CN118495958A - Method for preparing ceramic by enhanced gel injection molding - Google Patents
Method for preparing ceramic by enhanced gel injection molding Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000001746 injection moulding Methods 0.000 title claims abstract description 21
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 73
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000002002 slurry Substances 0.000 claims abstract description 47
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000000375 suspending agent Substances 0.000 claims abstract description 7
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 38
- 229910052582 BN Inorganic materials 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 15
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 8
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- 239000002245 particle Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 229910052580 B4C Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000001272 pressureless sintering Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 5
- 229920002678 cellulose Polymers 0.000 description 19
- 239000001913 cellulose Substances 0.000 description 19
- 239000002114 nanocomposite Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
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- 238000000465 moulding Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
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- 238000005452 bending Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
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- 239000004459 forage Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The application relates to a method for preparing ceramic by enhanced gel injection molding, which comprises the following steps: centrifuging the modified nano cellulose composite component, mixing the treated modified nano cellulose composite component with deionized water, adding acrylamide after ultrasonic treatment, stirring to obtain a suspension, adding N, N' -methylenebisacrylamide, a dispersing agent, a defoaming agent and a suspending agent into the suspension, and stirring to obtain a premix; adding ceramic powder and a sintering aid into the premix, stirring to obtain a prefabricated slurry, ball-milling the prefabricated slurry, vacuum defoaming, vibrating at a frequency of 5-10Hz during vacuum defoaming, and vacuum defoaming to obtain the slurry; adding a catalyst and an initiator into the slurry, stirring, pouring into a mold, and drying at constant temperature and constant humidity after the slurry is molded to obtain a blank; sintering the blank body, and preserving heat to obtain the silicon carbide ceramic product. The application has the effects of reducing the cracking of the blank and improving the strength of the product.
Description
Technical Field
The application relates to the field of ceramic preparation, in particular to a method for preparing ceramic by enhanced gel injection molding.
Background
In recent years, new colloidal molding such as press molding, gel casting machine direct solidification injection molding, and the like, in-situ solidification is an effective method for producing highly reliable, complex-shaped ceramic parts, and gel casting has been widely studied in the fields of porous materials, composite materials, functional materials; silicon carbide ceramics have excellent normal temperature mechanical properties such as high flexural strength, excellent oxidation resistance, good corrosion resistance, high abrasion resistance, and low coefficient of friction, and high temperature mechanical properties (strength, creep resistance, etc.) are the best of the known ceramic materials. The high temperature strength of the material sintered by hot pressing, pressureless sintering and hot isostatic pressing can be maintained to 1600 ℃, and the material with the best high temperature strength in ceramic materials is the material with the best high temperature strength, so that the product has very wide application in the heating and heat exchange industrial field.
However, microcrack and deformation occur during gel injection molding, and the biggest reason is that the gel drying condition is harsh; for sintering densification of ceramics, ultrafine powder is often used as a main raw material, slurry with high solid content of the ultrafine powder is difficult to obtain, for example, pressureless sintered silicon carbide is basically ultrafine powder, even if the solid content is only about 55% (VOL) after powder modification, the strength of a wet blank is very low, and cracking phenomenon is easy to occur.
Disclosure of Invention
In order to reduce the cracking phenomenon of gel-casting ceramic, the application provides a method for preparing ceramic by enhanced gel-casting.
The method for preparing the ceramic by the enhanced gel injection molding adopts the following technical scheme:
a method for preparing ceramic by enhanced gel injection molding comprises the following steps:
Preparing a premix: carrying out high-speed centrifugal treatment on the modified nano cellulose composite component to obtain treated modified nano cellulose composite component, mixing the treated modified nano cellulose composite component with deionized water, adding acrylamide into the mixture after ultrasonic treatment, stirring the mixture to obtain a suspension, adding N, N' -methylenebisacrylamide, a dispersing agent, a defoaming agent and a suspending agent into the suspension, and stirring the mixture to obtain a premix;
preparing slurry: adding ceramic powder and a sintering aid into the obtained premix, stirring to obtain a prefabricated slurry, ball-milling the prefabricated slurry, vacuum defoaming, vibrating at a frequency of 5-10Hz during vacuum defoaming, and vacuum defoaming to obtain the slurry;
Preparing a blank: adding a catalyst and an initiator into the slurry, stirring, pouring into a mold, and drying at constant temperature and constant humidity after the slurry is molded to obtain a blank;
Preparing silicon carbide ceramics: sintering the blank body, and preserving heat to obtain the silicon carbide ceramic product.
