CN117303914A - Preparation method of plastic ceramic biscuit - Google Patents

Preparation method of plastic ceramic biscuit Download PDF

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Publication number
CN117303914A
CN117303914A CN202311615453.0A CN202311615453A CN117303914A CN 117303914 A CN117303914 A CN 117303914A CN 202311615453 A CN202311615453 A CN 202311615453A CN 117303914 A CN117303914 A CN 117303914A
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ceramic
water
preparing
plasticizer
plastic
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CN117303914B (en
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刘娟
王娟娟
吴事江
林杨
刘飞
郭丽萍
王士维
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Shandong Ultraming Fine Ceramics Co ltd
Shanghai Institute of Ceramics of CAS
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Shandong Ultraming Fine Ceramics Co ltd
Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to the technical field of ceramic preparation, in particular to a preparation method of a plastic ceramic biscuit. The preparation method of the plastic ceramic biscuit comprises the following steps: (1) preparing a water-based ceramic slurry: firstly, uniformly dispersing ceramic powder, isobutene and maleic anhydride copolymer in water, and then adding a plasticizer and uniformly mixing to obtain water-based ceramic slurry with the solid content of 40-60 vol%; (2) preparing a ceramic biscuit: and (3) injecting the water-based ceramic slurry into a mould, forming ceramic gel by spontaneous solidification, demoulding and drying to obtain the plastic ceramic biscuit. According to the invention, the plasticizer is used for weakening Van der Waals force among polymer molecules, reducing crystallinity of polymer molecular chains, and simultaneously increasing mobility of the polymer molecular chains, so that plasticity of a ceramic gel network is improved without affecting essential properties of the ceramic gel network, and uniformity and plasticity of ceramic greenware are improved.

Description

Preparation method of plastic ceramic biscuit
Technical Field
The invention relates to the technical field of ceramic preparation, in particular to a preparation method of a plastic ceramic biscuit.
Background
Biscuit forming is an important step in ceramic manufacture and is a key factor affecting the performance and cost of ceramic parts. Compared with the traditional dry pressing or isostatic pressing ceramic molding method, the colloidal molding has outstanding advantages in preparing advanced ceramics with complex macroscopic structure and uniform microscopic structure.
Patent CN103130509a discloses a spontaneous solidification molding process, wherein the dispersion and solidification functions of ceramic slurry are realized by adding copolymer of isobutylene and maleic anhydride. The method has the advantages of in-situ solidification of slurry, near net-size forming, few additive types, small additive amount and the like, and becomes a research hot spot in the field of advanced ceramic preparation science.
In subsequent researches, patent CN115448704a found that spontaneous solidification molding of ceramic slurry is achieved only by means of isobutylene and maleic anhydride copolymer, the gel curing time is long, and sedimentation may occur in the gel curing stage of ceramic particles, so that the density distribution of a green body is uneven, and the green body is deformed by drying or cracked; therefore, the microwave auxiliary effect is adopted in the gel curing process, the gel curing time is greatly shortened, and the condition of uneven density distribution of the blank is avoided.
Although proper microwave power is adopted to accelerate the movement of ceramic particles and improve the gel curing speed, the ceramic biscuit formed by spontaneous solidification has low organic matter content and high bulk density, and the particles with high bulk density are mostly in direct hard contact and lack of plasticity, so that the ceramic biscuit obtained by a spontaneous solidification forming system has low plasticity and high brittleness, and the ceramic biscuit is easy to crack in the drying and carrying processes, and is difficult to machine.
Patent CN116924777a discloses a ceramic slurry, an alumina ceramic substrate and a preparation method thereof, wherein two kinds of polyvinyl butyrals with different molecular weights, fluxing agents, solvents and plasticizers are added into the slurry mainly comprising alumina, so that the slurry which is good in uniformity, good in dispersibility, good in stability, moderate in viscosity and fluidity and suitable for a tape casting forming process is obtained. However, the method is only suitable for casting molding, and because the casting molding usually adopts organic matters as solvents, the harm to operators and the environment is unavoidable, and the problems of low density of the biscuit, long time of the biscuit glue discharging, easy cracking in the glue discharging process and the like exist, the application of the method is limited, and the method is unfavorable for the production of large-size advanced ceramic parts.
