CN111253149B - 3D printing ceramic paste and preparation method thereof - Google Patents
3D printing ceramic paste and preparation method thereof Download PDFInfo
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Abstract
The invention is suitable for the technical field of materials, and provides a 3D printing ceramic paste and a preparation method thereof, wherein the method comprises the following steps: by using a dispersant on Al2O3Ball-milling pretreatment is carried out on the ceramic powder to obtain pretreated Al2O3Ceramic powder; adding resin, a dispersing agent, a defoaming agent, a plasticizer and a photoinitiator into a reaction container, and centrifugally stirring to obtain a resin mixed solution; pre-treated Al2O3Adding ceramic powder and a thickening agent into the resin mixed solution, and carrying out sectional centrifugal stirring to obtain the ceramic powder. The 3D printing ceramic paste is prepared by adopting a direct preparation mode, the operation mode is simple, the paste does not need to be prepared by a slurry conversion mode, the solid content of a system is not limited by the solid content of the slurry, the material is stirred by a two-stage centrifugal stirring process, the material is uniformly mixed, the effect is good, the solid content of the system can reach 80-87.5%, the shrinkage is small when the material is applied to 3D printing and degreasing sintering, and the mechanical property of a finished product is excellent.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a 3D printing ceramic paste and a preparation method thereof.
Background
In recent years, the 3D printing industry has gained rapid development with the help of national importance on manufacturing and heavily invested fresh air. The hot spot of the 3D printing industry in China is high nowadays, new materials and new equipment are continuously developed, and meanwhile, the 3D printing technology has strong reverberation in the application industry, so that a new gate is opened for the traditional manufacturing industry. Among them, the ceramic 3D printing technology, as a relatively new printing technology, has been developed by the first small-scale group to date, has become an important branch of the 3D printing technology, has positive research significance and good prospects, and is favored by the vast 3D printing practitioners and terminal application clients.
The ceramic 3D printing material is divided into a slurry system and a paste system, and the two systems have advantages and disadvantages, wherein the paste system has higher viscosity and is more difficult to disperse uniformly compared with the slurry system. The existing paste preparation technology utilizes a mode of heating and viscosity reduction of a system and ball milling to promote the system to be more uniform. Alternatively, a slurry is prepared and the paste is prepared by converting the slurry into a paste by evaporating the solvent. However, the existing ceramic paste preparation process is relatively complex in operation and high in cost, and the solid content and uniformity of a paste system still do not meet the requirements of users.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a 3D printing ceramic paste, and aims to solve the problems that the existing ceramic paste preparation process is relatively complex in operation and high in cost, and the solid content and uniformity of a paste system still do not meet the requirements of users.
The embodiment of the invention is realized in such a way that the preparation method of the 3D printing ceramic paste comprises the following raw materials in percentage by mass: 80 to 87.5 percent of Al2O3Ceramic powder, 10-17% of resin, 0.4-4.375% of dispersant, 0.1-1% of defoamer, 1.25-6% of plasticizer, 0.015-0.1% of photoinitiator and 0.5-4% of thickener;
the preparation method comprises the following steps:
weighing the components according to the formula for later use; by using a dispersant on Al2O3Ball-milling pretreatment is carried out on the ceramic powder to obtain pretreated Al2O3Ceramic powder; adding resin, a dispersing agent, a defoaming agent, a plasticizer and a photoinitiator into a reaction container, and carrying out centrifugal stirring to obtain a resin mixed solution, wherein the centrifugal rotation speed is 600-1000 r/min, and the time is 20-60 s; subjecting the pretreated Al2O3And adding ceramic powder and a thickening agent into the resin mixed solution, and carrying out two-stage centrifugal stirring to obtain the 3D printing ceramic paste.
The embodiment of the invention also provides the 3D printing ceramic paste, and the 3D printing ceramic paste is prepared by the preparation method of the 3D printing ceramic paste.
