM images of the fibers are shown in figure 2.
As can be seen from the graph, ZrO increases with the heat treatment temperature2The crystal form strength of the gamma-Al is more and more obvious2O3The lower the relative strength of the crystal phase (A), the more ZrO is stabilized at 1200 ℃2With gamma-Al2O3The state of complex phase crystallization, calculated as gamma-Al2O3Has a crystal content of 43%, ZrO2The crystal content of (2) was 57%.
Example 2
Firstly, preparing Al-Zr copolymerized oxide ceramic precursor
Dissolving aluminium isopropoxideHeating to 60 ℃ in n-propanol under stirring, adding acetylacetone with 0.5 times of mole fraction of aluminum isopropoxide, and heating and refluxing for 30 min; then, dropping the mixture into the reactor at a dropping rate of 5 drops/second in a mass ratio of 1: 6, dripping the mixed solution of water and n-propanol, and refluxing for 1.5 h; adding yttrium-stabilized poly-zirconium siloxane (yttrium acetylacetonate and propyl zirconate for copolymerization at 120 deg.C under reflux for 2 hr, wherein ZrO2:Y2O3The content of (b) is reduced to a mass ratio of 9: 1); distilling at 130 deg.C under vacuum degree of 450mbar for 2h under reduced pressure, and simultaneously replacing n-propanol with ethylene glycol methyl ether; then, continuously heating to 190 ℃, preserving the heat for 2 hours, and then cooling to room temperature to prepare an Al-Zr copolymerized oxide ceramic precursor with the softening point of 163 ℃; wherein the aluminum isopropoxide, the dosage of the poly-zirconium siloxane and the yttrium element are converted into Al2O3:ZrO2:Y2O3The mass fraction ratio of (A) to (B) is 80:18: 2;
the thermogravimetric curve of the precursor under the flowing air atmosphere of 10ml/min is shown in figure 4, and the ceramic yield of the precursor is about 47 percent, the weight loss of the precursor is quicker before 600 ℃, and the weight loss is not obvious after 600 ℃. Fig. 5 is a comprehensive analysis chart of the SEC refractive index chromatogram, the cumulative molar mass distribution, and the differential molar mass distribution of the precursor, and it can be seen from the chart that the molecular weight of the precursor is about 10000.
Second, preparing Al-Zr complex phase oxide continuous ceramic fiber
1) Melt spinning: heating the Al-Zr copolymerized oxide ceramic precursor prepared in the step to 185 ℃, carrying out melt spinning at the temperature of 200 ℃ after the precursor is melted into a uniform melt and residual bubbles are removed, wherein the hole of a filament outlet is 0.25mm, the extrusion force of a screw is 30MPa, and filament winding is carried out at the speed of 3000r/min to prepare a fiber precursor;
2) non-melting: placing the obtained fiber precursor in a constant temperature and humidity box, heating to 40 ℃, preserving heat for 30min at a relative humidity of 60%, heating to 90 ℃, preserving heat for 10min at a relative humidity of 85%, and cooling to room temperature to obtain infusible fiber;
3) inorganic treatment: placing the obtained infusible fiber in a high-temperature furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving heat for 4h, wherein the atmosphere in the furnace is air;
4) ceramic preparation: and (3) placing the obtained inorganic fiber in a high-temperature furnace, heating to 1400 ℃ at the speed of 20 ℃/min, preserving the temperature for 1h, and taking air as the atmosphere in the furnace to obtain the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention.
The average diameter of the obtained fiber was 12 μm; the crystal phase composition is alpha-Al2O3Phase and ZrO2The fiber has the tensile strength of 2.2GPa and the elastic tensile modulus of 275GPa after being mixed, and the strength retention rate of the fiber is 90 percent after being thermally treated for 0.5h at 1400 ℃ in air. XRD patterns of the fibers prepared at different temperatures are shown in figure 3.
