CN111825448B - Method for preparing straight-through-hole zirconia ceramic with compact hole wall by wet spinning dipping method - Google Patents
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Abstract
The invention provides a method for preparing a straight-through pore zirconia ceramic with a compact pore wall by a wet spinning dipping method, which is characterized by comprising the following steps: 1) preparing a monolithic precursor cell body by adopting a wet spinning method, stirring and dissolving a curing agent and a plasticizer in an organic solvent, adding carbon black ceramic powder to prepare a spinning solution, spraying the spinning solution into a gel tank through a spinning nozzle, and performing solidification forming to obtain the monolithic precursor cell body; 2) coating an interface layer by an immersion method, immersing the fibrous monolith precursor cell body into zirconia slurry, and controlling the thickness of the coating layer by dipping and pulling times to obtain the fibrous monolith precursor with the interface layer; 3) warm-pressing and forming; 4) vacuum degreasing; 5) hot pressing and sintering; 6) high-temperature oxidation to obtain the straight-through hole zirconia ceramics with compact hole walls. The through-hole zirconia ceramic obtained by the invention has the advantages that the hole wall is completely compact, the strength and the toughness are high, the thickness of the hole wall can reach 50 mu m, and the hole diameter can reach micron level.
Description
Technical Field
The invention provides a method for preparing a straight-through pore zirconia ceramic with a compact pore wall by a wet spinning dipping method, belonging to the technical field of preparation of porous ceramics.
Background
The porous ceramic has the characteristics of small volume density, high porosity, large specific surface area, selective permeability to liquid and gas media, energy absorption or damping characteristic and the like, particularly the straight-through porous ceramic has a parallel through honeycomb pore channel structure which is beneficial to the entrance of reactants and the discharge of products, the geometric surface is large, and the flow distribution of fluid in the straight-through porous ceramic is uniform, so that the straight-through porous ceramic is widely applied to various aspects such as gas-liquid filtration, purification and separation and the like. The traditional method for preparing the straight-through porous ceramic is mud extrusion molding, namely dry spinning molding, wherein a green body is aged and pugged in vacuum to enable the green body to have certain plasticity, and the green body is continuously molded through a neck mold with a certain shape under the extrusion action of a screw or a plunger of an extruder. However, the prepared through-hole ceramic has the following defects: first, the aperture is big, and the aperture is generally at the millimeter level, because the pug has plasticity, and the contractility is big, and the aperture undersize is easy to be blockked up. Secondly, the thickness of the hole wall is thinner, the extrusion pressure is higher, and the straight-through hole ceramic with the hole wall smaller than 1mm is difficult to form; thirdly, the hole wall is not compact, most of the raw materials for extrusion molding belong to barren materials, and the raw materials have no plasticity. It must be plasticized prior to extrusion, usually with the addition of a plasticizer or binder. Organic plasticizers such as dextrin, industrial syrup, carboxymethyl cellulose, polyvinyl acetate and polyvinyl alcohol are commonly used in industrial production. The addition of the organic plasticizer forms holes after sintering, reduces the compactness of the hole wall, and further ensures that the bending strength of the through hole ceramic prepared by extrusion molding is lower. Further reducing the aperture size of the through hole ceramic and improving the compactness of the hole wall has important theoretical significance and practical value for popularization and application of the through hole ceramic.