By adopting the technical scheme, the wet green body strength obtained by the method is improved, the modified nano cellulose composite component has good mechanical property, a stable gel network structure is formed between the modified nano cellulose composite component and the slurry component, fine fiber filaments exist between pores of the gel network structure, so that the slurry can be better contacted, the connection tightness between gel column-shaped green bodies is effectively improved, the cracking phenomenon of the prepared gel injection-molded green bodies is improved, and the quality and strength of the prepared silicon carbide ceramic product are improved.
Preferably, the sintering aid comprises one or both of carbon black and boron carbide, and the silicon carbide ceramic powder comprises one or both of primary silicon carbide powder particles and secondary silicon carbide powder particles.
Preferably, in the step of preparing the silicon carbide ceramic, green body sintering adopts pressureless sintering; the mass ratio of the silicon carbide ceramic powder to the carbon black to the boron carbide is (48-49) 1:0.3.
Preferably, in the step of preparing the silicon carbide ceramic, the green body sintering adopts reaction sintering; the mass ratio of the primary carbonized powder particles to the secondary carbonized silicon powder particles to the sintering aid is 1.5:1 (0.25-0.3).
By adopting the technical scheme, the pressureless sintered silicon carbide ceramic can be prepared by using the method, and structural ceramics of various materials such as reaction sintered silicon carbide, silicon nitride, aluminum oxide and the like can also be prepared; under different sintering methods, different sintering aids and silicon carbide ceramic powder are preferably proportioned, the stability of the prepared slurry is improved, and the quality and strength of the ceramic silicon carbide product obtained in the subsequent sintering process can be further improved.
Preferably, the acrylamide accounts for 0.03-0.05% of the total weight of the slurry, the catalyst accounts for 0.005-0.007% of the total weight of the blank, and the initiator accounts for 0.03-0.05% of the total weight of the blank.
By adopting the technical scheme, the stability of the prepared blank can be effectively improved by optimizing each component in the system within the mass range, so that the quality of the prepared ceramic product is improved.
Preferably, the modified nano-cellulose composite component accounts for 12-14% of the total mass of the slurry.
By adopting the technical scheme, the preferable ratio of the modified nanocellulose component is within the above range, so that the stability and the product strength of the prepared slurry can be further improved.
Preferably, the modified nanocellulose composite component comprises hydroxylated boron nitride, nanocellulose and polyethyleneimine.
By adopting the technical scheme, the hydroxylated boron carbide is of a layered structure, and has high heat conduction performance, thermal stability and oxidation resistance; the nanocellulose has the advantages of biodegradability, regenerability and excellent mechanical properties, and can enable the connection between each component in the slurry to be more compact; the polyethyleneimine is a branched polymer with a large number of amino groups on a molecular chain, has the advantages of functional filler and improving the interface performance of the composite material, and can cooperatively improve the integral strength of the modified nano cellulose composite component by combining the three components, so that the stability of the prepared nano cellulose composite component is improved, and the combination of all components in a green body is tighter, thereby improving the product quality and strength of the prepared green body material.
Preferably, the modified nanocellulose is prepared by the following method:
Mixing nanocellulose with deionized water to obtain nanocellulose suspension, adding hydroxylated boron nitride, performing ultrasonic treatment to obtain composite dispersion, performing suction filtration, and drying to obtain nanocellulose-boron nitride composite material;
And (3) regulating the pH value of the polyethyleneimine to be alkaline, adding the nanocellulose-boron nitride composite material, heating, stirring for reaction, centrifuging to obtain a prefabricated compound, mixing the composite prefabricated compound with deionized water, filtering, suction filtering, and freeze-drying to obtain the modified nanocellulose.
