CN102424603A - Method for preparing zirconia gradient porous ceramics with ice as template - Google Patents
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- CN102424603A CN102424603A CN2011102645290A CN201110264529A CN102424603A CN 102424603 A CN102424603 A CN 102424603A CN 2011102645290 A CN2011102645290 A CN 2011102645290A CN 201110264529 A CN201110264529 A CN 201110264529A CN 102424603 A CN102424603 A CN 102424603A
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Abstract
The invention relates to a method for preparing zirconia gradient porous ceramics with ice as a template. The method comprises: taking ice as a pore-forming template, adding distilled water, a Na2SiO3.9H2O binder, a yttrium oxide sintering aid and a ceramic powder water system dispersant into zirconia powder, conducting ball milling and mixing so as to obtain a stable suspending liquid, which, after vacuum pumping, is injected into a die for low temperature rapid freezing, carrying out vacuum freeze drying to a frozen sample, performing demoulding and then put it into a high temperature furnace for sintering, thus obtaining zirconia porous ceramics. The pore structure of the porous ceramics is completely decided by appearance characteristics of ice crystals. Compared with other porous preparation technologies, ice is an ideal template for making porous ceramics, and the process of the invention is characterized by environmental protection and low cost. The prepared zirconia porous ceramics have obvious gradient porous structures. The use of a binder in the invention can prevent a green body from cracking and deforming during drying, thus enhancing the mechanical strength of products. And adding of a yttrium oxide sintering aid can lower the sintering temperature. The prepared zirconia porous ceramics has compressive strength up to 8MPa.
Description
Technical field
The present invention relates to a kind of method for preparing ceramic foam, more particularly say, be meant that a kind of is the method that template prepares the zirconium oxide gradient ceramic foam with ice.
Background technology
Ceramic foam has equally distributed relatively micropore, low volume density, 3 D stereo network skeleton structure, high specific surface area and unique physical surface properties; The liquids and gases medium had good selection perviousness, energy absorption or damping characteristic; High temperature resistant; Corrosion-resistant etc., can be widely used in aspects such as gas-liquid filtration, support of the catalyst, purification separation, sound absorption damping, senior heat insulating products, biologic implant.
Along with science and technology and suitability for industrialized production development, liquid, solid Research of Separation Technique and exploitation to be had higher requirement, the millipore filtration technology and the microporous filtering ceramic that require high score to leave precision, high operating rate are very paid attention to.Gradient porous ceramics is owing to have asymmetrical pore structure; Realize that easily the small-bore is ventilative greatly, have the big air transmission coefficient of high filtering precision, backwash good effectiveness, in the filtering separation process, can improve filtering accuracy and filtration efficiency greatly; Also can reduce pressure drop; And then reduced production cost, and be specially adapted to the temperature height, have separation, high temperature fume dust removal and fine filtering etc. that corrodibility etc. contains the mixed stream of minuteness particle, realized more high-precision gradient separations.
At present, the technology of preparing of gradient porous ceramics can reduce: (1) different sites in base substrate is introduced the pore-forming material or the sintering aid of different content, obtains having bore diameter gradient distributed porous pottery behind the sintering; (2) flood organic formwork, duplicate and form the gradient hole with Gradient distribution; (3) will have the slurry of different pore-forming material content, carry out the moulding of layer-by-layer casting gel solidification, obtain bore diameter gradient distributed porous pottery behind the sintering; (4) adopt the centrifugal forming technology, utilize the different particle of globule size settling velocity in parting liquid different, thereby make separate particles form hole gradient continually varying ceramic foam.Aforesaid method often has disadvantage: at first, because its uneven structure makes complicated process of preparation and sintering relatively more difficult; Secondly, prepared sample structure is non-complete ideal gradient-structure, and various defectives are easy to generate.The high application that has seriously limited gradient porous ceramics of these shortcomings, especially cost.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, providing a kind of is the method that template prepares the zirconium oxide gradient ceramic foam with ice.The prepared ceramic foam of the present invention has gradient-structure, is made up of the composite structure of the micropore that distributes on directed duct and the hole wall, stratiform and two kinds of microstructures of porous.