Disclosure of Invention
Aiming at the problems of larger brittleness and poorer plasticity of a spontaneously solidified and formed ceramic biscuit, the invention provides a preparation method of the plastic ceramic biscuit, which utilizes a plasticizer to weaken Van der Waals force among polymer molecules, reduce crystallinity of polymer molecular chains, and simultaneously increase mobility of the polymer molecular chains, thereby improving plasticity of a ceramic gel network without influencing essential attributes of the ceramic biscuit, and further improving uniformity and plasticity of the ceramic biscuit.
The preparation method of the plastic ceramic biscuit comprises the following steps:
(1) Preparing water-based ceramic slurry: firstly, uniformly dispersing ceramic powder, isobutene and maleic anhydride copolymer in water, and then adding a plasticizer and uniformly mixing to obtain water-based ceramic slurry with the solid content of 40-60 vol%;
(2) Preparing a ceramic biscuit: and (3) injecting the water-based ceramic slurry into a mould, forming ceramic gel by spontaneous solidification, demoulding and drying to obtain the plastic ceramic biscuit.
In the invention, the ceramic powder is oxide ceramic powder, non-oxide ceramic powder or composite ceramic powder; preferably at least one of alumina powder, zirconia powder, yttria powder, silicon carbide powder, magnesia-alumina spinel powder and mullite powder; the median particle diameter of the ceramic powder is 50 nm-1 μm.
In the invention, the copolymer of isobutene and maleic anhydride is an aminated water-soluble copolymer of isobutene and maleic anhydride (poly [ (isobutene-alt-maleic acid, ammonium salt) -co- (isobutene-alt-maleic anhydride) ]) with a number average molecular weight of 5500-65000. The addition amount of the copolymer of isobutene and maleic anhydride is 0.1-1.3 wt.% of the mass of the ceramic powder, preferably 0.3-0.6 wt.% of the mass of the ceramic powder.
In the invention, the plasticizer is an alcohol plasticizer or a phthalate plasticizer which has both a polar group and a nonpolar chain segment. The addition amount of the plasticizer is 1-5wt% of the mass of the ceramic powder.
Preferably, the alcohol plasticizer is at least one of glycerol and polyethylene glycol (PEG-400); the phthalate plasticizer is at least one of dibutyl phthalate (DBP) and dioctyl phthalate (DOP).
In the step (1) of the present invention, the water-based ceramic slurry obtained was in 100 seconds -1 Viscosity at shear rate of less than 1Pa . s is suitable for casting and has gelation ability.
In the step (2), the water-based ceramic slurry is subjected to vacuum degassing and then is injected into a die for spontaneous solidification and molding.
Preferably, the die is a strip die with the shape of 9mm multiplied by 2mm multiplied by 50mm, so that the blank is convenient to demold, and the three-point flexural strength and impact toughness of the biscuit are tested.
Further preferably, the mold is a polytetrafluoroethylene mold or a plexiglass mold.
Preferably, the atmosphere for spontaneous solidification molding is air, the temperature is 15-40 ℃, and the solidification time is 1-24 h.
Preferably, the drying temperature is 15-40 ℃, the relative humidity is 30-85%, and the drying time is 8-72 h.