As can be seen, only c-ZrO was present at 1000 ℃2Crystallization of alpha-Al which starts to appear when the temperature is raised to 1200 deg.C2O3The crystalline phase has a sharper peak with the increase of the heat treatment temperature, the crystal form strength is stronger and the crystal grain size is larger.
Example 3
Firstly, preparing Al-Zr copolymerized oxide ceramic precursor
Dissolving aluminum isopropoxide in n-propanol, heating to 90 ℃ under stirring, adding acetylacetone with 0.9 times of mole fraction of aluminum isopropoxide, and heating and refluxing for 50 min; then dropping the mixture into the mixture with the mass ratio of 1: 1, dripping the mixed solution of water and n-propanol, and refluxing for 30 min; adding magnesium-stabilized zirconium oxide (magnesium acetylacetonate and zirconium oxide precursor propyl zirconate at 120 deg.C, reflux reacting, copolymerizing for 2 hr, and converting into ZrO2The mass ratio of MgO to MgO is 15: 1)); distilling at 125 deg.C under reduced pressure for 5.5h, and simultaneously replacing n-propanol with ethylene glycol methyl ether; continuously heating to 180 ℃, preserving the heat for 4 hours, and then cooling to room temperature to prepare an Al-Zr copolymerized oxide ceramic precursor with the softening point of 145 ℃; wherein the aluminum isopropoxide, the zirconium alkyl and the magnesium are converted into Al2O3:ZrO2The mass fraction ratio of MgO is 68:30: 2;
second, preparing Al-Zr complex phase oxide continuous ceramic fiber
1) Melt spinning: heating the Al-Zr copolymerized oxide ceramic precursor prepared in the step to 168 ℃, performing melt spinning at 190 ℃ after the precursor is melted into a uniform melt and residual bubbles are removed, wherein the aperture of a filament outlet is 0.5mm, the extrusion force of a screw is 15MPa, and filament winding is performed at the speed of 4000r/min to prepare a fiber precursor;
2) non-melting: placing the obtained fiber precursor in a constant temperature and humidity box, heating to 45 ℃, preserving heat for 50min at 50% relative humidity, heating to 75 ℃, preserving heat for 30min at 90% relative humidity, and cooling to room temperature to obtain infusible fiber;
3) inorganic treatment: placing the obtained infusible fiber in a high-temperature furnace, heating to 500 ℃ at the speed of 0.5 ℃/min, and keeping the temperature for 2 hours, wherein the atmosphere in the furnace is air;
4) ceramic preparation: and (3) placing the obtained inorganic fiber in a high-temperature furnace, heating to 1500 ℃ at the speed of 25 ℃/min, preserving the temperature for 2 hours, and taking air as the atmosphere in the furnace to obtain the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention.
The average diameter of the obtained fiber was 18 μm; the crystal phase composition is alpha-Al2O3Phase and ZrO2The fiber has tensile strength of 2.0GPa and elastic tensile modulus of 248GPa, and the strength retention rate of 88% after heat treatment at 1400 ℃ in air for 0.5 h. The SEM image of the fiber is shown in figure 5.