Disclosure of Invention
The invention aims to solve the problems of large aperture and non-compact pore wall of the existing through-hole ceramic, and provides a preparation method of the through-hole zirconia ceramic with compact pore wall. The technical scheme is as follows:
a method for preparing a straight-through pore zirconia ceramic with a compact pore wall by a wet spinning dipping method is characterized by comprising the following steps:
1) preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: firstly stirring and dissolving a curing agent and a plasticizer in an organic solvent, then adding carbon black ceramic powder, strongly stirring to prepare a spinning solution, then transferring the spinning solution to a stainless steel storage tank, vacuum degassing for 1-5 h, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.2-0.5 MPa, wherein the water temperature of the gel tank is 0-10 ℃, solidifying and forming, and then soaking for 8-24 h to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 200-2000 mu m, when weighing, the carbon black ceramic powder is weighed, then the curing agent is weighed according to the weight percentage, the plasticizer is 1-4%, the organic solvent is 100-200%, the curing agent is polyether sulfone, the plasticizer is dioctyl phthalate, the organic solvent is a mixture of N-methyl pyrrolidone and acetone, the mass ratio of the N-methyl pyrrolidone to the acetone is (4-9): 1, the carbon black ceramic powder consists of carbon black powder or charcoal powder;
2) coating an interface layer by a dipping method: firstly adding a binder into absolute ethyl alcohol, uniformly stirring, then adding zirconia ceramic powder, stirring for 4-12 hours to form zirconia slurry, coating by adopting a dipping method, dipping a fibrous monolithic precursor cell body into the zirconia slurry, and controlling the thickness of the coating by dipping and pulling times, wherein the binder is polyethylene glycol, and the zirconia ceramic powder is formed by zirconia powder, yttrium oxide powder and magnesium oxide powder according to the mass percentage of 94-98%: 1-3%: 1-3% of the raw materials;
3) warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor at the temperature of 60-100 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
4) vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.25-1 ℃/min, the temperature is increased to 600-700 ℃, and the temperature is kept for 0.5-1 h;
5) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere, wherein the sintering temperature is 1500-1600 ℃, the temperature is kept for 0.5-2 h, and the pressure is 20-60 MPa, so that the fiber monolithic ceramic is obtained;
6) high-temperature oxidation: oxidizing the fiber monolithic ceramics at 1000-1200 ℃ for 1-5 h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramics with compact hole walls, wherein the hole diameter is 100-1000 mu m, and the hole wall thickness is 50-200 mu m.
In the step 2), the preparation method of the zirconia slurry is to weigh zirconia ceramic powder, and then weigh 20-30% of polyethylene glycol and 500-1000% of absolute ethyl alcohol according to the weight percentage based on the weight of the zirconia ceramic powder.
The working principle of the invention is as follows: provides a new process for preparing the straight-through pore zirconia ceramics with compact pore walls by a wet spinning-hot pressing method. Firstly stirring and dissolving a curing agent and a plasticizer in an organic solvent, adding carbon black ceramic powder to form a spinning solution, extruding the spinning solution from fine holes of a spinning nozzle to form a thin stream, and then curing and forming in a solidification solution to obtain a monolithic fibrous precursor cell body, wherein the curing agent is polyether sulfone, the plasticizer is dioctyl phthalate, and the organic solvent is a mixture of N-methylpyrrolidone and acetone(ii) a Coating the zirconia slurry by adopting a dipping method to obtain a fibrous monolith precursor with an interface layer; parallel arrangement, warm-pressing forming, vacuum degreasing, hot-pressing sintering, and preparing the fiber monolithic ceramics, wherein the cell body is carbon black powder or charcoal powder material, and the interface layer is ZrO2A base material; and finally, oxidizing at the high temperature of 1000-1200 ℃, and removing the cell carbon black powder or the charcoal powder by oxidation to finally form the straight-through-hole zirconia ceramic with compact hole walls, wherein the structural schematic diagram is shown in figure 1.
Compared with the prior art, the invention has the following advantages:
1. the precursor cell body of the fibrous monolith is formed by a wet spinning method, and the continuous, superfine, high-toughness, compact and cylindrical precursor cell body of the fibrous monolith is prepared, wherein the diameter can reach 200 mu m, the length can reach 10m, and the fibrous monolith can not be broken when being bent by 180 degrees. Thoroughly overcomes the defects of extrusion molding of pug, poor flowability of the pug, and thick diameter, poor toughness and discontinuity of the fiber monolithic precursor;
2. the organic solvent is a mixture of N-methyl pyrrolidone and acetone, the mass ratio of the N-methyl pyrrolidone to the acetone is (5-10): 1, so that the dissolving speed of the curing agent polyether sulfone is high and uniform, no macromolecular aggregates exist, and the cell body of the obtained fibrous monolithic precursor is uniform in thickness;
3. dipping and coating an interface layer on the fibromonolith precursor cell body in zirconia slurry taking absolute ethyl alcohol as a solvent, wherein the fibromonolith precursor cell body is insoluble, is uniformly coated and is dried at a high speed, and the hole wall obtained after hot-pressing sintering is ultrathin and can reach 50 mu m in thickness;
4. the prepared straight-through hole zirconia ceramic has completely compact hole walls, so that the straight-through hole zirconia ceramic has higher bending strength;
5. the straight-through-hole zirconia ceramic is prepared through wet spinning, hot-pressing sintering and high-temperature oxidation, the hole diameter can reach micron level, which can not be realized by traditional pug extrusion molding;
6. the zirconium oxide phase transformation toughening mechanism is ZrO2When the ceramic is broken, the crack is expanded, the stress field at the tip of the crack induces t → m phase change, the volume of the phase change particle is expanded, and the stress is generated on the crack due to the volume expansion of the phase change particleForce, hindering crack propagation. Thus, only dense ZrO2The ceramic can be subjected to phase change toughening, and the wall of the through-hole zirconia ceramic prepared by the invention is compact, so that the ceramic has higher strength and better toughness.