According to the preparation method of the 3D printing ceramic paste provided by the embodiment of the invention, the scientific and reasonable raw material formula is adopted for compounding, the 3D printing ceramic paste is prepared in a direct preparation mode, the operation mode is simple, the paste is not required to be prepared in a slurry conversion mode, the solid content of a system is not limited by the solid content of the slurry, the materials are stirred by a centrifugal stirring process in two sections, the uniform mixing of the materials can be realized, the solid content of a mixed material system can reach 80% -87.5%, the uniformity is good, the paste is applied to 3D printing, the shrinkage during degreasing and sintering is small, and the mechanical property of a finished product is excellent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method of the 3D printing ceramic paste provided by the embodiment of the invention adopts a direct preparation mode, is simple in operation mode, does not need to prepare the paste in a slurry conversion mode, is not limited by the solid content of the slurry, can realize uniform mixing of the materials by stirring the materials through a centrifugal stirring process in two stages, can realize that the solid content of a mixed material system can reach 80-87.5%, and is good in uniformity, the paste is applied to 3D printing, the shrinkage is small during degreasing and sintering, and the mechanical property of a finished product is excellent.
The embodiment of the invention provides a preparation method of a 3D printing ceramic paste, which comprises the following raw materials in percentage by mass: 80 to 87.5 percent of Al2O3Ceramic powder, 10-17% of resin, 0.4-4.375% of dispersant, 0.1-1% of defoamer, 1.25-6% of plasticizer, 0.015-0.1% of photoinitiator and 0.5-4% of thickener.
In embodiments of the present invention, the dispersant is a solvent-based dispersing wetting agent, preferably using at least one of BYK-111, TEGO Dispers 610 or TEGO Dispers 656.
In the embodiment of the invention, the defoaming agent is preferably at least one of BYK-088, BYK-065, TEGO Foamaex 823 or TEGO Foamex 810.
In the embodiment of the present invention, the plasticizer is a phthalate plasticizer, preferably at least one of dibutyl phthalate and dioctyl phthalate.
In an embodiment of the present invention, the photoinitiator is a uv photoinitiator, preferably at least one of 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, or 2-isopropylthioxanthone.
In the embodiment of the invention, the thickening agent is preferably at least one of BYK-415, BYK-430 or BYK-431.
The preparation method comprises the following steps: weighing the components according to the formula for later use; by using a dispersant on Al2O3Ball-milling pretreatment is carried out on the ceramic powder to obtain pretreated Al2O3Ceramic powder; adding resin, a dispersing agent, a defoaming agent, a plasticizer and a photoinitiator into a reaction container, and carrying out centrifugal stirring to obtain a resin mixed solution, wherein the centrifugal rotation speed is 600-1000 r/min, and the time is 20-60 s; subjecting the pretreated Al2O3And adding ceramic powder and a thickening agent into the resin mixed liquid, and carrying out sectional centrifugal stirring to obtain the 3D printing ceramic paste.
In the embodiment of the invention, the pretreated Al is2O3Adding ceramic powder and a thickening agent into the resin mixed liquid, and carrying out sectional centrifugal stirring to obtain the 3D printing ceramic paste, which specifically comprises the following steps: subjecting the pretreated Al2O3Adding ceramic powder and a thickening agent into the resin mixed solution, and carrying out two-stage centrifugal stirring to obtain the 3D printing ceramic paste, wherein the rotating speed of the first-stage centrifugal stirring is 1200-1500 r/min and the time is 30s, and the rotating speed of the second-stage centrifugal stirring is 1400-2000 r/min and the time is 1400-2000 r/min60～120s。
In the embodiment of the invention, the pretreated Al is2O3Ceramic powder and a thickening agent are added into the resin mixed liquid, two-stage centrifugal stirring is carried out, and the 3D printing ceramic paste is obtained, wherein the rotating speed of the first-stage centrifugal stirring is 1200-1500 r/min, the time is 30s, the rotating speed of the second-stage centrifugal stirring is 1400-2000 r/min, and the time is 60-120 s, and the method specifically comprises the following steps: subjecting the pretreated Al2O3And adding ceramic powder and a thickening agent into the resin mixed solution, and carrying out two-stage centrifugal stirring to obtain the 3D printing ceramic paste, wherein the rotating speed of the first-stage centrifugal stirring is 1300r/min for 30s, the rotating speed of the second-stage centrifugal stirring is 1700r/min for 60 s.