According to the invention, the ceramic slurry with low viscosity, good fluidity and solid content of 40-60 vol.% is prepared by adding the copolymer of isobutene and maleic anhydride, and after the ceramic slurry is fully mixed, alcohol or phthalate plasticizers are added into the slurry and uniformly stirred, so that small molecules of the plasticizers are uniformly distributed among polymer molecular chains, the Van der Waals force among the polymer molecules is weakened, the crystallinity of the polymer molecular chains is reduced, and meanwhile, the mobility of the polymer molecular chains is increased, so that the intermolecular lubricant function is realized, the structural uniformity of a gel network is improved, the internal stress is reduced, and the brittleness of a biscuit is improved. The obtained ceramic slurry is subjected to vacuum degassing, then is injected into a mold with a formed shape to be spontaneously solidified and formed into ceramic gel, and the wet blank is fully solidified and then is demoulded; and drying to obtain the plastic ceramic biscuit. The addition of the proper plasticizer can improve the uniformity of the ceramic gel network structure, reduce the internal stress and avoid the risks of biscuit drying, carrying cracking and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the copolymer of isobutene and maleic anhydride is introduced into the water-based ceramic slurry as a gelling agent and a dispersing agent, and meanwhile, an alcohol plasticizer or phthalate plasticizer is introduced, so that the interaction between a polymer chain and a plasticizer chain in spontaneous solidification molding is improved, and the hard contact between ceramic particles in a biscuit is reduced, thereby macroscopically enhancing the plasticity of the biscuit;
(2) The preparation method of the ceramic biscuit is suitable for various ceramic powder with various particle sizes, wherein when the median particle size of the powder is 450nm, the impact toughness of the ceramic biscuit prepared by adding 2wt.% of plasticizer is improved by about 53%, and the perforation of the biscuit can be realized.
Drawings
FIG. 1 is a graph of the shear viscosity of the aqueous alumina ceramic slurries of examples 1-3 and comparative example 1;
FIG. 2 is a graph of force versus displacement curve for the alumina ceramic greenbars of examples 1-3 and comparative example 1;
FIG. 3 is a cross-sectional microstructure of the alumina ceramic greenbars of comparative example 1;
FIG. 4 is a cross-sectional microstructure of an alumina ceramic greenbar spline of example 2;
FIG. 5 is a graph showing a comparative example 1 and example 2 showing the results of punching (drill diameter: 5 mm) of alumina ceramic greenware wafers; in the figure, comparative example 1 is shown on the left and example 2 is shown on the right.
Detailed Description
The invention is further described below with reference to the drawings and examples.
The invention provides a preparation method of a plastic ceramic biscuit, which comprises the following steps: and preparing ceramic slurry with low viscosity, good fluidity and solid content of 40-60 vol.% by using an isobutene and maleic anhydride copolymer, fully mixing, adding a plasticizer into the ceramic slurry, uniformly stirring to obtain water-based ceramic slurry, then injecting the obtained water-based ceramic slurry into a mold with a certain shape, spontaneously solidifying and forming ceramic gel, fully solidifying, demolding, and drying to obtain the plastic ceramic biscuit.
The following specifically describes a preparation method of the plastic ceramic biscuit, which comprises the following steps:
(1) Preparing water-based ceramic slurry:
firstly, uniformly dispersing ceramic powder, isobutene and maleic anhydride copolymer in water, then adding a plasticizer accounting for 1-5wt% of the ceramic powder mass, and uniformly mixing to obtain a water-based ceramic slurry with the solid content of 40-60vol%, wherein the water-based ceramic slurry is 100s in weight -1 Viscosity at shear rate of less than 1Pa . s is suitable for casting and has gelation ability.
The copolymer of isobutene and maleic anhydride is aminated water-soluble copolymer of isobutene and maleic anhydride (poly [ (isobutene-alt-maleic acid, ammonium salt) -co- (isobutene-alt-maleic anhydride) ]) with the number average molecular weight of 5500-65000.
The addition amount of the copolymer of isobutene and maleic anhydride is 0.1-1.3 wt.% of the mass of the ceramic powder, preferably 0.3-0.6 wt.% of the mass of the ceramic powder; too high an amount of copolymer of isobutylene and maleic anhydride may result in the slurry not being gellable and too low may result in the slurry not being efficiently discharged and degassed due to too high a viscosity.