For achieving the above object, the technical scheme that the present invention adopts is:
1) at first, difference weighing 100g zirconia powder, 200g～400g zero(ppm) water, 30gNa
2SiO
39H
2O, 3g yttrium oxide and 2.6g ceramics powder aqueous systems dispersion agent in the stainless steel jar mill of packing into, add 650g stainless steel abrading-ball again, on ball mill, carry out abundant ball mill mixing then and are configured to stable suspension liquid in 12 hours;
2) secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3) afterwards; Suspension liquid is injected mould, then mould is placed-30 ℃～-40 ℃ the freezing suspension liquid that makes of vacuum freeze drier to freeze fully, the suspension liquid that will freeze again is thoroughly dry under vacuum state; The demoulding then obtains the ZrO identical shaped with forming mould
2The porous biscuit;
4) then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1300 ℃～1500 ℃ with the temperature rise rate of 10 ℃/min from room temperature, is incubated 2 hours;
5) last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of gradient-structure
2Ceramic foam.
The machine rotating speed of said step 1) ball milling is 600 rev/mins, and mechanical milling process adopts the mode of intermittent type ball milling, and every ball milling 1 hour stops ball mill cooling 1 hour.
Described ceramics powder aqueous systems dispersion agent is HFXZ-802.
Described ball mill adopts the planetary four-head fire ball of KQM-X4/B type grinding machine.
Described forming mould is a cylindrical-shaped structure, and mold material is a Vestolen PP 7052, and thickness is 2mm.
Described vacuum freeze drier is the LGJ-10D type.
The zircite porous ceramic ultimate compression strength of described preparation can reach 8MPa.
Frost drying technology (Freezing Casting) is that a kind of preparation technology is simple, practical, and the preparation method of more economical and environmental protection through regulation and control paste consistency and refrigerating process, can obtain to have orientation and gradient-structure ceramic foam.The mechanism of freeze-drying is to be the pore-creating template with ice; Freeze to contain the suspension liquid of ceramic particle; Then under suitable vacuum environment; Through heating ice is directly distilled and remove for steam, ceramic particle remains resident in ice intergranular form, obtains the porous microstructure of the negative replica of ice-crystal growth.Its characteristics are: (1) does not have any pollution to environment, need not to add organic or the inorganic chemistry objectionable impurities; (2) formation of pore texture is a kind of physical process, does not need special template, does not also need to remove like calcining, chemical etching etc. the process of template; (3) can obtain multiple yardstick pore structure and micropore and lamella composite structure simultaneously, for gradient porous structure design provides possibility; (4) facility investment is few, can realize the dead size moulding, is easy to apply.
The present invention is with zirconia powder, Na
2SiO
39H
2O (sticker), yttrium oxide (sintering aid), dispersion agent and the abundant ground and mixed of zero(ppm) water form stable suspension liquid, and after the vacuum stripping, freezing behind the casting is freezed the final vacuum lyophilize, and the demoulding then, sintering obtain zircite porous ceramic.Because ice takes up space in freezing body and has become the hole, has formed the porous blocks with ad hoc structure.Therefore, water has been brought into play the effect of pore-forming material in other words of pore-creating template.Can infer that structure that water congeals into ice and shape have directly determined the structure and the shape in hole.This method need not added organic pore-forming agents etc., has avoided environmental pollution, is a kind of environment-friendly type technique, and operating procedure is simple, and cost is low.Because prepared ceramic foam has gradient-structure, aspect filtration, has outstanding advantage.Sticker Na
2SiO
39H
2The adding of O makes the sample after the lyophilize keep certain intensity, deforms, ftractures and be unlikely when the demoulding.The adding of yttrium oxide sintering aid can reduce sintering temperature.Carry out vacuum suction behind the ball milling, can get rid of the bubble that produces in the mechanical milling process.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is the technical process that the present invention prepares zircite porous ceramic.
Fig. 2 is macroscopical digital photograph of the porous biscuit after-30 ℃ of freeze-dried-demouldings among the present invention.Wherein:
Fig. 2 (a) is positive macroscopical digital photograph, and Fig. 2 (b) is a side macroscopic view digital photograph.
Fig. 3 be among the present invention through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, macroscopical digital photograph of the ceramic foam that obtains.Wherein:
Fig. 3 (a) is positive macroscopic view sign indicating number photo, and Fig. 3 (b) is a side macroscopic view sign indicating number photo.
