CN112552074A - Low-shrinkage porous ceramic component, injection feed and preparation method thereof - Google Patents

Low-shrinkage porous ceramic component, injection feed and preparation method thereof Download PDF

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CN112552074A
CN112552074A CN202110092175.XA CN202110092175A CN112552074A CN 112552074 A CN112552074 A CN 112552074A CN 202110092175 A CN202110092175 A CN 202110092175A CN 112552074 A CN112552074 A CN 112552074A
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ceramic
injection
whisker
inorganic
porous ceramic
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CN112552074B (en
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丁涛
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Shenzhen Dingding Ceramic Technology Co ltd
Shandong Dingding Technology Development Co ltd
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Shenzhen Dingding Ceramic Technology Co ltd
Shandong Dingding Technology Development Co ltd
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Abstract

The application relates to the field of ceramics, and particularly discloses a low-shrinkage porous ceramic component, an injection feed and a preparation method thereof. Wherein the porous ceramic component comprises: inorganic skeleton whisker, inorganic bonding material and inorganic filling material, wherein the inorganic skeleton whisker and the inorganic filling material are inorganicThe skeleton whisker comprises SiC whisker and Al2O3Whisker and SiO2One or more of crystal whisker and AlN crystal whisker; the preparation method comprises the following steps: and uniformly ball-milling the treated ceramic components, mixing the ceramic components with an injection accelerator, an injection skeleton agent, an injection filler and a plasticizer, adding the mixture into a granulator to prepare injection molding feed after mixing is finished, finally injecting the injection molding feed into a ceramic blank, and performing rubber discharge and sintering to obtain the low-shrinkage porous ceramic. The low-shrinkage porous ceramic can be used in the fields of electronic cigarettes, atomization medical treatment and atomization beauty instruments, and has the advantages of low shrinkage rate, controllable size, high product qualification rate and the like.

Description

Low-shrinkage porous ceramic component, injection feed and preparation method thereof
Technical Field
The present application relates to the field of ceramics, and more particularly, it relates to a low shrinkage porous ceramic.
Background
The porous ceramic is a ceramic material with high porosity prepared by molding and high-temperature sintering processes, has the advantages of high temperature resistance, high pressure resistance, acid, alkali and organic medium corrosion resistance, good biological inertia, controllable pore structure, high porosity, long service life, small volume density, large specific surface area, good product regeneration performance and the like, and can be suitable for the fields of precise filtration and separation of various media, high-pressure gas exhaust and noise reduction, gas distribution, electrolytic diaphragms, electronic cigarette atomizing cores and the like.
The porous ceramic can not be shrunk in the glue discharging and sintering processes, the sintering shrinkage rate of general porous ceramic is 3-15%, the molding pressure, sintering temperature and uniformity, heating and cooling rates and material uniformity of the material can cause inconsistency of the sintering shrinkage rate, performance parameters such as the size, the internal pore diameter, the porosity, the strength and the water absorption of the porous ceramic product fluctuate, and the performance stability of the porous ceramic product is affected, so that the porous ceramic material with stable shrinkage is urgently required to be prepared in order to improve the performance of the porous ceramic product.
Disclosure of Invention
In order to obtain a porous ceramic material with stable shrinkage and improve the performance of a porous ceramic product, the application provides a low-shrinkage porous ceramic material and a preparation method of the low-shrinkage porous ceramic.
In a first aspect, the present application provides a low shrinkage porous ceramic component, which adopts the following technical scheme:
a low shrinkage porous ceramic component comprising the following raw materials: inorganic framework whisker, inorganic bonding material and inorganic filling material.
By adopting the technical scheme, the inorganic framework whisker material is adopted to form a network structure, so that a net-shaped support is provided for the whole porous ceramic; the inorganic bonding material is distributed around the inorganic material and is melted at high temperature, so that the framework materials are bonded together to form a firm mesh structure; the inorganic filling material is filled between the large intervals of the framework network and used for supporting the network structure, so that the network structure is not easy to collapse, and the three are mutually matched, so that the porous ceramic structure is firmer, and the effect of reducing the shrinkage rate is achieved.
Optionally, the inorganic framework whisker accounts for 45-80% of the mass of the ceramic component, the inorganic bonding material accounts for 10-45% of the mass of the ceramic component, and the inorganic filling material accounts for 5-15% of the mass of the ceramic component.
By adopting the technical scheme, the inorganic framework whisker, the inorganic bonding material and the inorganic filling material are in proper proportion, so that the framework material forms a network framework structure at the ceramic green body stage, and the stability of the network structure is maintained by the mutual matching of the inorganic filling material and the inorganic bonding material at the sintering stage, thereby maintaining the low shrinkage rate of the porous ceramic.
Optionally, the inorganic framework whisker comprises SiC whisker and Al2O3Whisker and SiO2One or more of crystal whisker and AlN crystal whisker.
By adopting the technical scheme, the crystal whisker is a whisker crystal with high strength, has better fracture toughness, excellent high-temperature creep resistance, uniform strength and higher wear resistance and corrosion resistance, and adopts SiC crystal whisker and Al crystal whisker as inorganic framework crystal whisker2O3Whisker and SiO2One or more of the crystal whiskers and the AlN crystal whiskers can enhance the strength and toughness of the ceramic, provide a support structure for the ceramic, enable the prepared ceramic product to be difficult to deform and maintain low shrinkage rate.