The plasticizer is an alcohol plasticizer or a phthalate plasticizer which has both a polar group and a nonpolar chain segment. The polar groups in the molecular chain of the copolymer of isobutene and maleic anhydride are shielded by the shielding effect of the polar groups in the plasticizer and the molecular chain of the copolymer of isobutene and maleic anhydride to reduce the secondary bonding between the macromolecular chain of the copolymer of isobutene and maleic acid and the macromolecular chain, so that the mobility of the molecular chain is improved. Wherein the alcohol plasticizer is at least one of glycerol and polyethylene glycol (PEG-400); the phthalate plasticizer is at least one of dibutyl phthalate (DBP) and dioctyl phthalate (DOP).
The addition amount of the plasticizer is 1-5wt% of the mass of the ceramic powder. When the addition amount of the plasticizer is too low, the ceramic biscuit cannot be effectively plasticized, and when the addition amount is too high, the distance between ceramic particles can be increased, so that the solid content of the biscuit is reduced.
The ceramic powder is oxide ceramic powder, non-oxide ceramic powder or composite ceramic powder; can be at least one of alumina powder, zirconia powder, yttrium oxide powder, silicon carbide powder, magnesia-alumina spinel powder and mullite powder; the median particle diameter of the ceramic powder is 50 nm-1 μm.
The dispersing and mixing modes can be planetary ball milling, ball milling stirring or ultrasonic mixing.
Taking alumina ceramic powder as an example, the preparation method of the water-based ceramic slurry comprises the following steps:
adding copolymer of isobutene and maleic anhydride as dispersing agent and gelatinizer into deionized water, stirring to dissolve fully, adding alumina ceramic powder, ball milling, stirring to disperse, mixing fully, adding plasticizer, ball milling, stirring, discharging and degassing to obtain water-base ceramic slurry with low viscosity and good flowability.
(2) Preparing a ceramic biscuit: and (3) carrying out vacuum degassing on the water-based ceramic slurry, injecting the water-based ceramic slurry into a die, sealing and standing for 1-24 h at 15-40 ℃ to carry out spontaneous solidification forming, demoulding after ceramic gel is formed, and placing a wet blank into a temperature-control humidity-control box to be dried to constant weight, wherein the temperature of the constant temperature humidity box is controlled to be 15-40 ℃, the relative humidity is controlled to be 30-85%, and the drying time is 8-72 h, so that the plastic ceramic biscuit is obtained.
The die is a strip-shaped die with the shape of 9mm multiplied by 2mm multiplied by 50mm, so that the blank is convenient to demold, and the three-point flexural strength and impact toughness of the biscuit are tested. The mold is a polytetrafluoroethylene mold or an organic glass mold.
The present invention will be described in more detail by way of examples. The raw materials used in the examples, unless otherwise specified, were all commercially available conventional raw materials; the process used in the examples, unless otherwise specified, is conventional in the art.
Example 1
The preparation method of the invention is adopted to prepare the plastic ceramic biscuit, and comprises the following steps:
(1) A water-based alumina ceramic slurry having a solids content of 54vol.% was prepared:
adding poly [ (isobutylene-alt-maleic acid, ammonium salt) -co- (isobutylene-alt-maleic anhydride) accounting for 0.3wt.% of the mass of the alumina ceramic powder into deionized water](number average molecular weight is 5500-65000) is dispersant and gelatinizer, stirring for dissolving, adding median particle diameter D 50 After ball milling and stirring for 0.5h, dibutyl phthalate accounting for 1wt.% of the mass of the alumina ceramic powder is added, ball milling and stirring are continued for 1h, and water-based alumina ceramic slurry with uniform dispersion and 54vol.% of solid content is obtained after discharging and degassing, wherein the water-based alumina ceramic slurry is prepared in 100s -1 Viscosity at shear rate of less than 1Pa . s；
(2) Preparing an alumina ceramic biscuit:
and (3) carrying out vacuum degassing on the water-based alumina ceramic slurry, respectively injecting the water-based alumina ceramic slurry into a strip mold with the diameter of 9mm multiplied by 2mm multiplied by 50mm and a round mold with the diameter of 23mm and the depth of 8.8mm, sealing and standing for 20 hours at room temperature (25 ℃) to carry out spontaneous solidification molding, demoulding after ceramic gel is formed, and placing the wet blank into a temperature-controlled humidity-controlled box with the temperature of 25 ℃ and the relative humidity of 80% to dry for 36 hours to obtain alumina ceramic biscuit sample bars and alumina ceramic biscuit wafers.