Fig. 4 be among the present invention through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1300 ℃ of sintering, the porous ceramic surface electron scanning micrograph that obtains.Wherein:
Fig. 4 (a) and (b), (c), (d) are the different multiples electron scanning micrograph.
Fig. 5 be among the present invention through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1300 ℃ of sintering, the ceramic foam side electron scanning micrograph that obtains.Wherein:
Fig. 5 (a) and (b) are the different multiples electron scanning micrograph.
Fig. 6 be among the present invention through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, the porous ceramic surface electron scanning micrograph that obtains.Wherein:
Fig. 6 (a) and (b), (c), (d), (e) are the different multiples electron scanning micrograph.
Fig. 7 be among the present invention through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, top, the ceramic foam side electron scanning micrograph that obtains.Wherein:
Fig. 7 (a) and (b) are the different multiples electron scanning micrograph.
Fig. 8 be among the present invention through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, middle part, the ceramic foam side that obtains electron scanning micrograph.Wherein:
Fig. 8 (a) and (b) are the different multiples electron scanning micrograph.
Fig. 9 be among the present invention through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, the ceramic foam side lower scan electron micrograph that obtains.Wherein:
Fig. 9 (a) and (b) are the different multiples electron scanning micrograph.
Embodiment
Embodiment 1: referring to Fig. 1:
1. at first, difference weighing 100g zirconia powder (Chemical Reagent Co., Ltd., Sinopharm Group), 200g zero(ppm) water, 30g Na
2SiO
39H
2O sticker (Kingsoft, Chengdu chemical reagent ltd), 3g yttrium oxide and 2.6g HFXZ-802 type ceramics powder aqueous systems dispersion agent (Hefei Xiang positizing subject skill ltd); In the stainless steel jar mill of packing into, and add 650g stainless steel abrading-ball, adopt the planetary four-head fire ball of KQM-X4/B type grinding machine to carry out abundant ball mill mixing 12 hours then; Be configured to stable suspension liquid; Drum's speed of rotation is 600 rev/mins, and every grinding is 1 hour in mechanical milling process, stops ball mill cooling 1 hour.
2. secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3. after; Suspension liquid is injected in the polypropylene molds; (Beijing Sihuan Scientific Instrument Factory Co., Ltd produces, and model: suspension liquid is freezed fully, and the suspension liquid that will freeze again successive drying under vacuum state is thorough then mould to be placed-30 ℃ vacuum freeze drier; The demoulding then obtains the column ZrO similar with the forming mould shape
2The porous biscuit.
4. then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1300 ℃ with the temperature rise rate of 10 ℃/min, is incubated 2 hours.
5. last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of ad hoc structure
2Ceramic foam.
6. use the porous biscuit after the vacuum lyophilization of the present invention as shown in Figure 2, sample does not have defectives such as macroscopic view cracking, distortion.Fig. 2 (a) is macroscopical digital photograph on porous biscuit surface, and visible surface has formed laminated structure; Fig. 2 (b) is the lateral macroscopical digital photograph of porous biscuit, and the side has formed the dendroid vesicular structure.Typical microstructure such as Fig. 4 and shown in Figure 5 of the zircite porous ceramic of preparation, Fig. 4 is the porous ceramic surface electron scanning micrograph that behind 1300 ℃ of sintering, prepares through the porous biscuit after-30 ℃ of freeze-dried-demouldings.Visible by figure, formed the dendroid vesicular structure that aligns, also there is more tiny micropore on the hole wall.Fig. 5 be through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1300 ℃ of sintering, the ceramic foam side electron scanning micrograph that obtains.Visible by figure, formed irregular vesicular structure.
7. the void content that adopts Archimedes's drainage to measure the zircite porous ceramic that uses the present invention's preparation is 56.79%.
8. adopt WAW-1000 microcomputer controlled electro-hydraulic servo universal testing machine to measure and use the ultimate compression strength of the zircite porous ceramic of the present invention's preparation to be 4.37MPa.Ultimate compression strength is lower, mainly is that sintering is insufficient, makes structure comparatively loose because sintering temperature is low, and stressed a little back structure is promptly destroyed.