By adopting the technical scheme, the nanocellulose and the hydroxylation boron nitride are compounded to prepare the nanocellulose-boron nitride composite material, so that the compatibility between the nanocellulose and the hydroxylation boron nitride is improved, and the overall human stability of the system can be further improved; the nanocellulose-boron nitride composite material is modified to polyethyleneimine, so that a large amount of amino groups are attached to the surface of the nanocellulose-boron nitride composite forage, the hydrogen bond density is reduced, the overall stability of the modified nanocellulose is improved, the strength of the composite material is enhanced, and the quality of a ceramic product prepared is improved.
Preferably, the mass ratio of the boron oxynitride, the nanocellulose and the polyethyleneimine is (0.42-0.48) 1:0.67.
By adopting the technical scheme, the mass ratio of the hydroxylated boron nitride, the nanocellulose and the polyethyleneimine is preferably within the range, so that the stability of the prepared nanocellulose composite material can be further improved.
Preferably, the hydroxylated boron nitride is prepared by the following method:
Mixing boron nitride with sodium hydroxide solution for hydrolysis, centrifugally washing, mixing with deionized water, ultrasonically centrifuging, taking supernatant, and performing suction filtration and drying to obtain hydroxylated boron nitride.
By adopting the technical scheme, the boron nitride is subjected to alkali treatment, and the liquid phase auxiliary ultrasonic is combined to prepare the hydroxylated boron nitride, so that the hydroxyl functional groups are modified on the surface, the dispersibility of the boron nitride in a system is improved, the compatibility among the boron nitride, the nanocellulose and the polyethyleneimine is improved, the compactness of the prepared slurry is further improved, and the quality and the strength of ceramic products are improved.
In summary, the present application includes at least one of the following beneficial technical effects:
Adding modified nano cellulose composite components into the slurry, constructing a stable gel network structure between the slurries, and forming tiny fiber filaments between gaps of the gel network structure, so that the connection tightness between the components of the slurry system is improved, the cracking phenomenon of a gel injection molded blank is improved, and the strength and quality of a ceramic product are further improved;
The application can prepare pressureless sintered silicon carbide ceramics, also can prepare structural ceramics made of various materials such as reaction sintered silicon carbide, silicon nitride, aluminum oxide and the like, and the wet blank prepared by adjusting the components and the proportion of the sintering auxiliary agent and the silicon carbide ceramic powder to adapt to different sintering conditions has high strength and strong stability;
The modified nanocellulose component obtained by compounding the hydroxylated boron nitride, the nanocellulose and the polyethyleneimine can play a role in cooperatively improving the strength of the green body after compounding, the combination of the components in the green body is tighter, and the components can be dispersed in a system more uniformly, so that the stability of the green body is improved, and the quality of a ceramic product obtained by the preparation is improved.
Detailed Description
The application is further illustrated by the following examples:
Material description: the dispersing agent is obtained by mixing DolaPIX CE and MQ-5088 according to the mass ratio of 1:1; the defoamer is n-octanol (CAS number: 111-87-5); the suspending agent is MQ-818; the catalyst is tetramethyl ethylenediamine; the initiator is an ammonium persulfate aqueous solution with the mass fraction of 5%; the length of the nanocellulose is 400-500nm, and the width is 4-5nm. The length-diameter ratio is 80-125.
Examples
Preparing a nanocomposite cellulose component:
Dispersing boron nitride powder in 5mol/L sodium hydroxide solution, hydrolyzing for 24 hours at 120 ℃, centrifuging after hydrolysis, repeatedly washing with deionized water for three times to remove residual sodium hydroxide, dispersing the washed boron nitride powder in 800ml deionized water, performing ultrasonic treatment in an ultrasonic dispersing instrument for 16 hours, centrifuging the obtained suspension at 2000rpm for 5 minutes after ultrasonic treatment to remove unpeeled boron nitride, vacuum-filtering the obtained supernatant, and drying for 12 hours at 60 ℃ to obtain hydroxylated boron nitride.