Example 2
The present example differs from example 1 only in that dibutyl phthalate was added in an amount of 2wt.% based on the mass of the alumina ceramic powder in step (1).
Example 3
The present example differs from example 1 only in that dibutyl phthalate was added in an amount of 5wt.% based on the mass of the alumina ceramic powder in step (1).
Example 4
The preparation method of the invention is adopted to prepare the plastic ceramic biscuit, and comprises the following steps:
(1) A water-based alumina ceramic slurry having a solids content of 40vol.% was prepared:
adding poly [ (isobutylene-alt-maleic acid, ammonium salt) -co- (isobutylene-alt-maleic anhydride) accounting for 0.1wt.% of the mass of the alumina ceramic powder into deionized water](number average molecular weight is 5500-65000) is dispersant and gelatinizer, stirring for dissolving, adding median particle diameter D 50 After ball milling and stirring for 0.5h, adding glycerol accounting for 1wt.% of the mass of the alumina ceramic powder, continuing ball milling and stirring for 1h, discharging and degassing to obtain water-based alumina ceramic slurry with uniform dispersion and 40vol.% of solid content, wherein the water-based alumina ceramic slurry is prepared for 100s -1 Viscosity at shear rate of less than 1Pa . s；
(2) Preparing an alumina ceramic biscuit:
and (3) carrying out vacuum degassing on the water-based alumina ceramic slurry, then injecting the water-based alumina ceramic slurry into a strip-shaped die with the thickness of 9mm multiplied by 2mm multiplied by 50mm, sealing and standing for 24 hours at 15 ℃ for spontaneous solidification forming, demoulding after ceramic gel is formed, and drying the wet blank in a temperature-control humidity-control box with the temperature of 15 ℃ and the relative humidity of 50% for 72 hours to obtain alumina ceramic biscuit bars.
Example 5
The preparation method of the invention is adopted to prepare the plastic ceramic biscuit, and comprises the following steps:
(1) A water-based alumina ceramic slurry having a solids content of 60vol.% was prepared:
adding poly [ (isobutylene-alt-maleic acid, ammonium salt) -co- (isobutylene-alt-maleic anhydride) accounting for 1.3wt.% of the mass of the alumina ceramic powder into deionized water](number average molecular weight is 5500-65000) is dispersant and gelatinizer, stirring for dissolving, adding median particle diameter D 50 After ball milling and stirring for 0.5h, polyethylene glycol (PEG-400) accounting for 2wt.% of the mass of the alumina ceramic powder is added, ball milling and stirring are continued for 1h, and water-based alumina ceramic slurry with uniform dispersion and 60vol.% of solid content is obtained after discharging and degassing, wherein the water-based alumina ceramic slurry is prepared in 100s -1 Viscosity at shear rate of less than 1Pa . s；
(2) Preparing an alumina ceramic biscuit:
and (3) carrying out vacuum degassing on the water-based alumina ceramic slurry, then injecting the water-based alumina ceramic slurry into a strip-shaped die with the thickness of 9mm multiplied by 2mm multiplied by 50mm, sealing and standing for 1h at 40 ℃ for spontaneous solidification forming, demoulding after ceramic gel is formed, and drying the wet blank in a temperature-control humidity-control box with the temperature of 40 ℃ and the relative humidity of 85% for 8h to obtain alumina ceramic biscuit bars.