Embodiment 2:
1. at first, difference weighing 100g zirconia powder (Chemical Reagent Co., Ltd., Sinopharm Group), 200g zero(ppm) water, 30g Na
2SiO
39H
2O sticker (Kingsoft, Chengdu chemical reagent ltd), 3g yttrium oxide and 2.6g HFXZ-802 type ceramics powder aqueous systems dispersion agent (Hefei Xiang positizing subject skill ltd); In the stainless steel jar mill of packing into, add 650g stainless steel abrading-ball, adopt the planetary four-head fire ball of KQM-X4/B type grinding machine to carry out abundant ball mill mixing 12 hours then; Be configured to stable suspension liquid; Drum's speed of rotation is 600 rev/mins, and every grinding is 1 hour in mechanical milling process, stops ball mill cooling 1 hour.
2. secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3. after; Suspension liquid is injected in the polypropylene molds; (Beijing Sihuan Scientific Instrument Factory Co., Ltd produces, and model: suspension liquid is freezed fully, and the suspension liquid that will freeze again successive drying under vacuum state is thorough then mould to be placed-30 ℃ vacuum freeze drier; The demoulding then obtains the column ZrO similar with the forming mould shape
2The porous biscuit.
4. then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1500 ℃ with the temperature rise rate of 10 ℃/min, is incubated 2 hours.
5. last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of ad hoc structure
2Ceramic foam.
6. use the porous biscuit after the vacuum lyophilization of the present invention as shown in Figure 2, sample does not have defectives such as macroscopic view cracking, distortion.Fig. 3 is macroscopical digital photograph of the ceramic foam that behind 1500 ℃ of sintering, prepares through the porous biscuit after-30 ℃ of freeze-dried-demouldings.Visible by figure, obvious variation does not take place in the structure and the shape of sintering front and rear gaps, and sample does not have defectives such as cracking, distortion.The typical microstructure of prepared zircite porous ceramic such as Fig. 6, Fig. 7, Fig. 8 and shown in Figure 9.Fig. 6 is the porous ceramic surface electron scanning micrograph that behind 1500 ℃ of sintering, prepares through the porous biscuit after-30 ℃ of freeze-dried-demouldings.Visible by figure, formed the approximate layered porous structure that aligns, also there is more tiny micropore on the hole wall, the structure by similar bridge between the lamella is connected to each other.
Fig. 7 be through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, top, the ceramic foam side electron scanning micrograph that obtains.Visible by figure, formed the approximate layered porous structure that aligns, having between the lamella builds bridge connects.
Fig. 8 be through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, middle part, the ceramic foam side that obtains electron scanning micrograph.Visible by figure, the structure generation considerable change in hole has formed the irregular cycle pore structure, and the hole is similar to directional profile.
Fig. 9 be through the porous biscuit after-30 ℃ of freeze-dried-demouldings behind 1500 ℃ of sintering, the ceramic foam side lower scan electron micrograph that obtains.Visible by figure, formed the irregular cycle pore structure, the hole is more and more tiny.
This shows that having formed top is that laminate structure, middle and lower part are the complex construction of vesicular structure, and from top to bottom, matrix is more and more finer and close, hole dimension is more and more littler, has constituted gradient porous structure.
7. the void content that adopts Archimedes's drainage to measure the zircite porous ceramic that uses the present invention's preparation is 26.77%.
8. adopt WAW-1000 microcomputer controlled electro-hydraulic servo universal testing machine to measure and use the ultimate compression strength of the zircite porous ceramic of the present invention's preparation to be 8.26MPa.Because sintering raises, grain growing is grown better abundant, and bonding strength increases between the particle, and ultimate compression strength raises.
Embodiment 3:
1. at first, difference weighing 100g zirconia powder (Chemical Reagent Co., Ltd., Sinopharm Group), 300g zero(ppm) water, 30g Na
2SiO
39H
2O sticker (Kingsoft, Chengdu chemical reagent ltd), 3g yttrium oxide and 2.6g HFXZ-802 type ceramics powder aqueous systems dispersion agent (Hefei Xiang positizing subject skill ltd); In the stainless steel jar mill of packing into, add 650g stainless steel abrading-ball, adopt the planetary four-head fire ball of KQM-X4/B type grinding machine to carry out abundant ball mill mixing 12 hours then; Be configured to stable suspension liquid; Drum's speed of rotation is 600 rev/mins, and every grinding is 1 hour in mechanical milling process, stops ball mill cooling 1 hour.
2. secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3. after; Suspension liquid is injected in the polypropylene molds; (Beijing Sihuan Scientific Instrument Factory Co., Ltd produces, and model: suspension liquid is freezed fully, and the suspension liquid that will freeze again successive drying under vacuum state is thorough then mould to be placed-30 ℃ vacuum freeze drier; The demoulding then obtains the column ZrO similar with the forming mould shape
2The porous biscuit.
4. then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1500 ℃ with the temperature rise rate of 10 ℃/min, is incubated 2 hours.
5. last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of ad hoc structure
2Ceramic foam.
6. the ceramic foam with method for preparing adopts Archimedes's drainage measurement of gas porosity, adopts WAW-1000 microcomputer controlled electro-hydraulic servo universal testing machine to measure its ultimate compression strength, adopts its microtexture of JSM-6390LV type sem observation.
Embodiment 4:
1. at first, difference weighing 100g zirconia powder (Chemical Reagent Co., Ltd., Sinopharm Group), 400g zero(ppm) water, 30g Na
2SiO
39H
2O sticker (Kingsoft, Chengdu chemical reagent ltd), 3g yttrium oxide and 2.6g HFXZ-802 type ceramics powder aqueous systems dispersion agent (Hefei Xiang positizing subject skill ltd); In the stainless steel jar mill of packing into, add 650g stainless steel abrading-ball, adopt the planetary four-head fire ball of KQM-X4/B type grinding machine to carry out abundant ball mill mixing 12 hours then; Be configured to stable suspension liquid; Drum's speed of rotation is 600 rev/mins, and every grinding is 1 hour in mechanical milling process, stops ball mill cooling 1 hour.
2. secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3. after; Suspension liquid is injected in the polypropylene molds; (Beijing Sihuan Scientific Instrument Factory Co., Ltd produces, and model: suspension liquid is freezed fully, and the suspension liquid that will freeze again successive drying under vacuum state is thorough then mould to be placed-30 ℃ vacuum freeze drier; The demoulding then obtains the column ZrO similar with the forming mould shape
2The porous biscuit.
4. then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1500 ℃ with the temperature rise rate of 10 ℃/min, is incubated 2 hours.
5. last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of ad hoc structure
2Ceramic foam.
6. the ceramic foam with method for preparing adopts Archimedes's drainage measurement of gas porosity, adopts WAW-1000 microcomputer controlled electro-hydraulic servo universal testing machine to measure its ultimate compression strength, adopts its microtexture of JSM-6390LV type sem observation.
Embodiment 5:
1. at first, difference weighing 100g zirconia powder (Chemical Reagent Co., Ltd., Sinopharm Group), 280g zero(ppm) water, 30g Na
2SiO
39H
2O sticker (Kingsoft, Chengdu chemical reagent ltd), 3g yttrium oxide and 2.6g HFXZ-802 type ceramics powder aqueous systems dispersion agent (Hefei Xiang positizing subject skill ltd); In the stainless steel jar mill of packing into, add 650g stainless steel abrading-ball, adopt the planetary four-head fire ball of KQM-X4/B type grinding machine to carry out abundant ball mill mixing 12 hours then; Be configured to stable suspension liquid; Drum's speed of rotation is 600 rev/mins, and every grinding is 1 hour in mechanical milling process, stops ball mill cooling 1 hour.
2. secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3. after; Suspension liquid is injected in the polypropylene molds; (Beijing Sihuan Scientific Instrument Factory Co., Ltd produces, and model: suspension liquid is freezed fully, and the suspension liquid that will freeze again successive drying under vacuum state is thorough then mould to be placed-36 ℃ vacuum freeze drier; The demoulding then obtains the column ZrO similar with the forming mould shape
2The porous biscuit.
4. then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1400 ℃ with the temperature rise rate of 10 ℃/min, is incubated 2 hours.
5. last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of ad hoc structure
2Ceramic foam.
6. the ceramic foam with method for preparing adopts Archimedes's drainage measurement of gas porosity, adopts WAW-1000 microcomputer controlled electro-hydraulic servo universal testing machine to measure its ultimate compression strength, adopts its microtexture of JSM-6390LV type sem observation.