Drawings
FIG. 1 is a schematic structural view of a through-hole zirconia ceramic having dense hole walls according to the present invention;
FIG. 2 is a photograph of a cross-section of a fibrous monolith precursor having an interface layer obtained in example 1 of the present invention.
In the figure: 1. the pore wall of the zirconia ceramic with the through pores; 2. a through hole of the through hole zirconia ceramic.
Detailed Description
Example 1
1. Preparing a precursor cell body of the fibrolite: firstly stirring and dissolving 10 g of polyether sulfone and 1 g of dioctyl phthalate in 80 g of N-methyl pyrrolidone and 20 g of acetone, then adding carbon black ceramic powder, wherein the carbon black ceramic powder consists of 100 g of carbon black powder, strongly stirring to prepare spinning solution, then transferring the spinning solution into a stainless steel storage tank, carrying out vacuum degassing for 1h, spraying the spinning solution into a gel tank filled with water through a spinning head under the nitrogen pressure of 0.2MPa, keeping the water temperature of the gel tank at 0 ℃, soaking for 8h after solidification forming to obtain a monolithic fiber precursor cell, wherein the diameter of the monolithic fiber precursor cell is 200 mu m;
2. coating an interface layer by a dipping method: firstly adding 20 g of polyethylene glycol into 500 g of absolute ethyl alcohol, uniformly stirring, then adding zirconia ceramic powder, stirring for 4h to form zirconia slurry, coating by adopting a dipping method, dipping a monolithic precursor cell body into the zirconia slurry, controlling the thickness of the coating by dipping and pulling times to obtain a monolithic precursor with an interface layer, wherein the thickness of the interface layer is 50 mu m, and the zirconia ceramic powder consists of 94 g of zirconia powder, 3 g of yttrium oxide powder and 3 g of magnesium oxide powder according to the mass percentage of 94%: 3%: 3 percent of the raw materials are mixed;
3. warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and carrying out warm pressing at 60 ℃ and 20MPa to compact the fiber monolithic precursor to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 600 ℃ at the heating speed of 0.25 ℃/min, and keeping the temperature for 0.5 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering under argon atmosphere, wherein the sintering temperature is 1500 ℃, the temperature is kept for 2h, and the pressure is 20MPa, so that the fiber monolithic ceramic is obtained;
6. high-temperature oxidation: oxidizing the fibromonolithic ceramic at 1000 ℃ for 5h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 100 mu m, and the hole wall thickness is 50 mu m.
Example 2
1. Preparing a precursor cell body of the fibrolite: firstly stirring and dissolving 20 g of polyether sulfone and 4 g of dioctyl phthalate in 180 g of N-methylpyrrolidone and 20 g of acetone, then adding carbon black ceramic powder, wherein the carbon black ceramic powder consists of 100 g of carbon black powder, strongly stirring to prepare spinning solution, then transferring the spinning solution into a stainless steel storage tank, carrying out vacuum degassing for 5h, spraying the spinning solution into a gel tank filled with water through a spinning head under the nitrogen pressure of 0.5MPa, keeping the water temperature of the gel tank at 10 ℃, and soaking for 24h after solidification forming to obtain a monolithic fiber precursor cell body, wherein the diameter of the monolithic fiber precursor cell body is 2000 mu m;
2. coating an interface layer by a dipping method: firstly adding 30 g of polyethylene glycol into 1000 g of absolute ethyl alcohol, uniformly stirring, then adding zirconia ceramic powder, stirring for 12h to form zirconia slurry, coating by adopting a dipping method, dipping a monolithic precursor cell body into the zirconia slurry, controlling the thickness of the coating by dipping and pulling times to obtain the monolithic precursor with an interface layer, wherein the thickness of the interface layer is 200 mu m, and the zirconia ceramic powder consists of 98 g of zirconia powder, 1 g of yttrium oxide powder and 1 g of magnesium oxide powder according to the mass percent of 98%: 1%: 1 percent of the components are mixed;
3. warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and carrying out warm pressing at 100 ℃ and 50MPa to compact the fiber monolithic precursor to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 700 ℃ at the heating speed of 1 ℃/min, and keeping the temperature for 1 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at 1600 ℃, keeping the temperature for 0.5h and the pressure of 60MPa to obtain the fiber monolithic ceramic;
6. high-temperature oxidation: oxidizing the fibromonolithic ceramic at 1200 ℃ for 1h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 1000 mu m, and the hole wall thickness is 200 mu m.