Example 6
The preparation method of the invention is adopted to prepare the plastic ceramic biscuit, and comprises the following steps:
(1) A water-based alumina ceramic slurry having a solids content of 54vol.% was prepared:
adding poly [ (isobutylene-alt-maleic acid, ammonium salt) -co- (isobutylene-alt-maleic anhydride) accounting for 0.6wt.% of the mass of the alumina ceramic powder into deionized water](number average molecular weight is 5500-65000) is dispersant and gelatinizer, stirring for dissolving, adding median particle diameter D 50 After ball milling and stirring for 0.5h, dioctylphthalate accounting for 5wt.% of the mass of the alumina ceramic powder is added, ball milling and stirring are continued for 1h, and water-based alumina ceramic slurry with uniform dispersion and 54vol.% of solid content is obtained after discharging and degassing, wherein the water-based alumina ceramic slurry is prepared in 100s -1 Viscosity at shear rate of less than 1Pa . s；
(2) Preparing an alumina ceramic biscuit:
and (3) carrying out vacuum degassing on the water-based alumina ceramic slurry, then injecting the water-based alumina ceramic slurry into a strip-shaped die with the thickness of 9mm multiplied by 2mm multiplied by 50mm, sealing and standing for 10 hours at the temperature of 30 ℃ for spontaneous solidification forming, demoulding after ceramic gel is formed, and drying the wet blank in a temperature-control humidity-control box with the temperature of 30 ℃ and the relative humidity for 24 hours to obtain the alumina ceramic biscuit sample strip.
Comparative example 1
This comparative example differs from example 1 only in that dibutyl phthalate plasticizer was not added in step (1).
Comparative example 2
The present comparative example differs from example 4 only in that no glycerol plasticizer was added in step (1).
The surfaces of the ceramic biscuit sample bars prepared in each example and comparative example are polished until the surfaces are defect-free and four sides are parallel, and the performance test is carried out after the widths and the heights of the sample bars are recorded. The method comprises the steps of performing three-point flexural strength test on a ceramic biscuit spline by using a universal tester (the loading speed is 0.5 mm/min), obtaining a force-displacement curve of the spline, and calculating the flexural strength of the spline according to the following formula:
σ=3FL/2bh 2 ；
wherein F is the maximum breaking load (N) and L is the span (30 mm); b is the sample width (mm) and h is the sample thickness (mm).
The ceramic green bars were subjected to impact toughness testing using a pendulum impact tester (impact speed of 3.5 min/s), and the impact toughness of the bars (ISO 179-1:2010) was calculated according to the following formula:
a cU =（E C /hb）×10 3 ；
wherein E is C The impact energy (J) consumed to break the bar, b is the sample width (mm), and h is the sample thickness (mm).
The above flexural strength and impact toughness values are average values of five bars.
In addition, shear viscosity tests were performed on the water-based alumina ceramic slurries prepared in examples 1 to 3 and comparative example 1 using a rotary rheometer; section microstructure observation was performed on the ceramic greenbars prepared in example 2 and comparative example 1 using a scanning electron microscope; the ceramic greenware discs prepared in example 2 and comparative example 1 were perforated using a drill with a diameter of 5mm for plastic comparison.
The test results are shown in Table 1 and FIGS. 1 to 5, and the impact toughness and flexural strength are both expressed as "average value.+ -. Standard deviation".
TABLE 1
As can be seen from Table 1, the impact toughness of the ceramic biscuit of comparative example 1, to which no plasticizer was added, was 0.62KJ/m for the alumina ceramic powder having a median particle diameter of 450nm 2 The ceramic greenware with 2wt.% DBP plasticizer added in example 2 had an impact toughness of 0.95KJ/m 2 About 53% improvement over comparative example 1, indicating improved greenbody plasticity and reduced standard deviation, indicating improved structural uniformity of the plasticized greenbody; in addition, since the improvement of the impact toughness of the green body bar is accompanied by the decrease of the flexural strength, the addition amount of the plasticizer is preferably kept at 1 to 5wt.%. Similarly, the ceramic biscuit of comparative example 2, to which no plasticizer was added, had an impact toughness of 0.82KJ/m for a ceramic powder having a median particle diameter of 150nm 2 The ceramic biscuit of example 4, to which 1wt.% glycerol plasticizer was added, had an impact toughness of 0.96KJ/m 2 The improvement is about 17% compared with comparative example 2, and the plasticizing effect is better.