And dispersing 239.23g of nanocellulose in deionized water, stirring at 500rpm for 30min, performing ultrasonic treatment for 5min to obtain nanocellulose dispersion, adding 100.48g of prepared hydroxylated boron nitride into the nanocellulose dispersion, stirring at 500rpm for 60min, performing ultrasonic treatment for 30min to obtain mixed solution, filtering the mixed solution through a cellulose acetate microporous filter membrane with the pore diameter of 0.22 mu m, performing vacuum-assisted suction filtration, and drying the obtained solid for 12h at 60 ℃ to obtain the boron nitride-nanocellulose composite component.
And (3) regulating the pH value of 160.29g of polyethyleneimine to 10, mixing the boron nitride-nanocellulose composite component prepared by the method with 1000ml of deionized water, adding polyethyleneimine, heating to 100 ℃ and stirring at 200rpm for reaction for 10 hours, centrifuging the reacted solution for 10 minutes, discharging supernatant, repeating for 3 times, adding 1000ml of deionized water again for dispersion, carrying out suction filtration through a 100nm filter membrane, and transferring to the environment of-20 ℃ for freeze drying for 24 hours to obtain the nanocomposite cellulose component.
The ceramic prepared by enhanced gel injection molding is prepared by the following method:
Preparing a premix: and (3) carrying out high-speed centrifugal treatment on 240g of the composite nano cellulose component at a speed of 12500r/min for 10min to obtain a treated composite nano cellulose component, mixing the treated composite nano cellulose component with 300g of deionized water, carrying out ultrasonic vibration for 20min, adding 56g of acrylamide, continuing stirring for 2h to obtain a suspension, sequentially adding 8g of N, N' -methylenebisacrylamide, 40g of dispersing agent, 10g of defoaming agent and 10g of suspending agent into the suspension, and stirring for 2h to obtain a premix.
Preparing slurry: 768g of F240 silicon carbide powder, 512g of F1200 silicon carbide powder and 153.6g of carbon black are sequentially added into the premix liquid, stirring is carried out for 15min at a rotating speed of 2000rpm, the prefabricated slurry is obtained, ball milling is carried out on the prefabricated slurry for 12h, the ball milling rotating speed is 50r/min, then vacuum defoaming is carried out for 10min, and vibration treatment is carried out on the defoaming and the frequency of 5Hz at the same time, thus obtaining the slurry.
Preparing a blank: adding 0.1g of catalyst and 0.8g of initiator into the slurry, stirring at 6000rpm for 3min at 15 ℃, pouring into a mold, and molding, wherein the molded green body is kept at 40 ℃ and dried at 40% humidity, and the drying system is low temperature, high humidity and low humidity, so as to obtain the green body.
Preparing silicon carbide ceramics: and (3) performing reaction sintering on the dried green body at 1700 ℃, and preserving heat for 5 hours to obtain the silicon carbide ceramic product.
Examples
Preparing a nanocomposite cellulose component:
Dispersing boron nitride powder in 5mol/L sodium hydroxide solution, hydrolyzing for 24 hours at 120 ℃, centrifuging after hydrolysis, repeatedly washing with deionized water for three times to remove residual sodium hydroxide, dispersing the washed boron nitride powder in 800ml deionized water, performing ultrasonic treatment in an ultrasonic dispersing instrument for 16 hours, centrifuging the obtained suspension at 2000rpm for 5 minutes after ultrasonic treatment to remove unpeeled boron nitride, vacuum-filtering the obtained supernatant, and drying for 12 hours at 60 ℃ to obtain hydroxylated boron nitride.
232.56G of nanocellulose is dispersed in deionized water, stirred for 30min at a rotating speed of 500rpm and subjected to ultrasonic treatment for 5min to obtain nanocellulose dispersion, 111.63g of prepared hydroxylated boron nitride is added into the nanocellulose dispersion, stirred for 60min at a rotating speed of 500rpm, then subjected to ultrasonic treatment for 30min to obtain mixed liquor, the mixed liquor is filtered through a cellulose acetate microporous filter membrane with a pore diameter of 0.22 mu m, and vacuum assisted suction filtration is carried out, and the obtained solid is dried for 12h at 60 ℃ to obtain the boron nitride-nanocellulose composite component.