Example 3
1. Preparing a precursor cell body of the fibrolite: stirring and dissolving 15 g of polyether sulfone and 2 g of dioctyl phthalate in 131.25 g of N-methyl pyrrolidone and 18.75 g of acetone, adding carbon black ceramic powder, wherein the carbon black ceramic powder consists of 100 g of charcoal powder, strongly stirring to prepare spinning liquid, then transferring the spinning liquid into a stainless steel storage tank, carrying out vacuum degassing for 2h, spraying the spinning liquid into a gel tank filled with water through a spinning head under the nitrogen pressure of 0.4MPa, wherein the water temperature of the gel tank is 5 ℃, and soaking for 12h after solidification forming to obtain a monolithic precursor cell, wherein the diameter of the monolithic precursor cell is 1000 mu m;
2. coating an interface layer by a dipping method: firstly adding 25 g of polyethylene glycol into 800 g of absolute ethyl alcohol, uniformly stirring, then adding zirconia ceramic powder, stirring for 8h to form zirconia slurry, coating by adopting a dipping method, dipping a monolithic precursor cell body into the zirconia slurry, controlling the thickness of the coating by dipping and pulling times to obtain a monolithic precursor with an interface layer, wherein the thickness of the interface layer is 100 mu m, and the zirconia ceramic powder consists of 96 g of zirconia powder, 2 g of yttrium oxide powder and 2 g of magnesium oxide powder according to the mass percent of 96%: 2%: 2 percent of the raw materials are mixed;
3. warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and carrying out warm pressing at 80 ℃ and 30MPa to compact the fiber monolithic precursor to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.5 ℃/min, the temperature is increased to 650 ℃, and the temperature is kept for 0.75 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at 1550 ℃, keeping the temperature for 1h and the pressure of 40MPa to obtain the fiber monolithic ceramic;
6. high-temperature oxidation: oxidizing the fibromonolithic ceramic at 1100 ℃ for 4h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 500 mu m, and the hole wall thickness is 100 mu m.
Example 4
1. Preparing a precursor cell body of the fibrolite: firstly stirring and dissolving 18 g of polyether sulfone and 3 g of dioctyl phthalate in 150 g of N-methyl pyrrolidone and 30 g of acetone, then adding carbon black ceramic powder consisting of 100 g of charcoal powder, strongly stirring to prepare spinning solution, then transferring the spinning solution into a stainless steel storage tank, degassing for 4h in vacuum, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.3MPa, wherein the water temperature of the gel tank is 5 ℃, and soaking for 20h after solidification and forming to obtain a monolithic precursor cell, wherein the diameter of the monolithic precursor cell is 1200 mu m;
2. coating an interface layer by a dipping method: firstly adding 27 g of polyethylene glycol into 700 g of absolute ethyl alcohol, uniformly stirring, then adding zirconia ceramic powder, stirring for 6h to form zirconia slurry, coating by adopting a dipping method, dipping a monolithic precursor cell body into the zirconia slurry, controlling the thickness of the coating by dipping and pulling times to obtain the monolithic precursor with an interface layer, wherein the thickness of the interface layer is 80 mu m, and the zirconia ceramic powder consists of 95 g of zirconia powder, 2 g of yttrium oxide powder and 3 g of magnesium oxide powder according to the mass percentage of 95%: 2%: 3 percent of the raw materials are mixed;
3. warm-pressing and forming: cutting a fiber monolith precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging in parallel in the graphite die, and carrying out warm pressing at 70 ℃ and 40MPa to compact the precursor so as to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 650 ℃ at the heating speed of 0.5 ℃/min, and keeping the temperature for 0.5 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at 1560 ℃ for 1h under 40MPa to obtain fiber monolithic ceramics;
6. high-temperature oxidation: oxidizing the fibrous monolith ceramic at 1050 ℃ for 3h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 600 mu m, and the hole wall thickness is 80 mu m.