In the embodiment of the invention, the dispersant is adopted to react with Al2O3Ball-milling pretreatment is carried out on the ceramic powder to obtain pretreated Al2O3The ceramic powder comprises the following steps: al by using dispersant and absolute ethyl alcohol2O3And performing ball milling and drying pretreatment on the ceramic powder, wherein the ball milling rotation speed is 180-230 r/min, and the time is 1.5-3 h.
In the embodiment of the invention, Al is treated by using a dispersing agent and absolute ethyl alcohol2O3Ball milling and drying pretreatment are carried out on the ceramic powder, the ball milling rotating speed is 180-230 r/min, and the time is 1.5-3 h, and the method specifically comprises the following steps: by using dispersant and absolute ethyl alcohol to Al2O3Ball milling and drying pretreatment are carried out on the ceramic powder, the ball milling rotating speed is 200r/min, the time is 2h, and the drying temperature is 60 ℃.
In the embodiment of the invention, the resin, the dispersant, the defoamer, the plasticizer and the photoinitiator are added into a reaction container for centrifugal stirring to obtain a resin mixed solution, wherein the step of centrifugal rotation speed of 600-1000 r/min for 20-60 s specifically comprises the following steps: adding resin, a dispersing agent, a defoaming agent, a plasticizer and a photoinitiator into a reaction container, and carrying out centrifugal stirring to obtain a resin mixed solution, wherein the centrifugal rotation speed is 800r/min, and the time is 20 s.
In an embodiment of the present invention, the resin includes a monofunctional monomer and a multifunctional monomer; the monofunctional group monomer is at least one of isobornyl acrylate, 2-phenoxyethyl acrylate or isobornyl methacrylate; the polyfunctional monomer is at least one of propoxylated glycerol triacrylate, trimethylolpropane triacrylate and ethoxylated trimethylolpropane trimethacrylate.
Preferably, the monofunctional monomer and the multifunctional monomer are used in a weight ratio of 2: 1. The viscosity of the monofunctional monomer is preferably less than 20cps, and the viscosity of the polyfunctional monomer is preferably less than 500 cps. As the solids content increases, the viscosity of the system increases. And the monomer resin with relatively low viscosity is selected, so that more lifting space can be reserved for lifting solid content, and the higher solid content can be favorably reached.
Preferably, the Al is2O3Purity of ceramic powder>99.7%, a particle diameter of 0.5 to 2 μm, and a BET specific surface area of 1 to 15m2(ii) in terms of/g. The higher the purity, the better the performance of the finished ceramic product and the easier the sintering. Al selected from the above particle diameter and specific surface2O3The powder is relatively easy to disperse, is not easy to agglomerate and is beneficial to preparing higher solid content.
The embodiment of the invention also provides the 3D printing ceramic paste, and the 3D printing ceramic paste is prepared by the preparation method of the 3D printing ceramic paste.
The starting materials used in the examples of the present invention were all commercially available unless otherwise specified in the present invention.
The technical solution and the technical effect of the present invention will be further described by specific examples.
Example 1
For Al2O3Pretreating ceramic powder:
3000g of Al are weighed2O3The ceramic powder was put into a 2L ball mill, 2kg of ground zirconium balls were added, then 500mL of anhydrous ethanol was poured, and 15g of a dispersant (BYK-111) was added. Beginning ball milling at the rotation speed of 200r/min for 2h, drying the collected slurry at 60 ℃ after the ball milling is finished, and grinding to obtain a pretreatmentTreated Al2O3Ceramic powder.