And (3) regulating the pH value of 155.81g of polyethyleneimine to 10, mixing the boron nitride-nanocellulose composite component prepared by the method with 1000ml of deionized water, adding polyethyleneimine, heating to 100 ℃ and stirring at 200rpm for reaction for 10 hours, centrifuging the reacted solution for 10 minutes, discharging supernatant, repeating for 3 times, adding 1000ml of deionized water again for dispersion, carrying out suction filtration through a 100nm filter membrane, and transferring to the environment of-20 ℃ for freeze drying for 24 hours to obtain the nanocomposite cellulose component.
The ceramic prepared by enhanced gel injection molding is prepared by the following method:
Preparing a premix: centrifuging 350g of the composite nano cellulose component at a speed of 12500r/min for 10min to obtain a treated composite nano cellulose component, mixing the treated composite nano cellulose component with 350g of deionized water, ultrasonically oscillating for 20min, adding 100g of acrylamide, continuously stirring for 2h to obtain a suspension, sequentially adding 10g of N, N' -methylenebisacrylamide, 125g of dispersing agent, 17.5g of defoaming agent and 12.5g of suspending agent into the suspension, and stirring for 2h to obtain a premix.
Preparing slurry: 882.6g of F240 silicon carbide powder, 588.4g of F1200 silicon carbide powder and 176.52g of carbon black are sequentially added into the premix, and stirred at a rotating speed of 2000rpm for 30min to obtain a pre-slurry, the pre-slurry is ball-milled for 16h at a ball milling rotating speed of 30r/min, then vacuum defoamation is carried out for 10min, and the defoamation is carried out simultaneously with vibration treatment at a frequency of 10Hz to obtain the slurry.
Preparing a blank: adding 0.125g of catalyst and 1g of initiator into the slurry, stirring at 6000rpm for 3min at 15 ℃, pouring into a mold, and molding, wherein the molded green body is kept at 40 ℃ and dried at 40% humidity, and the drying system is low temperature, high humidity and low humidity, so as to obtain the green body.
Preparing silicon carbide ceramics: and (3) performing reaction sintering on the dried blank at the temperature of 1710 ℃ and preserving heat for 2 hours to obtain the silicon carbide ceramic product.
Examples
Preparing a nanocomposite cellulose component:
Dispersing boron nitride powder in 5mol/L sodium hydroxide solution, hydrolyzing for 24 hours at 120 ℃, centrifuging after hydrolysis, repeatedly washing with deionized water for three times to remove residual sodium hydroxide, dispersing the washed boron nitride powder in 800ml deionized water, performing ultrasonic treatment in an ultrasonic dispersing instrument for 16 hours, centrifuging the obtained suspension at 2000rpm for 5 minutes after ultrasonic treatment to remove unpeeled boron nitride, vacuum-filtering the obtained supernatant, and drying for 12 hours at 60 ℃ to obtain hydroxylated boron nitride.
235.85G of nanocellulose is dispersed in deionized water, stirred for 30min at a rotating speed of 500rpm and subjected to ultrasonic treatment for 5min to obtain nanocellulose dispersion, 106.13g of prepared hydroxylated boron nitride is added into the nanocellulose dispersion, stirred for 60min at a rotating speed of 500rpm, then subjected to ultrasonic treatment for 30min to obtain mixed liquor, the mixed liquor is filtered through a cellulose acetate microporous filter membrane with a pore diameter of 0.22 mu m, and vacuum assisted suction filtration is carried out, and the obtained solid is dried for 12h at 60 ℃ to obtain the boron nitride-nanocellulose composite component.
And (3) regulating the pH value of 158.02g of polyethyleneimine to 10, mixing the boron nitride-nanocellulose composite component prepared by the method with 1000ml of deionized water, adding polyethyleneimine, heating to 100 ℃ and stirring at 200rpm for reaction for 10 hours, centrifuging the reacted solution for 10 minutes, discharging supernatant, repeating for 3 times, adding 1000ml of deionized water again for dispersion, carrying out suction filtration through a 100nm filter membrane, and transferring to the environment of-20 ℃ for freeze drying for 24 hours to obtain the nanocomposite cellulose component.