Example 4
Firstly, preparing Al-Zr copolymerized oxide ceramic precursor
Dissolving aluminum isopropoxide in n-propanol, heating to 80 ℃ under stirring, adding acetylacetone with 0.7 times of mole fraction of aluminum isopropoxide, and heating and refluxing for 1 h; then, dropping the mixture into the reactor at a dropping rate of 5 drops/s according to a mass ratio of 1: 10, dripping the mixed solution of water and glycol ethyl ether, and refluxing for 2 h; adding yttrium-stabilized poly-zirconium siloxane (yttrium acetylacetonate and poly-zirconium oxygen alkane precursor propyl zirconate for reflux reaction at 120 deg.C, copolymerizing for 2h, and converting into ZrO2And Y2O3In a mass ratio of 10: 1); distilling at 130 deg.C under reduced pressure for 3.5h, and simultaneously inverting n-propanol with ethylene glycol diethyl ether; continuously heating to 200 ℃, preserving the heat for 1h, and then cooling to room temperature to prepare an Al-Zr copolymerized oxide ceramic precursor with the softening point of 180 ℃; wherein the dosage of aluminum isopropoxide, the dosage of zirconium-oxygen alkane and the dosage of yttrium are converted into Al2O3:ZrO2:Y2O3The mass fraction ratio of 89:10: 1;
second, preparing Al-Zr complex phase oxide continuous ceramic fiber
1) Melt spinning: heating the Al-Zr copolymerized oxide ceramic precursor prepared in the step to 200 ℃, carrying out melt spinning at the temperature of 230 ℃ after the precursor is melted into a uniform melt and residual bubbles are removed, wherein the aperture of a filament outlet is 0.1mm, the extrusion force of a screw is 25MPa, and filament winding is carried out at the speed of 8000r/min to prepare a fiber precursor;
2) non-melting: placing the obtained fiber precursor in a constant temperature and humidity box, heating to 40 ℃, preserving heat for 40min at 50% relative humidity, heating to 85 ℃, preserving heat for 20min at 95% relative humidity, and cooling to room temperature to obtain infusible fiber;
3) inorganic treatment: placing the obtained infusible fiber in a high temperature furnace, heating to 700 ℃ at the speed of 0.5 ℃/min, and keeping the temperature for 1.5h, wherein the atmosphere in the furnace is air;
4) ceramic preparation: and (3) placing the obtained inorganic fiber in a high-temperature furnace, heating to 1300 ℃ at the speed of 30 ℃/min, preserving the heat for 50min, and taking air as the atmosphere in the furnace to obtain the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention.
The average diameter of the obtained fiber was 8 μm; the crystal phase composition is alpha-Al2O3Phase, gamma-Al2O3Phase and ZrO2The fiber has the tensile strength of 2.3GPa and the elastic tensile modulus of 308GPa after being mixed, and the strength retention rate of the fiber is 82 percent after being thermally treated for 0.5h at 1400 ℃ in air.
Example 5
Firstly, preparing Al-Zr copolymerized oxide ceramic precursor
Dissolving aluminum isopropoxide in n-propanol, heating to 85 ℃ under stirring, adding acetylacetone with 0.6 times of mole fraction of aluminum isopropoxide, and heating and refluxing for 1.5 h; then dropping the mixture into the reactor at a dropping rate of 4 drops/s according to a mass ratio of 1:2.5, dripping the mixed solution of water and ethylene glycol monomethyl ether, and refluxing for 1 h; adding cerium-stabilized zirconium-oxygen alkane precursor (acetylacetone cerium and zirconium-oxygen alkane precursor zirconium propyl ester are reacted and copolymerized for 2h at 120 ℃ by reflux, and the mixture is converted into ZrO2And Y2O3In a mass ratio of 18: 1)); distilling at 135 deg.C under reduced pressure for 5.5h, and simultaneously replacing n-propanol with ethylene glycol methyl ether; continuously heating to 170 ℃, preserving heat for 3h, and then cooling to room temperature to prepare an Al-Zr copolymerized oxide ceramic precursor with a softening point of 126 ℃; wherein the dosage of aluminum isopropoxide, the dosage of zirconium-oxygen alkane and the dosage of yttrium are converted into Al2O3:ZrO2:CeO2The mass fraction ratio of (A) to (B) is 50:47: 3;
second, preparing Al-Zr complex phase oxide continuous ceramic fiber
1) Melt spinning: heating the Al-Zr copolymerized oxide ceramic precursor prepared in the step to 145 ℃, carrying out melt spinning at the temperature of 170 ℃ after the precursor is melted into a uniform melt and residual bubbles are removed, wherein the aperture of a filament outlet is 0.7mm, the extrusion force of a screw is 20MPa, and filament winding is carried out at the speed of 2000r/min to prepare a fiber precursor;
2) non-melting: placing the obtained fiber precursor in a constant temperature and humidity box, heating to 55 ℃, preserving heat for 10min at 40% relative humidity, heating to 70 ℃, preserving heat for 50min at 75% relative humidity, and cooling to room temperature to obtain infusible fiber;
3) inorganic treatment: placing the obtained infusible fiber in a high-temperature furnace, heating to 800 ℃ at the speed of 2 ℃/min, and keeping the temperature for 1h, wherein the atmosphere in the furnace is air;
4) ceramic preparation: and (3) placing the obtained inorganic fiber in a high-temperature furnace, heating to 1100 ℃ at the speed of 15 ℃/min, preserving the heat for 1.5h, and taking air as the atmosphere in the furnace to obtain the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention.