Preparing a 3D printing ceramic paste:
200g of isoborneol acrylate, 100g of trimethylolpropane triacrylate, 60g of dibutyl phthalate (plasticizer), 17.2g of BYK-111 (dispersant), 4.3g of BYK-088 (defoamer) and 0.9g of 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone (photoinitiator) are weighed in a centrifugal stirrer, the speed is 1000r/min, and the stirring is carried out for 30 s. After the components were completely dissolved, 1725.8g of the pretreated Al was added to the vessel2O3And (3) setting a stirring program of the ceramic powder and 38.3g of BYK-415 (thickening agent), firstly stirring for 30s at a rotation speed of 1200r/min, then stirring for 60s at a rotation speed of 1600r/min, and collecting the 3D printing ceramic paste with the solid content of 80% after stirring. The 3D ceramic paste can be directly used for printing on a computer by corresponding equipment.
Example 2
For Al2O3Pretreating ceramic powder:
3000g of Al are weighed2O3The ceramic powder was put into a 2L ball mill, 2kg of ground zirconium balls were added, then 500mL of anhydrous ethanol was poured, and 15g of a dispersant (BYK-111) was added. Beginning ball milling for 2 hours at the rotating speed of 200r/min, drying the collected slurry at 60 ℃ after the ball milling is finished, and grinding to obtain pretreated Al2O3Ceramic powder.
Preparing a 3D printing ceramic paste:
200g of isoborneol methacrylate, 100g of trimethylolpropane triacrylate, 60g of dibutyl phthalate (plasticizer), 22.7g of BYK-111 (dispersant), 3.2g of BYK-088 (defoamer) and 0.9g of 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone (photoinitiator) are weighed in a centrifugal stirrer, the stirring speed is 800r/min, and the stirring speed is 20 s. After the components were completely dissolved, 2278.1g of pretreated Al as described above were added to the vessel2O3Setting a stirring program of ceramic powder and 32.5g of BYK-430 (thickening agent), stirring for 30s at the rotating speed of 1300r/min, then stirring for 60s at the rotating speed of 1700r/min, and collecting the mixture after stirring to obtain 84 solid content% of ceramic paste. The 3D ceramic paste can be directly used for printing on a computer by corresponding equipment.
Example 3
For Al2O3Pretreating ceramic powder:
weighing 3500g of Al2O3The ceramic powder was put into a 2L ball mill, 2kg of ground zirconium balls were added, 500mL of anhydrous ethanol was poured, and 17.5g of a dispersant (BYK-111) was added. Beginning ball milling for 2 hours at the rotating speed of 200r/min, drying the collected slurry at 60 ℃ after the ball milling is finished, and grinding to obtain pretreated Al2O3Ceramic powder.
Preparing a 3D printing ceramic paste:
200g of isoborneol methacrylate, 100g of trimethylolpropane triacrylate, 60g of dibutyl phthalate (plasticizer), 30.3g of BYK-111 (dispersant), 3.2g of BYK-088 (defoamer) and 0.9g of 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone (photoinitiator) are weighed in a centrifugal stirrer, the stirring speed is 800r/min, and the stirring speed is 20 s. After the components were completely dissolved, 3040.3g of pretreated Al as described above were added to the vessel2O3And (3) setting a stirring program of the ceramic powder and 21.5g of BYK-430 (thickening agent), stirring for 30s at the rotating speed of 1500r/min, then stirring for 60s at the rotating speed of 2000r/min, and collecting ceramic paste with the solid content of 87.5% after stirring. The 3D ceramic paste can be directly used for printing on a computer by corresponding equipment.
Comparative example 1
Compared with the example 2, in the comparative example 1, in the step of preparing the 3D printing ceramic paste, the stirring program is set, the stirring is performed for 30s at the rotation speed of 1200r/min, and then the stirring is performed for 60s at the rotation speed of 1600r/min, so that the stirring program is replaced by the stirring program, and the stirring is performed for 90s at the rotation speed of 1200 r/min. Namely, one-stage centrifugal stirring is adopted.