The ceramic prepared by enhanced gel injection molding is prepared by the following method:
Preparing a premix: and (3) centrifuging 322g of the composite nano cellulose component at a speed of 12500r/min for 10min to obtain a treated composite nano cellulose component, mixing the treated composite nano cellulose component with 320g of deionized water, ultrasonically oscillating for 20min, adding 78g of acrylamide, continuously stirring for 2h to obtain a suspension, sequentially adding 9.2g of N, N' -methylenebisacrylamide, 80.5g of dispersing agent, 13.8g of defoaming agent and 11.5g of suspending agent into the suspension, and stirring for 2h to obtain a premix.
Preparing slurry: adding 1368.92g of silicon carbide ultrafine powder, 28.52g of carbon black and 8.56g of boron carbide into the premix in sequence, stirring at a rotating speed of 2000rpm for 30min to obtain a pre-slurry, ball-milling the pre-slurry for 14h at a ball milling rotating speed of 40r/min, then vacuum defoaming for 10min, and vibrating at a frequency of 10Hz while defoaming to obtain the slurry.
Preparing a blank: adding 0.115g of catalyst and 0.92g of initiator into the slurry, stirring at 6000rpm for 3min at 15 ℃, pouring into a mold, and molding, wherein the molded green body is kept at 40 ℃ and dried at 40% humidity, and the drying system is low temperature, high humidity and low humidity, so as to obtain the green body.
Preparing silicon carbide ceramics: and (3) carrying out pressureless sintering on the dried green body at 2100 ℃ and preserving heat for 3.5h to obtain the silicon carbide ceramic product.
Examples
Example 4 based on example 3, the superfine powder of silicon carbide of 1369.66g, the carbon black of 27.95g and the boron carbide of 8.39g are added in the process of preparing the slurry in example 4; in the process of preparing the silicon carbide ceramic powder, the pressureless sintering temperature is 2200 ℃.
Examples
Example 5 based on example 3, example 5 differs from example 3 in that the N, N' -methylenebisacrylamide added in example 5 is 7g.
Examples
Example 6 based on example 3, example 6 differs from example 3 in that 11g of N, N' -methylenebisacrylamide are added in example 6.
Examples
Example 7 differs from example 3 in that 0.05g of catalyst was added in example 7, based on example 3.
Examples
Example 8 differs from example 3 in that 0.2g of catalyst was added in example 8, based on example 3.
Examples
Example 9 based on example 3, example 9 differs from example 3 in that 0.6g of initiator is added in example 9.
Examples
Example 10 based on example 3, example 10 differs from example 3 in that 1.2g of initiator is added in example 10.
Examples
Example 11 based on example 3, example 11 differs from example 3 in that in the preparation of the nanocomposite cellulose component, 88.67g of hydroxylated boron carbide, 246.31g of nanocellulose and 165.02g of polyethylenimine are used.
Examples
Example 12 based on example 3, example 12 differs from example 3 in that in the preparation of the nanocomposite cellulose component, 122.18g of hydroxylated boron carbide, 226.24g of nanocellulose and 151.58g of polyethylenimine are used.
Examples
Example 13 based on example 3, example 13 differs from example 3 in that in example 13 no polyethyleneimine is added in the preparation of the nanocomposite cellulose component.
Examples
Example 14 based on example 3, example 14 differs from example 3 in that no hydroxylated boron nitride is added in the preparation of the nanocomposite cellulose component in example 14.
Examples
Example 15 based on example 3, example 15 differs from example 3 in that in example 15, the hydroxylated boron nitride is replaced by a common boron nitride in the preparation of the nanocomposite cellulose component.
Comparative example 1
Comparative example 1 based on example 3, the nanocomposite cellulose component was replaced with ordinary nanocellulose in comparative example 1.
Comparative example 2
Comparative example 2 based on example 3, the nanocomposite cellulose component was replaced with an equal amount of deionized water in comparative example 2.
Performance test
The following performance tests were performed on the samples of examples 1-15, comparative examples 1-2:
(1) Drying performance test: the wet green sheet was subjected to drying treatment, and the dried green sheet was observed and recorded, and the results are shown in table 1.