The average diameter of the obtained fiber was 24 μm; the crystal phase composition is gamma-Al2O3Phase and ZrO2The fiber has the tensile strength of 2.3GPa and the elastic tensile modulus of 300GPa after being mixed, and the strength retention rate of the fiber is 70 percent after being thermally treated for 0.5h at 1400 ℃ in air.
Example 6
Firstly, preparing Al-Zr copolymerized oxide ceramic precursor
The same precursor as in example 3;
second, preparing Al-Zr complex phase oxide continuous ceramic fiber
1) Melt spinning: the same as in example 3;
2) non-melting: the same as in example 3;
3) inorganic treatment: placing the obtained infusible fiber in a high-temperature furnace, heating to 500 ℃ at the speed of 2 ℃/min, and keeping the temperature for 1h, wherein the atmosphere in the furnace is steam;
4) ceramic preparation: the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention can be obtained by the same way as the embodiment 3.
The average diameter of the obtained fiber was 18 μm; the crystal phase composition is alpha-Al2O3Phase and ZrO2The fiber has the tensile strength of 2.2GPa and the elastic tensile modulus of 307GPa, and the strength retention rate of 88 percent after heat treatment for 0.5h at 1400 ℃ in air.
Example 7
Firstly, preparing Al-Zr copolymerized oxide ceramic precursor
The same precursor as in example 2;
second, preparing Al-Zr complex phase oxide continuous ceramic fiber
1) Melt spinning: the same as example 2;
2) non-melting: the same as example 2;
3) inorganic treatment: the same as example 2;
4) ceramic preparation: and (3) placing the obtained inorganic fiber in a high-temperature furnace, heating to 1400 ℃ at the speed of 10 ℃/min, preserving the temperature for 1h, and taking air as the atmosphere in the furnace to obtain the Al-Zr complex phase oxide continuous ceramic fiber provided by the invention.
The average diameter of the obtained fiber was 12 μm; the crystal phase composition is gamma-Al2O3Phase and ZrO2The fiber has the tensile strength of 2.0GPa and the elastic tensile modulus of 274GPa after being mixed, and the strength retention rate of the fiber is 92 percent after being thermally treated at 1400 ℃ for 0.5h in air.

Claims (10)

1. A method for preparing an Al-Zr complex phase oxide continuous ceramic fiber, comprising:
1) carrying out melt spinning on the Al-Zr copolymerized oxide ceramic precursor to obtain a fiber precursor;
2) carrying out non-melting treatment on the fiber protofilament to obtain non-melting fiber;
3) and sequentially carrying out inorganic sintering and high-temperature sintering on the infusible fiber to obtain the Al-Zr complex phase oxide continuous ceramic fiber.