Comparative example 2
Compared with example 2, the step of formulating the 3D printing ceramic paste in comparative example 2 is: 200g of isoborneol methacrylate, 100g of trimethylolpropane triacrylate, 60g of dibutyl phthalate (plasticizer), 22.7g ofBYK-111 (dispersant), 3.2g of BYK-088 (defoamer) and 0.9g of 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone (photoinitiator) were ball-milled in a ball mill. After the components were completely dissolved, 2278.1g of pretreated Al as described above were added to the vessel2O3And (3) carrying out ball milling on the ceramic powder and 32.5g of BYK-430 (thickening agent), and collecting the obtained 3D ceramic paste after the ball milling is finished.
Comparative example 3
Compared with example 2, the procedure of formulating the 3D printing ceramic paste in comparative example 3 was: 200g of isoborneol methacrylate, 100g of trimethylolpropane triacrylate, 60g of dibutyl phthalate (plasticizer), 30.3g of BYK-111 (dispersant), 3.2g of BYK-088 (defoamer) and 0.9g of 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone (photoinitiator) are weighed out and mechanically stirred in a stirrer. After the components were completely dissolved, 3040.3g of pretreated Al as described above were added to the vessel2O3And (3) stirring the ceramic powder and 21.5g of BYK-430 (thickening agent), and collecting the 3D ceramic paste after stirring.
Comparative examples 4 to 7
Compared with the example 2, the first-stage centrifugal stirring rotation speeds in the step of preparing the 3D printing ceramic paste in the comparative examples 4-7 are 1000, 1100, 1600 and 1700r/min respectively, and the rest preparation conditions and the raw material use amounts are the same as those in the example 2.
Comparative examples 8 to 11
Compared with the example 2, the second-stage centrifugal stirring rotation speeds in the step of preparing the 3D printing ceramic paste in the comparative examples 8-11 are 1200, 1300, 2100 and 2200r/min respectively, and the rest preparation conditions and the raw material use amounts are the same as those in the example 2.
Comparative examples 12 to 15
Compared with the example 2, the dosage and mixing ratio of the monofunctional monomer and the polyfunctional monomer in the resin in the raw material formula of the comparative examples 12 to 15 are respectively as follows: 0:1, 1:0, 1:1 and 1:2, and the other preparation conditions and the raw material amounts are the same as those of example 2.
Comparative examples 16 to 19
Compared with example 2, the usage amounts of the dispersants in comparative examples 16 to 19 respectively account for 0%, 0.3%, 4.5% and 5% of the total mass of the 3D printing ceramic paste system, and the rest preparation conditions and raw material usage amounts are the same as those in example 2.
Comparative examples 20 to 22
Compared with example 2, the usage amounts of the photoinitiators in comparative examples 20 to 22 respectively account for 0%, 0.15% and 0.2% of the total mass of the 3D printing ceramic paste system.
The performance effect of the 3D printing ceramic paste prepared by the preparation method of the 3D printing ceramic paste provided by the embodiment of the invention is further explained by performing the following performance test on the prepared 3D printing ceramic paste.
Testing a sample: the 3D printing ceramic paste prepared by the preparation method provided by the embodiment 1-3 of the invention; the 3D printing ceramic paste prepared by the preparation method provided by the comparative examples 1-22 is adopted.
The test method comprises the following steps:
1. and (3) fineness test: and (3) placing the ceramic material on a scraper fineness meter, and performing fineness test according to the using method of the scraper fineness meter in the ink or paint industry. The place where particle aggregation or scratching occurred was observed as a result of the particle size test.
2. Cured thickness at 70% power: the ceramic material is flatly paved under a laser (with the thickness of about 2 mm) of a 3D printer, then the laser power percentage of the printer is set to be 70%, laser is controlled to scan a rectangular test piece with the size of 10 x 30mm on the material layer in a single time, and after the scanning is finished, the test piece is taken down to test the thickness of the test piece, namely the curing thickness.