(2) The bending strength test is carried out on the samples by taking the GB/T6569-2006 fine ceramic bending strength test method as a detection standard, each sample is tested for three times at room temperature, an average value is taken, and the detection result is filled in the table 1.
(3) The vickers hardness of the samples was calculated by measuring with a vickers hardness tester using the standard of GB 16534-2009 method for testing fine ceramics at room temperature, and each sample was tested three times, and the average value was obtained after the measurement, and the results are recorded in table 1.
TABLE 1 test results for examples 1-15, comparative examples 1-2 samples
| Detecting items | Surface condition after drying | Flexural Strength/MPa | Hardness (GPa) |
| Example 1 | No cracking | 432 | 24 |
| Example 2 | No cracking | 434 | 25 |
| Example 3 | No cracking | 456 | 28 |
| Example 4 | No cracking | 458 | 28 |
| Example 5 | No cracking | 437 | 21 |
| Example 6 | No cracking | 433 | 22 |
| Example 7 | No cracking | 428 | 21 |
| Example 8 | No cracking | 423 | 22 |
| Example 9 | No cracking | 424 | 20 |
| Example 10 | No cracking | 422 | 21 |
| Example 11 | No cracking | 425 | 22 |
| Example 12 | No cracking | 426 | 20 |
| Example 13 | No cracking | 422 | 20 |
| Example 14 | No cracking | 428 | 22 |
| Example 15 | No cracking | 425 | 23 |
| Comparative example 1 | Slight cracking | 399 | 18 |
| Comparative example 2 | Cracking and deformation | 387 | 15 |
Data analysis
As shown in Table 1, the blanks of examples 1-4 all have no cracking phenomenon after being dried, the bending strength is 430MPa or more, the hardness is 24Gpa or more, and the silicon carbide ceramic prepared by the application has good stability and strength.
As is clear from Table 1, when the content of N, N' -methylenebisacrylamide is too high or too low, the content of the catalyst is too high or too low, and the content of the initiator is too high or too low, which affects the stability of the whole system, so that the stability of the prepared green body is lowered, and thus the flexural strength and hardness of examples 5 to 10 are slightly lowered.
In the preparation of the nanocomposite cellulose component in examples 11 and 12, the mass ratio among the hydroxylated boron carbide, the nanocellulose and the polyethyleneimine is not within the range defined by the application, and when the content of the hydroxylated boron nitride is too small, the hydroxyl content in the system is reduced, so that the dispersion effect of the nanocomposite cellulose in the blank is reduced, and the overall uniformity of the system is influenced; when the content of the hydroxylated boron carbide is too large, the tightness of the connection between the nanocomposite cellulose components to the respective components in the system is difficult to be further improved, so that the properties of each of example 11 and example 12 are reduced.
The polyethylene imine is not added in the embodiment 13, so that the improvement effect between the hydroxylated boron carbide and the nanocellulose is difficult to achieve, the strength of the nanocomposite cellulose component is reduced, and the stability of a green body is reduced, so that each performance of the embodiment 13 is reduced.
In example 14, the dispersion effect of nanocellulose was reduced, aggregation was caused in the system, the solid content of the system was affected, and the human stability and strength of the system were also affected, so that the properties of example 14 were reduced.
In example 15, the hydroxylated boron carbide is replaced by the common boron carbide, so that the dispersibility of the nanocellulose composite material is reduced, sedimentation occurs in the system, and the uniformity of the prepared ceramic system is affected, so that the performances of example 15 are reduced.
In comparative example 1, the composite nanofiber component cellulose is replaced by common nanocellulose, so that the dispersion performance of the common nanocellulose in a system is difficult to improve, and meanwhile, the thermal stability and the strength are difficult to further improve, so that the performances of comparative example 1 are reduced.
In comparative example 2, the composite nanocellulose component is not added, so that each component in the green body is difficult to combine tightly, a stable network crosslinking structure is formed, and the stability of the green body is affected.