2. The method of claim 1, wherein: the method for preparing the Al-Zr co-polymer oxide ceramic precursor in the step 1) comprises the following steps:
dissolving an aluminum source in an aluminum source solvent, adding a complexing agent, and refluxing for 0.5-1.5 h;
then any one of the mixed liquid a-c is dripped into the mixture to be refluxed for 0.5 to 2 hours;
then adding a zirconium source stabilized by a metal stabilizer containing an acetylacetone ligand to perform reduced pressure distillation;
continuously heating to 160-200 ℃, preserving the heat for 1-5h, and cooling to room temperature to obtain the Al-Zr co-polymer oxide ceramic precursor;
the mixed solution a consists of water and ethylene glycol monomethyl ether;
the mixed solution b consists of water and ethylene glycol monoethyl ether;
the mixed solution c consists of water and n-propanol.
3. The method according to claim 1 or 2, characterized in that: the aluminum source is selected from at least one of aluminum isopropoxide, aluminum n-propoxide and aluminum ethoxide;
the aluminum source solvent is selected from at least one of n-propanol, methanol and isopropanol;
the complexing agent is selected from at least one of acetylacetone, monoethanolamine, diethanolamine and diacetyl;
the crystal form stabilizer is selected from MgO, CaO and CeO2And Y2O3At least one of;
the zirconium source is selected from at least one of a poly-zirconium-siloxane, zirconium chloride and zirconium nitrate; the polymerization degree of the poly-zirconium siloxane is 3-3000 specifically; specifically 100-;
the dosage of the aluminum source, the zirconium source and the crystal form stabilizer is converted into Al2O3:ZrO2:MgO/CaO/CeO2/Y2O3The mass fraction ratio of (A) is 50-95: 4-47: 1-3;
the molar amount of the complexing agent is 0.3-0.9 times of that of the aluminum source;
in the mixed solution a, the mass ratio of the water to the ethylene glycol monomethyl ether is 1: 1 to 7;
in the mixed solution b, the mass ratio of the water to the ethylene glycol ethyl ether is 1: 1-10;
in the mixed solution c, the mass ratio of the water to the n-propanol is 1: 1 to 7;
the adding mode of the mixed solution a-c is dropwise adding; the dropping speed is 0.5-5 drops/s;
in the step of reduced pressure distillation, the temperature is 115-135 ℃;
the time is 0.5-6 h.
4. A method according to any one of claims 1 to 3, wherein: in the step 1) of melt spinning, the softening point of the Al-Zr co-polymer oxide ceramic precursor is 80-180 ℃;
the temperature of the melt spinning is higher than the softening point of the fiber;
the aperture of the filament outlet hole is 0.1-1 mm;
the extrusion force of the screw is 5-30 MPa;
the spinning speed is 1000-8000 r/min.
5. The method according to any one of claims 1 to 4, wherein: the step 2) non-melting treatment comprises the following steps: and (3) placing the fiber precursor in a constant temperature and humidity box, firstly heating to 40-55 ℃, preserving heat for 10-50min at 40-60% relative humidity, then heating to 70-90 ℃, preserving heat for 10-50min at 75-95% relative humidity, and cooling to room temperature.
6. The method according to any one of claims 1 to 5, wherein: in the step 3) of inorganic treatment, the rate of raising the temperature from room temperature to the inorganic treatment temperature is 0.5-3 ℃/min;
the inorganic temperature is 400-800 ℃;
the inorganic time is 30min-4 h;
the inorganic atmosphere is selected from at least one of air, oxygen and water vapor;
the cooling to room temperature is carried out naturally;
in the ceramic step, the speed of raising the temperature from room temperature to the ceramic temperature is 10-30 ℃/min; specifically 25 ℃/min;
the ceramic temperature is 1100-1500 ℃;
the ceramic time is 30 min-2 h; in particular 1 h;
the atmosphere for ceramization is air.