3. Three-point bending strength: and testing according to a national standard GB/T6569 and 2006 fine ceramic bending test method to obtain the three-point bending strength of the finished product.
And (3) testing results: details are shown in table 1 below.
TABLE 1
The test results in table 1 show that the 3D printing ceramic paste prepared by the preparation method of the 3D printing ceramic paste provided by the embodiment of the present invention has no visible particle agglomeration after 2 μm gap blade coating, and the three-point bending strength of the prepared sample strip is above 908MPa after the test.
Comparing the test results of comparative example 1 and example 2, it can be seen that the 3D printed ceramic paste prepared by one-stage centrifugal stirring is coated with visible particle agglomeration through 5 μm gap scraping, and the three-point bending strength is 700MPa, which is significantly inferior to example 2, but the curing thickness of the two is not significantly different. Therefore, the invention adopts a two-stage centrifugal stirring process to obviously improve the uniformity of the paste and the three-point bending strength.
Comparative example 2 a ball milling process was used to prepare a 3D printed ceramic paste, which could not be dispersed due to too high system viscosity.
Comparing the test results of the comparative example 3 and the example 2, it can be seen that the 3D printing ceramic paste prepared by mechanical stirring is coated with visible particle agglomeration through a 20 μm gap, the curing thickness is 140 μm, and the three-point bending strength is 200MPa, i.e. the three properties are significantly inferior to those of the example 2. Therefore, the invention adopts a two-stage centrifugal stirring process to obviously improve the uniformity, the solidification thickness and the three-point bending strength of the paste.
Comparing the test results of comparative examples 4-7 with example 2, it can be seen that the rotational speeds of the first stage of centrifugal stirring are changed to 1000, 1100, 1600, 1700r/min, and the rest of the preparation conditions and the raw material usage are the same as those of example 2, the prepared 3D printing ceramic paste is coated with visible particle agglomeration through 4-5 μm gap scraping, the three-point bending strength is lower than 900MPa, and the influence on the curing thickness is not great. It can be seen that the rotating speed of the first-stage centrifugal stirring has a direct influence on the fineness and the three-point bending strength of the 3D printing ceramic paste, and has little influence on the curing thickness. And when the rotating speed of the first-stage centrifugal stirring is 1300r/min, the performance of the prepared 3D printing ceramic paste is particularly outstanding.
Comparing the test results of the comparative examples 8-11 with the test results of the example 2, it can be seen that the rotating speeds of the second-stage centrifugal stirring are changed to 1200r/min and 1300r/min respectively, the rest preparation conditions and the raw material use amounts are the same as those of the example 2, the prepared 3D printing ceramic paste is coated with visible particle agglomeration through a 9-10 mu m gap, and the three-point bending strength is lower than 900 MPa; when the rotation speed was increased to 2100, 2200r/min, the fineness of the 3D printed ceramic paste was comparable to example 2, but the three-point bending strength was decreased. When the rotation speed of the second-stage centrifugal stirring is 1700r/min, the above performance of the prepared 3D printing ceramic paste is particularly prominent.
Comparing the test results of comparative examples 12-15 with those of example 2, it can be seen that adjusting the amount and the mixing ratio of the monofunctional monomer and the polyfunctional monomer in the resin has little influence on the fineness of the 3D printed ceramic paste, but when all the monofunctional monomers are present in the resin, the curing thickness is significantly reduced; when all the resins are multifunctional monomers, the three-point bending strength is obviously reduced and is only 300MPa, and the three-point bending strength is only one third of that of example 2. When the using mixing ratio of the monofunctional monomer and the polyfunctional monomer of the resin is 2:1, the mechanical property of the prepared 3D printing ceramic paste is optimal.