Embodiment 6:
1. at first, difference weighing 100g zirconia powder (Chemical Reagent Co., Ltd., Sinopharm Group), 350g zero(ppm) water, 30g Na
2SiO
39H
2O sticker (Kingsoft, Chengdu chemical reagent ltd), 3g yttrium oxide and 2.6g HFXZ-802 type ceramics powder aqueous systems dispersion agent (Hefei Xiang positizing subject skill ltd); In the stainless steel jar mill of packing into, add 650g stainless steel abrading-ball, adopt the planetary four-head fire ball of KQM-X4/B type grinding machine to carry out abundant ball mill mixing 12 hours then; Be configured to stable suspension liquid; Drum's speed of rotation is 600 rev/mins, and every grinding is 1 hour in mechanical milling process, stops ball mill cooling 1 hour.
2. secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3. after; Suspension liquid is injected in the polypropylene molds; (Beijing Sihuan Scientific Instrument Factory Co., Ltd produces, and model: suspension liquid is freezed fully, and the suspension liquid that will freeze again successive drying under vacuum state is thorough then mould to be placed-40 ℃ vacuum freeze drier; The demoulding then obtains the column ZrO similar with the forming mould shape
2The porous biscuit.
4. then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1350 ℃ with the temperature rise rate of 10 ℃/min, is incubated 2 hours.
5. last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of ad hoc structure
2Ceramic foam.
6. the ceramic foam with method for preparing adopts Archimedes's drainage measurement of gas porosity, adopts WAW-1000 microcomputer controlled electro-hydraulic servo universal testing machine to measure its ultimate compression strength, adopts its microtexture of JSM-6390LV type sem observation.
Claims (7)
1. one kind is the method that template prepares the zirconium oxide gradient ceramic foam with ice, it is characterized in that:
1) at first, difference weighing 100g zirconia powder, 200g～400g zero(ppm) water, 30gNa
2SiO
39H
2O, 3g yttrium oxide and 2.6g ceramics powder aqueous systems dispersion agent in the stainless steel jar mill of packing into, add 650g stainless steel abrading-ball again, on ball mill, carry out abundant ball mill mixing then and are configured to stable suspension liquid in 12 hours;
2) secondly, with the suspension liquid bubble that the eliminating suspension liquid produces in mechanical milling process in the closed container that connects vacuum pump of packing into;
3) afterwards; Suspension liquid is injected mould, then mould is placed-30 ℃～-40 ℃ the freezing suspension liquid that makes of vacuum freeze drier to freeze fully, the suspension liquid that will freeze again is thoroughly dry under vacuum state; The demoulding then obtains the ZrO identical shaped with forming mould
2The porous biscuit;
4) then, with the ZrO of the demoulding
2The porous biscuit is put into the high temperature cabinet-type electric furnace, rises to 1300 ℃～1500 ℃ with the temperature rise rate of 10 ℃/min from room temperature, is incubated 2 hours;
5) last, insulation naturally cools to room temperature with stove after finishing, and promptly obtains having the ZrO of gradient-structure
2Ceramic foam.
2. according to claim 1 is the method that template prepares the zirconium oxide gradient ceramic foam with ice; It is characterized in that: the machine rotating speed of said step 1) ball milling is 600 rev/mins; Mechanical milling process adopts the mode of intermittent type ball milling, and every ball milling 1 hour stops ball mill cooling 1 hour.
3. according to claim 1 is the method that template prepares the zirconium oxide gradient ceramic foam with ice, it is characterized in that: described ceramics powder aqueous systems dispersion agent is HFXZ-802.
4. according to claim 1 is the method that template prepares the zirconium oxide gradient ceramic foam with ice, it is characterized in that: described ball mill adopts the planetary four-head fire ball of KQM-X4/B type grinding machine.
5. according to claim 1 is the method that template prepares the zirconium oxide gradient ceramic foam with ice, it is characterized in that: described forming mould is a cylindrical-shaped structure, and mold material is a Vestolen PP 7052, and thickness is 2mm.
6. according to claim 1 is the method that template prepares the zirconium oxide gradient ceramic foam with ice, it is characterized in that: described vacuum freeze drier is the LGJ-10D type.