Optionally, the inorganic bonding material is low-temperature glass powder with a melting point of 500-800 ℃ and a fineness of 500-2000 meshes.
By adopting the technical scheme, the inorganic bonding material is added, and the low-temperature glass powder can bond the inorganic framework whiskers together, so that the structure is firmer, the anti-shrinkage effect is achieved, the added inorganic bonding material can resist aging, and the form and position tolerance is easy to guarantee, so that the service life and the performance of the porous ceramic are improved; and the addition of the low-temperature glass powder with the melting point temperature of 500-800 ℃ can achieve the effect of reducing the sintering temperature during sintering, thereby effectively avoiding the shrinkage of the ceramic product from being influenced by overhigh sintering temperature.
Optionally, the inorganic filler material comprises Al2O3、ZnO、ZrO2、SiO2One or more of MgO and CaO.
By adopting the technical scheme, Al is selected2O3、ZnO、ZrO2、SiO2One or more of MgO and CaO is used as an inorganic filling material and is filled among the network frameworks to form a 'nail-pricking' structure, so that macropores in the network structure are reduced, the mechanical property of the porous ceramic is improved, and the low shrinkage rate of the ceramic is maintained.
In a second aspect, the application provides a low shrinkage porous ceramic injection feed, which comprises 50-70% of a ceramic component and 29-60% of an organic component by weight.
By adopting the technical scheme, the ceramic feed for subsequent forming can be prepared by reasonably proportioning the ceramic component and the organic component.
Optionally, the organic component comprises, by weight, 1-5% of an injection accelerator, 5-10% of an injection skeleton agent, 12-20% of an injection filler, 1-5% of a plasticizer and 10-20% of a pore-forming agent.
By adopting the technical scheme, the organic component and the porous ceramic component interact to form slurry with certain fluidity at a certain temperature; wherein the injection filler is melted in a heated state, and the injection slurry is endowed with fluidity; the injection accelerator can greatly reduce the viscosity of the injection slurry, enhance the fluidity of the injection slurry and facilitate the transportation of the slurry in the injection process; the injection skeleton agent can endow the green body with strength and maintain the green body not to collapse and deform in the process of rubber discharging; the plasticizer can increase the plasticity of the injection slurry and accelerate the molding and demolding of the injection slurry and a green body; the pore-forming agent is added in the injection feeding preparation stage, the green body is left in the green body after being formed, and the pore-forming agent is completely volatilized in the binder removal sintering process, so that the formation of micropores in the atomizing core ceramic is realized.
In a third aspect, the present application provides a method for preparing a low shrinkage porous ceramic, comprising the steps of:
(1) drying the inorganic bonding material at the temperature of 100-250 ℃ for 1-5 h; carrying out heat treatment on the inorganic framework material and the inorganic filling material at a high temperature of 650-950 ℃ for 1-4 h;
(2) adding a ball milling medium into the ceramic component treated in the step (1) for ball milling, and sieving the ceramic component by a 10-mesh sieve after the ball milling to obtain ball-milled ceramic component powder;
(3) heating and melting an injection accelerator, an injection skeleton agent, an injection filler and a plasticizer;
(4) adding the ceramic component powder subjected to ball milling in the step (2) and a pore-forming agent into the melted product in the step (3) for banburying;
(5) granulating a product obtained by banburying in the step (4) to obtain injection molding feed;
(6) performing injection molding on the injection molding feed obtained in the step (5) to obtain a ceramic green body;
(7) embedding the ceramic green body obtained in the step (6) into corundum Al with the granularity of 500-1200 meshes2O3Carrying out glue discharging in the buried burning powder;
(8) sintering the ceramic green body subjected to the rubber discharge in the step (7);
(9) sieving the product obtained in the step (8) by a 30-mesh sieve to remove the buried sintering powder, and obtaining the sintered atomized ceramic;
(10) and (4) carrying out post-treatment on the sintered atomized ceramic obtained in the step (9) to obtain an atomized ceramic product. Optionally, the preparation method of the low-shrinkage porous ceramic includes the following steps:
(1) drying the inorganic bonding material at the temperature of 100-250 ℃ for 1-5 h; carrying out heat treatment on the inorganic framework material and the inorganic filling material at a high temperature of 650-950 ℃ for 1-4 h;
(2) placing the ceramic component treated in the step (1) into a ball milling tank, adding zirconium balls with the diameter of 8-12 mm into the ball milling tank, carrying out ball milling for 2-6 h at the rotating speed of 100-350 r/min, and sieving by using a 10-mesh screen after ball milling to obtain ball-milled ceramic component powder;
(3) adding an injection accelerator, an injection skeleton agent, an injection filler and a plasticizer into an internal mixer charging basket, heating and melting, and stirring at a rotating speed of 15-60 r/min for 30-60 min after melting;
(4) slowly adding the ceramic component powder subjected to ball milling in the step (2) and a pore-forming agent into the product stirred in the step (3), stirring at a rotating speed of 15-60 r/min for 30-60 min after the addition is finished, and banburying at the temperature of 60-200 ℃ for 1-4 h after the stirring is finished;
(5) adding the product obtained in the banburying step (4) into a granulator for granulation to obtain injection molding feed with the granularity of 1-3 mm;
(6) adding the injection molding feed obtained in the step (5) into a charging barrel of an injection molding machine for melting, and performing injection molding after melting to obtain a ceramic green body;
(7) embedding the ceramic green body obtained in the step (6) into corundum Al with the granularity of 500-1200 meshes2O3Carrying out glue discharging in the buried burning powder;
(8) putting the ceramic green body subjected to the rubber removal in the step (7) into a sintering furnace for sintering;
(9) sieving the product obtained in the step (8) by a 30-mesh sieve to remove the buried sintering powder, and obtaining the sintered atomized ceramic;
(10) and (3) carrying out post-treatment on the sintered atomized ceramic obtained in the step (9) to obtain an atomized ceramic product, wherein the processing technology comprises the steps of jolting, boiling and drying, wherein the jolting is carried out at the frequency of 20-40 KHz for 10-60 min, the boiling is carried out at the temperature of more than 95 ℃ for 1-2 h, and the drying is carried out at the drying temperature of 100-250 ℃ for 2-8 h.