7. An Al-Zr complex phase oxide continuous ceramic fiber obtained by the method of any one of claims 1 to 6.
8. The Al-Zr complex phase oxide continuous ceramic fiber according to claim 7, wherein: the Al-Zr multiphase oxide continuous ceramic fiber is made of Al2O3、ZrO2And a crystal form stabilizer;
the crystal form stabilizer is specifically selected from MgO, CaO and CeO2And Y2O3At least one of;
the Al is2O3、ZrO2And the weight ratio of the crystal form stabilizer is 50-95: 4-47: 1-3;
the tensile strength of the Al-Zr complex phase oxide continuous ceramic fiber is not less than 2.0 Gpa;
the tensile elastic modulus of the Al-Zr complex phase oxide continuous ceramic fiber is not less than 200 GPa;
the crystalline phase of the Al-Zr complex phase oxide continuous ceramic fiber is selected from alpha-Al2O3Phase, gamma-Al2O3Phase and ZrO2At least two of the phases.
9. The Al-Zr complex phase oxide continuous ceramic fiber according to claim 7 or 8, characterized in that: the average diameter of the Al-Zr complex phase oxide continuous ceramic fiber is 5-30 mu m;
the retention rate of the tensile strength of the Al-Zr complex phase oxide continuous ceramic fiber is not lower than 70 percent after the Al-Zr complex phase oxide continuous ceramic fiber is treated for 30min at the temperature of 1400 ℃ in the air.
10. Use of the Al-Zr complex phase oxide continuous ceramic fiber according to any one of claims 7 to 9 for the preparation of a material having at least one of structural reinforcement and high temperature insulation properties.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286406A (en) * 2022-07-25 2022-11-04 中国人民解放军国防科技大学 Fiber-reinforced zirconia ceramic matrix composite and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1584155A (en) * 2004-06-11 2005-02-23 山东大学 Zirconium oxide fabrics prepared from organic polyzirconium fore spinning solution by silk process
KR20070112505A (en) * 2006-05-22 2007-11-27 최봉환 Ceramic fiber product for protecting a high temperature material
CN107266077A (en) * 2016-04-08 2017-10-20 中国科学院化学研究所 A kind of ultra-fine zirconium carbide ceramics fiber and preparation method thereof
CN107986797A (en) * 2017-12-11 2018-05-04 苏州图纳新材料科技有限公司 Solid union ceramic forerunner, composite fibre cotton and preparation method thereof
CN108570725A (en) * 2017-03-08 2018-09-25 中国科学院化学研究所 A kind of melt spinning raw material of aluminium oxide continuous fiber, preparation method and aluminium oxide continuous fiber obtained
CN110592724A (en) * 2019-09-04 2019-12-20 中国科学院化学研究所 Hf-Al-Si complex phase oxide ceramic fiber and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1584155A (en) * 2004-06-11 2005-02-23 山东大学 Zirconium oxide fabrics prepared from organic polyzirconium fore spinning solution by silk process
KR20070112505A (en) * 2006-05-22 2007-11-27 최봉환 Ceramic fiber product for protecting a high temperature material
CN107266077A (en) * 2016-04-08 2017-10-20 中国科学院化学研究所 A kind of ultra-fine zirconium carbide ceramics fiber and preparation method thereof
CN108570725A (en) * 2017-03-08 2018-09-25 中国科学院化学研究所 A kind of melt spinning raw material of aluminium oxide continuous fiber, preparation method and aluminium oxide continuous fiber obtained
CN107986797A (en) * 2017-12-11 2018-05-04 苏州图纳新材料科技有限公司 Solid union ceramic forerunner, composite fibre cotton and preparation method thereof
CN110592724A (en) * 2019-09-04 2019-12-20 中国科学院化学研究所 Hf-Al-Si complex phase oxide ceramic fiber and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
G.B.罗森伯格: "《美国耐火材料》", 30 November 1981 *
陈代荣等: "《连续陶瓷纤维的制备、结构、性能和应用：研究现状及发展方向》", 《现代技术陶瓷》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286406A (en) * 2022-07-25 2022-11-04 中国人民解放军国防科技大学 Fiber-reinforced zirconia ceramic matrix composite and preparation method thereof

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