7. according to claim 1 is the method that template prepares the zirconium oxide gradient ceramic foam with ice, it is characterized in that: the zircite porous ceramic ultimate compression strength of described preparation can reach 8MPa.
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| CN107827457A (en) * | 2017-12-18 | 2018-03-23 | 洛阳名力科技开发有限公司 | A kind of preparation method of porous oxidation zircon ceramic |
| CN108083811A (en) * | 2017-12-14 | 2018-05-29 | 西安交通大学 | A kind of double gradient porous ceramics materials and preparation method thereof |
| CN110204768A (en) * | 2019-05-08 | 2019-09-06 | 南京航空航天大学 | Phase transition method prepares porous material containing liquid |
| CN113149696A (en) * | 2021-04-22 | 2021-07-23 | 上海交通大学 | Micron-sized yttrium oxide stabilized zirconia ceramic foam material with layered pore structure and preparation method thereof |
| WO2021243522A1 (en) * | 2020-06-01 | 2021-12-09 | 苏州君诺新材科技有限公司 | Method for manufacturing fluorescent ceramic containing pores |
| CN113896529A (en) * | 2021-10-11 | 2022-01-07 | 中国科学院金属研究所 | Directional porous ceramic and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050128A (en) * | 2007-04-13 | 2007-10-10 | 中国科学院上海硅酸盐研究所 | Modified freeze dehydration method for preparing porous material |
| CN101293783A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院理化技术研究所 | Method for preparing inorganic stephanoporate composite material with freeze dehydration |
-
2011
- 2011-09-07 CN CN2011102645290A patent/CN102424603A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050128A (en) * | 2007-04-13 | 2007-10-10 | 中国科学院上海硅酸盐研究所 | Modified freeze dehydration method for preparing porous material |
| CN101293783A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院理化技术研究所 | Method for preparing inorganic stephanoporate composite material with freeze dehydration |
Non-Patent Citations (4)
| Title |
|---|
| 《Scripta Materialia》 20081225 Changqing Hong et al. "Ultra-high-porosity zirconia ceramics fabricated by novel" 第563-566页 1-7 , * |
| 《材料研究学报》 20091031 曹阳 等 "以冰为模板制备超轻多孔氧化锆块材" 第518－523页 1-7 第23卷, 第5期 * |
| CHANGQING HONG ET AL.: ""Ultra-high-porosity zirconia ceramics fabricated by novel"", 《SCRIPTA MATERIALIA》 * |
| 曹阳 等: ""以冰为模板制备超轻多孔氧化锆块材"", 《材料研究学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2545578C1 (en) * | 2014-01-09 | 2015-04-10 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Пермский национальный исследовательский политехнический университет" | Method of making ceramic articles |
| CN104193382A (en) * | 2014-08-19 | 2014-12-10 | 中国石油天然气股份有限公司 | Shale-structure-like material and preparation method thereof |
| CN104193382B (en) * | 2014-08-19 | 2016-01-06 | 中国石油天然气股份有限公司 | A kind of imitative shale structured material and preparation method thereof |
| CN108083811A (en) * | 2017-12-14 | 2018-05-29 | 西安交通大学 | A kind of double gradient porous ceramics materials and preparation method thereof |
| CN107827457A (en) * | 2017-12-18 | 2018-03-23 | 洛阳名力科技开发有限公司 | A kind of preparation method of porous oxidation zircon ceramic |
| CN110204768A (en) * | 2019-05-08 | 2019-09-06 | 南京航空航天大学 | Phase transition method prepares porous material containing liquid |
| CN110204768B (en) * | 2019-05-08 | 2022-04-22 | 南京航空航天大学 | Preparation of porous material containing liquid by phase-change method |
| WO2021243522A1 (en) * | 2020-06-01 | 2021-12-09 | 苏州君诺新材科技有限公司 | Method for manufacturing fluorescent ceramic containing pores |
| CN113149696A (en) * | 2021-04-22 | 2021-07-23 | 上海交通大学 | Micron-sized yttrium oxide stabilized zirconia ceramic foam material with layered pore structure and preparation method thereof |
| CN113896529A (en) * | 2021-10-11 | 2022-01-07 | 中国科学院金属研究所 | Directional porous ceramic and preparation method thereof |
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