By adopting the technical scheme, the inorganic framework material and the inorganic filling material are subjected to heat treatment at the temperature of 650-950 ℃, so that on one hand, impurities such as water, organic matters and the like in the inorganic framework material and the inorganic filling material can be removed; on the other hand, because the heat treatment temperature is higher than the sintering temperature of the porous ceramic, the shrinkage of the porous ceramic blank body caused by the sintering shrinkage of the inorganic framework material and the inorganic filling material can be effectively avoided, and the low sintering shrinkage rate of the porous ceramic green body is further reduced.
During grinding, a ball milling medium is added, so that the materials can be fully stirred, and the ceramic components are uniformly mixed; slowly adding the ceramic component and the pore-forming agent into the melted organic component can avoid agglomeration caused by too fast addition of the ceramic component to influence subsequent material forming; banburying for 1-4 h at the temperature of 60-200 ℃, can better promote the dispersibility among ceramic components and between the ceramic components and organic components, and can promote the banburying slurry to have stable viscosity, thereby being more beneficial to the injection molding of the ceramic slurry, promoting the stability of injection green bodies, and obtaining stable porous ceramic after sintering.
As the corundum Al with the granularity of 500-1200 meshes is adopted2O3The burning powder provides a certain support for the product after glue discharging, so that the collapse and the fragmentation of a green body caused by the temporary non-function of the inorganic adhesive can be avoided, and the problem that the ceramic product is scrapped due to the fact that the ceramic bodies are contacted and bonded together in the sintering stage can be prevented.
Optionally, the glue discharging temperature of the glue discharging is 300-400 ℃, and the glue discharging time is 12-24 hours.
By adopting the technical scheme, the glue discharging temperature of 300-400 ℃ and the glue discharging time of 12-24 h are adopted, so that organic components in the ceramic green body can be discharged, and carbon residue cannot be generated to influence the performance of the ceramic product.
Optionally, the sintering temperature of the sintering is 550-850 ℃, the heat preservation time is 15 min-120 min, the sintering temperature rise rate is 15-35 ℃/min, the temperature reduction rate is 15-30 ℃/min, and the temperature is reduced to 22-28 ℃.
By adopting the technical scheme, a sintering temperature system of fast rising and fast falling is implemented, on one hand, the shrinkage deformation of the porous ceramic caused by the flowing of the inorganic bonding material in the ceramic blank due to the excessive melting of the inorganic bonding material can be avoided, and on the other hand, the temperature rising and falling speed can also avoid the phenomenon that the porous ceramic is cracked due to the thermal stress generated by the uneven heating inside and outside the product due to the too fast temperature reduction.
In summary, the present application has the following beneficial effects:
1. the main component of the ceramic is inorganic skeleton whisker, and the ceramic is matched with inorganic bonding material and inorganic bonding material
The organic filler material can form a network skeleton structure which can maintain the low sintering shrinkage rate of the ceramic.
2. The preferred inorganic skeleton whisker used in the application comprises SiC whisker and Al2O3Whisker and SiO2
One or more of the crystal whiskers and the AlN crystal whiskers can enhance the strength and toughness of the prepared porous ceramic.
3. The application relates to a preparation method of low-shrinkage porous ceramic, and the low-shrinkage porous ceramic obtained by the preparation method
The porous ceramic injection feeding can not only improve the performance of the ceramic, but also better keep the dispersion degree of the ceramic components, thereby being more beneficial to the increase of the strength of the ceramic, and increasing the reliability and the service life of the product.
4. The atomized product that this application preparation obtained, the size is unanimous, size and the corresponding unburned bricks size ratio after the ceramic forming sintering: 0.995-1.005, the shrinkage tends to be zero, the deviation of the ceramic size among batches is less than 0.5%, the mold forming size is the size of the sintered product, the aperture and the porosity of the atomized product are consistent with the designed aperture and porosity, the stability of the product can be improved, the porosity of the atomized product is controllable, and the product qualification rate is high and reaches more than 98%.