Fig. 1 is a graph showing the shear viscosity of the aqueous alumina ceramic slurries of examples 1 to 3 and comparative example 1, and it can be seen from fig. 1 that the 4 curves substantially overlap, and that the addition of the plasticizer has little effect on the viscosity of the aqueous alumina ceramic slurry.
Fig. 2 is a graph showing force-displacement curve relationships of the alumina ceramic greenbody bars in examples 1 to 3 and comparative example 1, and it can be seen from fig. 2 that the addition of the plasticizer widens the peak shape of the force-displacement curve of the greenbody, and the plasticity of the greenbody is improved.
Fig. 3 to 4 are cross-sectional microstructure diagrams of the alumina ceramic greenbody bars in comparative example 1 and example 2, respectively, and as can be seen from fig. 3 to 4, the microstructure of the ceramic greenbody before and after the plasticizer is added is similar, which shows that the addition of the plasticizer has no obvious influence on the self-solidification molding compactness of the ceramic greenbody.
FIG. 5 is a graph showing a comparative example 1 and example 2 showing the results of punching (drill diameter: 5 mm) of alumina ceramic greenware wafers; it can be seen that the plasticized ceramic biscuit remains intact after perforation without cracking.

Claims (9)

1. A preparation method of a plastic ceramic biscuit is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing water-based ceramic slurry: firstly, uniformly dispersing ceramic powder, isobutene and maleic anhydride copolymer in water, and then adding a plasticizer and uniformly mixing to obtain water-based ceramic slurry with the solid content of 40-60 vol%;
(2) Preparing a ceramic biscuit: injecting the water-based ceramic slurry into a mould, forming ceramic gel by spontaneous solidification, demoulding and drying to obtain a plastic ceramic biscuit;
the plasticizer is an alcohol plasticizer or a phthalate plasticizer which has both a polar group and a nonpolar chain segment; the addition amount of the plasticizer is 1-5wt% of the mass of the ceramic powder.
2. The method for preparing a plastic ceramic biscuit according to claim 1, wherein: the copolymer of isobutene and maleic anhydride is aminated water-soluble copolymer of isobutene and maleic anhydride, and the number average molecular weight is 5500-65000.
3. The method for preparing a plastic ceramic biscuit according to claim 2, wherein: the addition amount of the isobutene and maleic anhydride copolymer is 0.1-1.3 wt% of the mass of the ceramic powder.
4. The method for preparing a plastic ceramic biscuit according to claim 1, wherein: the alcohol plasticizer is at least one of glycerol and polyethylene glycol.
5. The method for preparing a plastic ceramic biscuit according to claim 1, wherein: the phthalate plasticizer is at least one of dibutyl phthalate and dioctyl phthalate.
6. The method for preparing a plastic ceramic biscuit according to claim 1, wherein: in the step (1), the obtained water-based ceramic slurry is in a range of 100s -1 Viscosity at shear rate of less than 1Pa . s。
7. The method for preparing a plastic ceramic biscuit according to claim 1, wherein: in the step (2), the water-based ceramic slurry is subjected to vacuum degassing and then is injected into a die for spontaneous solidification and molding.
8. The method for preparing a plastic ceramic biscuit according to claim 1, wherein: the atmosphere for spontaneous solidification forming is air, the temperature is 15-40 ℃, and the solidification time is 1-24 h.
9. The method for preparing a plastic ceramic biscuit according to claim 1, wherein: the drying temperature is 15-40 ℃, the relative humidity is 30-85%, and the drying time is 8-72 h.