The present embodiment is merely illustrative of the present application, and the present application is not limited thereto, and a worker can make various changes and modifications without departing from the scope of the technical idea of the present application. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of claims.
Claims (10)
1. A method for preparing ceramic by enhanced gel injection molding is characterized in that: the method comprises the following steps:
Preparing a premix: carrying out high-speed centrifugal treatment on the modified nano cellulose composite component to obtain treated modified nano cellulose composite component, mixing the treated modified nano cellulose composite component with deionized water, adding acrylamide into the mixture after ultrasonic treatment, stirring the mixture to obtain a suspension, adding N, N' -methylenebisacrylamide, a dispersing agent, a defoaming agent and a suspending agent into the suspension, and stirring the mixture to obtain a premix;
preparing slurry: adding ceramic powder and a sintering aid into the obtained premix, stirring to obtain a prefabricated slurry, ball-milling the prefabricated slurry, vacuum defoaming, vibrating at a frequency of 5-10Hz during vacuum defoaming, and vacuum defoaming to obtain the slurry;
Preparing a blank: adding a catalyst and an initiator into the slurry, stirring, pouring into a mold, and drying at constant temperature and constant humidity after the slurry is molded to obtain a blank;
Preparing silicon carbide ceramics: sintering the blank body, and preserving heat to obtain the silicon carbide ceramic product.
2. The method for preparing ceramic by enhanced gel injection molding according to claim 1, wherein: the sintering aid comprises one or two of carbon black and boron carbide, and the ceramic powder comprises one or two of primary silicon carbide powder particles and secondary silicon carbide powder particles.
3. The method for preparing ceramic by enhanced gel injection molding according to claim 2, wherein: in the preparation of the silicon carbide ceramic, green body sintering adopts pressureless sintering; the mass ratio of the silicon carbide ceramic powder to the carbon black to the boron carbide is (48-49) 1:0.3.
4. The method for preparing ceramic by enhanced gel injection molding according to claim 2, wherein: in the preparation of the silicon carbide ceramic, the green body sintering adopts reaction sintering; the mass ratio of the primary carbonized powder particles to the secondary carbonized silicon powder particles to the sintering aid is 1.5:1 (0.25-0.3).
5. The method for preparing ceramic by enhanced gel injection molding according to claim 1, wherein: the content of the acrylamide is 0.03-0.05% of the total weight of the slurry, the content of the catalyst is 0.005-0.007% of the total weight of the blank, and the content of the initiator is 0.03-0.05% of the total weight of the blank.
6. The method for preparing ceramic by enhanced gel injection molding according to claim 1, wherein: the modified nano cellulose composite component accounts for 12-14% of the total mass of the slurry.
7. The method for preparing ceramic by enhanced gel injection molding according to claim 1, wherein: the modified nanocellulose composite component comprises hydroxylated boron nitride, nanocellulose and polyethyleneimine.
8. The method for preparing ceramic by enhanced gel injection molding according to claim 7, wherein: the modified nanocellulose is prepared by the following method:
Mixing nanocellulose with deionized water to obtain nanocellulose suspension, adding hydroxylated boron nitride, performing ultrasonic treatment to obtain composite dispersion, performing suction filtration, and drying to obtain nanocellulose-boron nitride composite material;
And (3) regulating the pH value of the polyethyleneimine to be alkaline, adding the nanocellulose-boron nitride composite material, heating, stirring for reaction, centrifuging to obtain a prefabricated compound, mixing the composite prefabricated compound with deionized water, filtering, suction filtering, and freeze-drying to obtain the modified nanocellulose.
9. The method for preparing ceramic by enhanced gel injection molding according to claim 7, wherein: the mass ratio of the hydroxylated boron nitride, the nanocellulose and the polyethyleneimine is (0.42-0.48) 1:0.67.
10. The method for preparing ceramic by enhanced gel injection molding according to claim 7, wherein: the hydroxylated boron nitride is prepared by the following method:
Mixing boron nitride with sodium hydroxide solution for hydrolysis, centrifugally washing, mixing with deionized water, ultrasonically centrifuging, taking supernatant, and performing suction filtration and drying to obtain hydroxylated boron nitride.
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