Examples
The present application will be described in further detail with reference to examples. Source of raw materials
SiC whisker: the product model is SiC-008, and the manufacturer is Shanghai Moguo nanotechnology Limited company;
Al2O3whisker: the product model is alumina whisker Al2O3Whiskers, manufacturer is Qinhuang Yinuo high new materials development Co., Ltd;
SiO2whisker: the product model is MG-SiO215, the manufacturer is Shanghai Moghai Nscience and technology limited;
AlN whiskers: the product model is hexagonal AlN whisker, and the manufacturer is the science and technology limited company of the new materials in Western Ans;
low-temperature glass powder: the product model is high-temperature coating film-forming additive low-temperature glass powder, and the manufacturer is Fushan crystal grain material science and technology company;
example 1
A low-shrinkage porous ceramic comprises the following raw materials: 40kg of SiC whisker, 5kg of low-temperature glass powder and ZrO25kg, 5kg of injection accelerator, 5kg of injection skeleton agent, 30kg of injection filler and 1kg of plasticizer, wherein dibutyl phthalate and pore-forming agent are selected in the embodiment.
The length of the whisker can be 3-30 um, the diameter of the whisker can be 1-3 um, the length-diameter ratio can be 1-30, the injection accelerator can be one or two of stearic acid and oleic acid, stearic acid is selected in the embodiment, the injection framework agent can be one or more of high-density polyethylene, medium-density polyethylene, low-density polyethylene and polypropylene, polypropylene is selected in the embodiment, the injection filler can be one of paraffin and acetal resin, paraffin is selected in the embodiment, the plasticizer can be one or more of dioctyl phthalate, dibutyl phthalate and diethyl phthalate, the pore-forming agent can be one or more of polymethyl methacrylate, starch and carbon powder, and polymethyl methacrylate is selected in the embodiment.
A low-shrinkage porous ceramic is prepared by the following steps: 40kg of SiC whisker and ZrO25kg of low-temperature glass powder is subjected to heat treatment at a high temperature of 650 ℃ for 4h, 5kg of low-temperature glass powder is dried at a temperature of 100 ℃ for 3h, then the treated components are placed in a ball milling tank, 300kg of zirconium balls with the diameter of 8mm are added, ball milling is carried out at a rotating speed of 150r/min for 2h, and the mixture is sieved by a 10-mesh screen after ball milling is finished to obtain ceramic component powder.
Adding 5kg of stearic acid, 30kg of polypropylene and 1kg of paraffin into an internal mixer for melting, stirring at the rotating speed of 20r/min for 30min and uniformly stirring after melting, slowly adding the uniformly ground ceramic component powder and 40kg of polymethyl methacrylate after uniformly stirring, stirring at the rotating speed of 20r/min for 30min, uniformly mixing the materials under the extrusion and shearing actions of the internal mixer, then carrying out internal mixing at the temperature of 80 ℃ for 3h, adding the internally mixed product into a granulator for granulation, and obtaining the injection molding feed with the granularity of 2 mm.
Adding injection molding feed into a sol device for sol dissolving, wherein the sol temperature can be selected from 60-200 ℃, the sol temperature is selected from 120 ℃ in the embodiment, injecting the sol into a mold at a certain injection molding pressure, wherein the injection molding pressure can be 2-50T, the injection molding pressure can be 35T in the embodiment, in order to avoid immediately solidifying the sol after injection, the mold needs to be kept at a certain temperature, which can be 50-250 ℃, and the injection molding pressure is selected from 160 ℃; the total time for putting the sol into a mold can be 1-15 s, 8s is selected in the embodiment, and the ceramic green body is obtained after automatic cooling and forming after injection molding.
Embedding the ceramic green body into corundum Al with the granularity of 500 meshes2O3And (3) burning the powder in a burying way, carrying out binder removal at the highest temperature of 380 ℃, increasing and decreasing the temperature of binder removal, keeping the temperature for 15h in total, putting the ceramic blank subjected to binder removal into a sintering furnace, heating to 800 ℃ at the heating rate of 15 ℃/min, sintering for 60min, then cooling to 22 ℃ at the speed of 30 ℃/min, and sieving the sintered product with a 30-mesh sieve to remove the buried burning powder, thereby obtaining the sintered atomized ceramic.
The atomization ceramic is subjected to jolting, boiling and drying, wherein the jolting frequency can be 20-40 KHz, the jolting frequency is preferably 35KHz, the jolting time can be 10-60 min, the boiling temperature can be 95-100 ℃, the boiling time can be 98 ℃, the boiling time can be 2-8 h, the drying temperature can be 100-250 ℃, the drying time can be 180 ℃, the drying time can be 2-8 h, the drying time is preferably 6h, and the moisture content of the dried atomization ceramic product is less than 0.1%.
Example 2
The difference from example 1 is that: 56kg of SiC whisker, 7kg of low-temperature glass powder and ZrO27kg, 1kg of injection accelerator, 20kg of injection skeleton agent, 12kg of injection filler, 5kg of plasticizer and 10kg of pore-forming agent.
Example 3
The difference from example 1 is that: 48kg of SiC whisker, 6kg of low-temperature glass powder and ZrO26kg, 2.5kg of injection accelerator, 15kg of injection skeleton agent, 21kg of injection filler, 2.5kg of plasticizer and 25kg of pore-forming agent.
Example 4
The difference from example 3 is that: al (Al)2O348Kg of whiskers, 6Kg of phosphate and SiO26Kg。
Example 5
The difference from example 3 is that: SiO 2248kg of whiskers, 6kg of low-temperature glass powder and 6kg of MgO.