Claims (2)
1. A method for preparing a straight-through pore zirconia ceramic with a compact pore wall by a wet spinning dipping method is characterized by comprising the following steps:
1) preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: firstly stirring and dissolving a curing agent and a plasticizer in an organic solvent, then adding carbon black ceramic powder, strongly stirring to prepare a spinning solution, then transferring the spinning solution to a stainless steel storage tank, vacuum degassing for 1-5 h, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.2-0.5 MPa, wherein the water temperature of the gel tank is 0-10 ℃, solidifying and forming, and then soaking for 8-24 h to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 200-2000 mu m, when weighing, the carbon black ceramic powder is weighed, then the curing agent is weighed according to the weight percentage, the plasticizer is 1-4%, the organic solvent is 100-200%, the curing agent is polyether sulfone, the plasticizer is dioctyl phthalate, the organic solvent is a mixture of N-methyl pyrrolidone and acetone, the mass ratio of the N-methyl pyrrolidone to the acetone is (4-9): 1, the carbon black ceramic powder consists of carbon black powder or charcoal powder;
2) coating an interface layer by a dipping method: firstly adding a binder into absolute ethyl alcohol, uniformly stirring, then adding zirconia ceramic powder, stirring for 4-12 h to form zirconia slurry, coating by adopting a dipping method, dipping a monolithic precursor cell body into the zirconia slurry, controlling the thickness of the coating by dipping and pulling times to obtain the monolithic precursor with an interface layer, wherein the thickness of the interface layer is 50-200 mu m, the binder is polyethylene glycol, and the zirconia ceramic powder is formed by zirconia powder, yttrium oxide powder and magnesia powder according to the mass percent of 94-98%: 1-3%: 1-3% of the raw materials;
3) warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor at the temperature of 60-100 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
4) vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, and performing vacuum degreasing at the heating speed of 0.25-1 ℃/min to 600-700 ℃, and keeping the temperature for 0.5-1 h;
5) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere, wherein the sintering temperature is 1500-1600 ℃, the temperature is kept for 0.5-2 h, and the pressure is 20-60 MPa, so that the fiber monolithic ceramic is obtained;
6) high-temperature oxidation: oxidizing the fiber monolithic ceramics at 1000-1200 ℃ for 1-5 h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramics with compact hole walls, wherein the hole diameter is 100-1000 mu m, and the hole wall thickness is 50-200 mu m.
2. The wet spinning impregnation process of making a straight through pore zirconia ceramic with dense pore walls according to claim 1 wherein: in the step 2), the preparation method of the zirconia slurry comprises the steps of weighing zirconia ceramic powder, and then weighing 20-30% of polyethylene glycol and 500-1000% of absolute ethyl alcohol according to the weight percentage based on the weight of the zirconia ceramic powder.
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| CN102173830A (en) * | 2010-12-30 | 2011-09-07 | 山东理工大学 | Process for preparing laminar zirconium boride superhigh-temperature ceramic by casting-impregnation method |
| CN107983177A (en) * | 2017-12-07 | 2018-05-04 | 山东理工大学 | Cross section is the preparation method of petal-shaped bi-component asymmetric hollow fiber ceramic membrane |
| CN108794033A (en) * | 2018-06-28 | 2018-11-13 | 中国科学院兰州化学物理研究所 | A kind of self toughening fibrous monolithic ceramic structural ceramics and preparation method thereof |
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| CN102173830A (en) * | 2010-12-30 | 2011-09-07 | 山东理工大学 | Process for preparing laminar zirconium boride superhigh-temperature ceramic by casting-impregnation method |
| CN107983177A (en) * | 2017-12-07 | 2018-05-04 | 山东理工大学 | Cross section is the preparation method of petal-shaped bi-component asymmetric hollow fiber ceramic membrane |
| CN108794033A (en) * | 2018-06-28 | 2018-11-13 | 中国科学院兰州化学物理研究所 | A kind of self toughening fibrous monolithic ceramic structural ceramics and preparation method thereof |
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