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2825711A (en) * 1954-06-28 1958-03-04 Du Pont Plastisol compositions, process of preparing same, water vapor permeable coated fabrics prepared therefrom and processes therefor
CN1390808A (en) * 2002-07-17 2003-01-15 清华大学 Process for preparing ceramic sheet by water-base doctor blading method
JP2010182665A (en) * 2009-01-08 2010-08-19 Nippon Shokubai Co Ltd Manufacturing method of ceramic sheet for fuel cell
US20130056911A1 (en) * 2011-09-01 2013-03-07 Watt Fuel Cell Corp. Process for producing tubular ceramic structures
CN104085041A (en) * 2014-07-23 2014-10-08 中国科学院上海硅酸盐研究所 Method for preparing large-size ceramic biscuit
CN106478104A (en) * 2015-08-24 2017-03-08 中国科学院上海硅酸盐研究所 A kind of method that new type gel cast prepares silicon carbide ceramics with reference to solid-phase sintering
JP2017186184A (en) * 2016-04-01 2017-10-12 株式会社日本触媒 Binder for manufacturing ceramic sintered body
CN108164269A (en) * 2017-12-29 2018-06-15 华东理工大学 A kind of production method of the controllable gel injection-moulding green compact of modulus
CN108748611A (en) * 2018-06-15 2018-11-06 中国科学院上海硅酸盐研究所 A kind of forming method of ceramic body
CN108863394A (en) * 2017-05-10 2018-11-23 中国科学院上海硅酸盐研究所 A kind of method that gel pouring combination freeze-drying prepares porous ceramics
CN111253153A (en) * 2020-01-22 2020-06-09 新沂市锡沂高新材料产业技术研究院有限公司 Method for preparing toughened large-size ultrathin YAG transparent ceramic biscuit based on Isodam gel system
CN113501713A (en) * 2021-06-29 2021-10-15 南通大学 Preparation of Li based on Isodam gel casting technology3MgNbO6Method for microwave dielectric ceramic
CN115180959A (en) * 2022-07-19 2022-10-14 郑州大学 Forming method of environment-friendly water-based gel system silicon nitride ceramic substrate

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2825711A (en) * 1954-06-28 1958-03-04 Du Pont Plastisol compositions, process of preparing same, water vapor permeable coated fabrics prepared therefrom and processes therefor
CN1390808A (en) * 2002-07-17 2003-01-15 清华大学 Process for preparing ceramic sheet by water-base doctor blading method
JP2010182665A (en) * 2009-01-08 2010-08-19 Nippon Shokubai Co Ltd Manufacturing method of ceramic sheet for fuel cell
US20130056911A1 (en) * 2011-09-01 2013-03-07 Watt Fuel Cell Corp. Process for producing tubular ceramic structures
CN104085041A (en) * 2014-07-23 2014-10-08 中国科学院上海硅酸盐研究所 Method for preparing large-size ceramic biscuit
CN106478104A (en) * 2015-08-24 2017-03-08 中国科学院上海硅酸盐研究所 A kind of method that new type gel cast prepares silicon carbide ceramics with reference to solid-phase sintering
JP2017186184A (en) * 2016-04-01 2017-10-12 株式会社日本触媒 Binder for manufacturing ceramic sintered body
CN108863394A (en) * 2017-05-10 2018-11-23 中国科学院上海硅酸盐研究所 A kind of method that gel pouring combination freeze-drying prepares porous ceramics
CN108164269A (en) * 2017-12-29 2018-06-15 华东理工大学 A kind of production method of the controllable gel injection-moulding green compact of modulus
CN108748611A (en) * 2018-06-15 2018-11-06 中国科学院上海硅酸盐研究所 A kind of forming method of ceramic body
CN111253153A (en) * 2020-01-22 2020-06-09 新沂市锡沂高新材料产业技术研究院有限公司 Method for preparing toughened large-size ultrathin YAG transparent ceramic biscuit based on Isodam gel system
CN113501713A (en) * 2021-06-29 2021-10-15 南通大学 Preparation of Li based on Isodam gel casting technology3MgNbO6Method for microwave dielectric ceramic
CN115180959A (en) * 2022-07-19 2022-10-14 郑州大学 Forming method of environment-friendly water-based gel system silicon nitride ceramic substrate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
周美玲等: "《材料工程基础》", 北京工业大学出版社, pages: 233 *
毕见强等: "《特种陶瓷工艺与性能》", 31 July 2018, 哈尔滨工业大学出版社, pages: 233 *

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