Example 6
The difference from example 3 is that: al (Al)2O320kg of crystal whisker, 28kg of AlN crystal whisker totally, 6kg of low-temperature glass powder and Al2O32kg and ZnO4 kg.
Example 7
The difference from example 3 is that: al (Al)2O320kg of crystal whisker, 28kg of AlN crystal whisker, 6kg of low-temperature glass powder and phosphate, and ZrO21kg、SiO23kg and CaO2 kg.
Example 8
The difference from example 6 is that: al (Al)2O310kg of crystal whisker, 17kg of AlN crystal whisker, 27kg of low-temperature glass powder and Al2O32kg and ZnO4 kg.
Example 9
The difference from example 6 is that: al (Al)2O315kg of whiskers, 21kg of AlN whiskers, 15kg of low-temperature glass powder and Al2O35kg、ZnO4kg。
Example 10
The difference from example 6 is that: al (Al)2O320kg of crystal whisker, 28kg of AlN crystal whisker, 9kg of low-temperature glass powder and Al2O31kg、ZnO2kg。
Example 11
Mixing Al2O336kg of whisker and AlN whisker and Al2O34kg and 5kg of ZnO are subjected to heat treatment at the high temperature of 700 ℃ for 3h, 15kg of low-temperature glass powder is dried at the temperature of 100 ℃ for 4h, then the treated components are placed in a ball milling tank, 300kg of zirconium balls with the diameter of 8mm are added, ball milling is carried out at the rotating speed of 100r/min for 2h, and the materials are sieved by a 10-mesh screen after ball milling is finished to obtain ceramic component powder.
Adding 2.5kg of stearic acid, 15kg of polypropylene, 21kg of paraffin and 2.5kg of dibutyl phthalate into an internal mixer for melting, stirring uniformly at the rotating speed of 15r/min for 30min after melting, adding 25kg of uniformly ground ceramic component powder and polymethyl methacrylate after stirring uniformly, stirring at the rotating speed of 15r/min for 30min, mixing the materials uniformly under the extrusion and shearing actions of the internal mixer, then carrying out internal mixing at the temperature of 60 ℃ for 4h, adding the internally mixed product into a granulator for granulation, and obtaining the injection molding feed with the granularity of 1 mm.
Adding injection molding feed into a sol device for sol dissolving, wherein the sol temperature can be selected from 60-200 ℃, 60 ℃ is selected in the embodiment, and then injecting the sol into a mold at a certain injection pressure, wherein the injection pressure can be 2-50T, 35T is selected in the embodiment, in order to avoid immediately solidifying the injected sol, the mold needs to be kept at a certain temperature, which can be 50-250 ℃, and 160 ℃ is selected in the embodiment; the total time for putting the sol into a mold can be 1-15 s, 8s is selected in the embodiment, and the ceramic green body is obtained after automatic cooling and forming after injection molding.
Embedding the ceramic green body into corundum Al with the granularity of 500 meshes2O3And (3) carrying out gel removal in the buried burning powder at the highest temperature of 400 ℃, wherein the total temperature rise and fall time and the heat preservation time are 12h, putting the ceramic green body subjected to gel removal into a sintering furnace, heating to 850 ℃ at the heating rate of 15 ℃/min, sintering for 15min, then cooling to 22 ℃ at the speed of 30 ℃/min, and sieving a sintered product through a 30-mesh sieve to remove the buried burning powder, thereby obtaining the sintered atomized ceramic.
The atomization ceramic is subjected to jolting, boiling and drying, wherein the jolting frequency can be 20-40 KHz, the jolting frequency is preferably 35KHz, the jolting time can be 10-60 min, the boiling temperature can be 95-100 ℃, the boiling time can be 98 ℃, the boiling time can be 2-8 h, the drying temperature can be 100-250 ℃, the drying time can be 180 ℃, the drying time can be 2-8 h, the drying time is preferably 6h, and the moisture content of the dried atomization ceramic product is less than 0.1%.
Example 12
Mixing Al2O336kg of whisker and AlN whisker and Al2O34kg of ZnO and 5kg of ZnO are subjected to heat treatment at the high temperature of 950 ℃, the heat treatment time is 1h, and the glass is low in temperatureDrying 15kg of powder at 250 ℃ for 2h, then placing the treated components in a ball milling tank, adding 120kg of zirconium balls with the diameter of 12mm, carrying out ball milling at the rotating speed of 350r/min for 6h, and sieving through a 10-mesh sieve after ball milling to obtain ceramic component powder.
Adding injection molding feed into a sol device for sol, wherein the sol temperature can be selected from 60-200 ℃, and the sol temperature is selected from 200 ℃ in the embodiment.
Adding 2.5kg of stearic acid, 15kg of polypropylene, 21kg of paraffin and 2.5kg of dibutyl phthalate into an internal mixer for melting, stirring uniformly at the rotating speed of 60r/min for 60min after melting, adding 25kg of uniformly ground ceramic component powder and polymethyl methacrylate after stirring uniformly, stirring at the rotating speed of 60r/min for 60min, mixing the materials uniformly under the extrusion and shearing actions of the internal mixer, then carrying out internal mixing at the temperature of 200 ℃ for 1h, adding the internally mixed product into a granulator for granulation, and obtaining the injection-molded feed with the granularity of 3 mm.
Embedding the ceramic green body into corundum Al with the granularity of 1200 meshes2O3And (3) carrying out gel removal in the buried burning powder at the highest temperature of 300 ℃, wherein the gel removal temperature rise and fall time and the heat preservation time are 24h in total, putting the ceramic blank subjected to gel removal into a sintering furnace, heating to 550 ℃ at the heating rate of 35 ℃/min, sintering for 120min, then cooling to 28 ℃ at the speed of 15 ℃/min, and sieving the sintered product with a 30-mesh sieve to remove the buried burning powder, thereby obtaining the sintered atomized ceramic.
The rest is the same as in example 11.
Example 13
Mixing Al2O336kg of whisker and AlN whisker and Al2O34kg and 5kg of ZnO are subjected to heat treatment at the high temperature of 800 ℃ for 3h, 15kg of low-temperature glass powder is dried at the temperature of 150 ℃ for 1h, then the treated components are placed in a ball milling tank, 120kg of zirconium balls with the diameter of 10mm are added, ball milling is carried out at the rotating speed of 200r/min for 4h, and the materials are sieved by a 10-mesh screen after ball milling is finished to obtain ceramic component powder.
Adding injection molding feed into a sol device for sol, wherein the sol temperature can be selected from 60-200 ℃, and the temperature is selected from 120 ℃ in the embodiment.
Adding 2.5kg of stearic acid, 15kg of polypropylene, 21kg of paraffin and 2.5kg of dibutyl phthalate into an internal mixer for melting, stirring at the rotating speed of 40r/min for 50min after melting, stirring uniformly, adding 25kg of uniformly ground ceramic component powder and polymethyl methacrylate, stirring at the rotating speed of 40r/min for 50min, mixing the materials uniformly under the extrusion and shearing actions of the internal mixer, then carrying out internal mixing at the temperature of 150 ℃ for 2h, adding the internally mixed product into a granulator for granulation, and obtaining the injection molding feed with the granularity of 2 mm.
Embedding the ceramic green body into corundum Al with the granularity of 1000 meshes2O3And (3) burning the powder in a burying way, carrying out binder removal at the highest temperature of 350 ℃, wherein the binder removal heating and cooling time and the heat preservation time are 18h in total, putting the ceramic blank subjected to binder removal into a sintering furnace, heating to 680 ℃ at the heating rate of 25 ℃/min, sintering for 100min, then cooling to 25 ℃ at the speed of 20 ℃/min, and sieving the sintered product with a 30-mesh sieve to remove the buried burning powder, thereby obtaining the sintered atomized ceramic.
The rest is the same as in example 11.
Example 14
And putting the ceramic green body after the binder removal into a sintering furnace, heating to 550 ℃ at the heating rate of 15 ℃/min, sintering for 120min, then cooling to 22 ℃ at the speed of 30 ℃/min, and sieving a sintered product with a 30-mesh sieve to remove the embedded sintering powder to obtain the sintered atomized ceramic.
The rest is the same as in example 13.
Example 15
And placing the ceramic green body after the binder removal into a sintering furnace, heating to 850 ℃ at the heating rate of 35 ℃/min, sintering for 120min, then cooling to 22 ℃ at the speed of 30 ℃/min, and sieving a sintered product with a 30-mesh sieve to remove the embedded sintering powder to obtain the sintered atomized ceramic.
The rest is the same as in example 13.
Comparative example
Comparative example 1
The difference from example 3 is that: 18kg of SiC whisker, 24kg of low-temperature glass powder and Al2O3 18kg。
Comparative example 2
The difference from example 3 is that: 54kg of SiC whisker, 4kg of low-temperature glass powder and Al2O3 2kg。
Comparative example 3
The difference from example 3 is that: SiO 2219kg、Al2O319kg of SiC10kg, 6kg of low-temperature glass powder, ZrO26kg。
Comparative example 4
The difference from example 3 is that: 48kg of SiC whisker and 6kg of low-temperature glass powder.
Comparative example 5
Placing the ceramic green body after the binder removal into a sintering furnace, sintering for 100min at 680 ℃, naturally cooling, sieving a sintered product with a 30-mesh sieve to remove embedded sintering powder after cooling, and obtaining sintered atomized ceramic, wherein the rest is the same as the embodiment 13.
Comparative example 6
And (3) placing the ceramic green body after the glue discharging into a sintering furnace, heating to 680 ℃ at a heating rate of 50 ℃/min, sintering for 100min, and then cooling to 25 ℃ at a speed of 40 ℃/min. The rest is the same as in example 13.
Comparative example 7
And (3) placing the ceramic green body after the glue discharging into a sintering furnace, heating to 680 ℃ at a heating rate of 10 ℃/min, sintering for 100min, and then cooling to 25 ℃ at a speed of 10 ℃/min. The rest is the same as in example 13.
Comparative example 8
The method comprises the steps of mixing 25kg of silicon dioxide micro powder, 15kg of silicon dioxide aerogel and 10kg of quartz fiber serving as raw materials and 20kg of water glass serving as a binding agent on a ball mill for 2 hours, and then adding 5% of a binding agent into mixed powder to be rolled uniformly. The sample is formed by a semidry method, the specification of the sample is 100mm multiplied by 15mm, and the forming pressure is 100 MPa. The sample was dried at 110 ℃ for 24 hours, then heat-treated at 900 ℃ and kept warm for 3 hours to obtain a porous ceramic.
Performance test
Measuring the dimensions of the ceramic formed and sintered of examples 1 to 15 and comparative examples 1 to 7 and the corresponding green body dimensions, calculating and recording the ratio of the dimensions of the ceramic formed and sintered to the corresponding green body dimensions, thereby determining the shrinkage; the strength and thermal conductivity of the ceramics after molding and sintering of the ceramics of examples 1 to 15 and comparative examples 1 to 7 were examined. The strength is measured according to GBT 8489-2006 fine ceramic compression strength test method, the thermal conductivity is measured according to the standard GB/T17911.8-2002 refractory ceramic fiber product thermal conductivity test method, and the measurement results are detailed in Table 1.
The result of the detection
TABLE 1 porous ceramic Properties statistics
Ratio of Shrinkage (%) Strength (N/mm)2） Thermal conductivity (W/(m.K))
Example 1 0.9958 0.42 58.22 10.25
Example 2 0.9964 0.36 60.37 12.16
Example 3 0.9990 0.10 80.58 11.66
Example 4 0.9985 0.15 75.89 15.36
Example 5 0.9987 0.13 77.56 9.28
Example 6 0.9993 0.07 83.48 13.36
Example 7 0.9991 0.09 82.79 8.84
Example 8 0.9988 0.12 78.64 16.22
Example 9 0.9994 0.06 84.71 14.17
Example 10 0.9992 0.08 82.27 8.26
Example 11 0.9995 0.05 85.39 16.15
Example 12 0.9994 0.06 84.26 15.61
Example 13 0.9997 0.03 85.18 17.98
Example 14 0.9995 0.05 84.27 9.74
Example 15 0.9996 0.04 85.37 10.15
Comparative example 1 0.9612 3.88 41.25 5.28
Comparative example 2 0.8923 10.77 45.31 4.34
Comparative example 3 0.8842 11.58 22.65 2.86
Comparative example 4 0.8463 15.37 46.57 3.55
Comparative example 5 0.8011 19.89 50.38 6.38
Comparative example 6 0.8315 16.85 48.29 7.26
Comparative example 7 0.7952 20.48 49.66 6.15
Comparative example 8 0.8836 11.64 24.96 2.96
As can be seen from the combination of examples 1-3, the ceramic components, the injection accelerator, the injection skeleton agent, the injection filler, the plasticizer and the pore-forming agent are in different proportions, and example 3 is the best, namely 48kg of SiC whisker, 6kg of low-temperature glass powder and ZrO2The shrinkage rate of the porous ceramic prepared by 6kg, 2.5kg of injection accelerator, 15kg of injection skeleton agent, 21kg of injection filler, 2.5kg of plasticizer and 25kg of pore-forming agent is 0.1 percent at the lowest.
In connection with examples 4-7, it can be seen that different inorganic framework whiskers, inorganic binder material and inorganic filler material in the ceramic composition also affect the shrinkage of the porous ceramic, wherein in examples 4-6, example 6 is optimal, i.e. the ceramic composition is added in an amount of Al2O320kg of crystal whisker, 28kg of AlN crystal whisker totally, 6kg of low-temperature glass powder and Al2O3The shrinkage of the porous ceramic prepared from 2kg and ZnO4kg was 0.07% at the lowest.
It can be seen from the combination of examples 8-10 that different ratios of the inorganic skeleton whiskers, the inorganic binder and the inorganic filler also affect the shrinkage of the porous ceramic, wherein in examples 7-9, example 9 is the most preferable, i.e. Al is selected to be added2O315kg of crystal whisker, 21kg of AlN crystal whisker and low-temperature glass15kg of powder, Al2O3The shrinkage of the porous ceramic prepared from 5kg and ZnO4kg is 0.06% at the lowest.
In examples 11-13, the shrinkage of the porous ceramic obtained by using the process parameters of the preparation process of example 13 was 0.03% at the lowest, as can be seen from the combination of examples 11-13, wherein different process parameters all affect the shrinkage of the ceramic.
Combining with examples 13-15, it can be seen that different temperature control measures can affect the shrinkage rate of the finally obtained porous ceramic during the sintering process, and in examples 13-15 of the present application, the temperature control measure of example 13, that is, the ceramic green body after glue removal, is placed in a sintering furnace, heated to 680 ℃ at a heating rate of 25 ℃/min for sintering for 100min, and then cooled to 25 ℃ at a cooling rate of 20 ℃/min, so that the shrinkage rate of the prepared porous ceramic is at least 0.03%.
By combining examples 1 to 13 and comparative example 8, wherein comparative example 8 is a preparation method of porous ceramic commonly used in the prior art, it can be seen that the porous ceramic prepared by the technical scheme of the application has significantly improved shrinkage and strength compared with the porous ceramic in the prior art.
As can be seen by combining examples 1 to 10 and comparative examples 1 to 4 with Table 1, the ceramic component added in the present application, in which the inorganic skeleton whiskers mainly include SiC whiskers, Al2O3Whisker and SiO2One or more of crystal whiskers and AlN crystal whiskers are added, the adding amount of the crystal whiskers and the AlN crystal whiskers is 45-80% of the mass of the ceramic component, inorganic bonding material low-temperature glass powder is added, the adding amount of the inorganic bonding material low-temperature glass powder is 10-45% of the mass of the ceramic component, and inorganic filling material Al is added2O3、ZnO、ZrO2、SiO2One or more of MgO and CaO, the addition amount of which is 5-15% of the mass of the ceramic components, and the shrinkage rate of the porous ceramic can be reduced by reasonable proportion under the combined action of the three components, so that the shrinkage rate of the ceramic is less than 0.5%. And adding 60 percent of inorganic framework whisker Al based on the mass of the ceramic component2O3Crystal whisker and AlN crystal whisker, 25 percent of adhesive low-temperature glass powder of the mass of ceramic group component and 25 percent of inorganic filling material Al of the mass of ceramic group component2O315% in total with ZnO, and a shrinkage ratio thereofA minimum of only 0.06% was reached.
By combining the examples 11 to 15 and the comparative examples 5 to 7 and combining the table 1, it can be seen that the sintering shrinkage can be well reduced by the preparation method, and the sintering temperature control scheme of heating to 550-850 ℃ at a heating rate of 15-35 ℃/min for sintering for 15-120 min and then cooling to 22-28 ℃ at a speed of 15-30 ℃/min can avoid shrinkage deformation of the porous ceramic due to melting of the inorganic bonding material, and can avoid cracking caused by nonuniform heating inside and outside due to too fast cooling, and can effectively reduce the shrinkage of the porous ceramic.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. A low shrinkage porous ceramic composition characterized by: the ceramic component comprises the following raw materials: inorganic framework whisker, inorganic bonding material and inorganic filling material.
2. The low shrinkage porous ceramic composition of claim 1, wherein: the inorganic framework whisker accounts for 45-80% of the mass of the ceramic component, the inorganic bonding material accounts for 10-45% of the mass of the ceramic component, and the inorganic filling material accounts for 5-15% of the mass of the ceramic component.
3. The low shrinkage porous ceramic composition of claim 1, wherein: the inorganic framework whisker comprises SiC whisker and Al2O3Whisker and SiO2One or more of crystal whisker and AlN crystal whisker.
4. The low shrinkage porous ceramic composition of claim 1, wherein: the inorganic bonding material is low-temperature glass powder with the melting point of 500-800 ℃ and the fineness of 500-2000 meshes.
5. The low shrinkage porous ceramic composition of claim 1, wherein: the inorganic filler material comprises Al2O3、ZnO、ZrO2、SiO2One or more of MgO and CaO.
6. A low-shrinkage porous ceramic injection feed is characterized in that: the ceramic material comprises, by weight, 50-70% of a ceramic component and 29-60% of an organic component.
7. A low shrinkage porous ceramic injection feed as defined in claim 6, wherein: the organic component comprises, by weight, 1-5% of an injection accelerator, 5-10% of an injection skeleton agent, 12-20% of an injection filler, 1-5% of a plasticizer and 10-20% of a pore-forming agent.
8. A preparation method of low-shrinkage porous ceramic is characterized by comprising the following steps:
(1) drying the inorganic bonding material at the temperature of 100-250 ℃ for 1-5 h; carrying out heat treatment on the inorganic framework material and the inorganic filling material at a high temperature of 650-950 ℃ for 1-4 h;
(2) adding a ball milling medium into the ceramic component treated in the step (1) for ball milling, and sieving the ceramic component by a 10-mesh sieve after the ball milling to obtain ball-milled ceramic component powder;
(3) heating and melting an injection accelerator, an injection skeleton agent, an injection filler and a plasticizer;
(4) adding the ceramic component powder subjected to ball milling in the step (2) and a pore-forming agent into the melted product in the step (3) for banburying;
(5) granulating a product obtained by banburying in the step (4) to obtain injection molding feed;
(6) performing injection molding on the injection molding feed obtained in the step (5) to obtain a ceramic green body;
(7) burying the ceramic green body obtained in the step (6) into a ceramic green body with the particle size of 500-1200 meshesCorundum Al2O3Carrying out glue discharging in the buried burning powder;
(8) sintering the ceramic green body subjected to the rubber discharge in the step (7);
(9) sieving the product obtained in the step (8) by a 30-mesh sieve to remove the buried sintering powder, and obtaining the sintered atomized ceramic;
(10) and (4) carrying out post-treatment on the sintered atomized ceramic obtained in the step (9) to obtain an atomized ceramic product.
9. The method for preparing a low shrinkage porous ceramic according to claim 8, wherein: and (7) discharging the glue at the glue discharging temperature of 300-400 ℃ for 12-24 h.
10. The method for preparing a low shrinkage porous ceramic according to claim 8, wherein: and (4) sintering, wherein the sintering temperature is 550-850 ℃, the heat preservation time is 15 min-120 min, the sintering temperature rise rate is 15-35 ℃/min, the temperature reduction rate is 15-30 ℃/min, and the temperature is reduced to 22-28 ℃.
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CN111153686A (en) * 2020-01-14 2020-05-15 东莞市陶陶新材料科技有限公司 Porous ceramic for electronic cigarette, atomizing core containing porous ceramic and preparation method of atomizing core
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US8076185B1 (en) * 2006-08-23 2011-12-13 Rockwell Collins, Inc. Integrated circuit protection and ruggedization coatings and methods
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CN113880603A (en) * 2021-11-11 2022-01-04 深圳市汉清达科技有限公司 Porous ceramic composition and preparation method thereof

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