Comparing the test results of comparative examples 16-19 with those of example 2, it can be seen that when no dispersant is used in the system, the system will not disperse, and as the dispersant usage increases to 0.3%, it is scraped with visible particle agglomeration through a 12 μm gap, and the three-point bending strength is only 564MPa, which is significantly inferior to example 2. When the amount of the dispersant was increased to 4.5% and 5%, the fineness thereof was equivalent to that of example 2, but the three-point bending strength was slightly inferior to that of example 2. The quality and the cost of the 3D printing ceramic paste are comprehensively considered, and the usage amount of the dispersing agent is preferably 0.4-4.375% of the total mass of the 3D printing ceramic paste system.
Comparing the test results of comparative examples 20 to 22 with those of example 2, it can be seen that the effect of adjusting the amount of the photoinitiator on the fineness of the 3D printed ceramic paste is not great, but when the amount of the photoinitiator is 0, the printing cannot be performed, and when the amount of the photoinitiator exceeds 1%, the three-point bending strength of the prepared 3D printed ceramic paste is rather deteriorated. Therefore, the usage amount of the photoinitiator is preferably 0.015 to 0.1 percent of the total mass of the system
In summary, the preparation method of the 3D printing ceramic paste provided by the embodiment of the invention adopts the scientific and reasonable raw material formula for compounding, and adopts a direct preparation mode to prepare the 3D printing ceramic paste, the operation mode is simple, the paste does not need to be prepared in a slurry conversion mode, the solid content of the system is not limited by the solid content of the slurry, the materials are stirred by a two-stage centrifugal stirring process, the uniform mixing of the materials can be realized, the solid content of the mixed material system can reach 80% -87.5%, the uniformity is good, the paste is applied to 3D printing, the shrinkage during degreasing and sintering is small, and the mechanical property of the finished product is excellent. No visible particle agglomeration is generated after 2 mu m clearance blade coating, and the three-point bending strength of the produced sample strip is over 900MPa after testing.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The preparation method of the 3D printing ceramic paste is characterized in that the 3D printing ceramic paste comprises the following raw materials in percentage by mass: 80 to 87.5 percent of Al2O3Ceramic powder, 10-17% of resin, 0.4-4.375% of dispersant, 0.1-1% of defoamer, 1.25-6% of plasticizer, 0.015-0.1% of photoinitiator and 0.5-4% of thickener;
the preparation method comprises the following steps:
weighing the components according to the formula for later use;
by using a dispersant on Al2O3Ball-milling pretreatment is carried out on the ceramic powder to obtain pretreated Al2O3Ceramic powder;
adding resin, a dispersing agent, a defoaming agent, a plasticizer and a photoinitiator into a reaction container, and carrying out centrifugal stirring to obtain a resin mixed solution, wherein the centrifugal rotation speed is 600-1000 r/min, and the time is 20-60 s;
subjecting the pretreated Al2O3Adding ceramic powder and a thickening agent into the resin mixed solution, and carrying out two-stage centrifugal stirring to obtain the 3D printing ceramic paste, wherein the rotating speed of the first-stage centrifugal stirring is 1200-1500 r/min for 30s, the rotating speed of the second-stage centrifugal stirring is 1400-2000 r/min for 60-120 s;
the resin comprises a monofunctional monomer and a polyfunctional monomer; the weight ratio of the using amount of the monofunctional group monomer to the multifunctional group monomer is 2: 1;
the monofunctional group monomer is at least one of isobornyl acrylate, 2-phenoxyethyl acrylate or isobornyl methacrylate;
the polyfunctional monomer is at least one of propoxylated glycerol triacrylate, trimethylolpropane triacrylate and ethoxylated trimethylolpropane trimethacrylate.
2. The method of preparing a 3D printed ceramic paste according to claim 1, wherein the pretreated Al is applied2O3Ceramic powder and a thickening agent are added into the resin mixed liquid, two-stage centrifugal stirring is carried out, and the 3D printing ceramic paste is obtained, wherein the rotating speed of the first-stage centrifugal stirring is 1200-1500 r/min, the time is 30s, the rotating speed of the second-stage centrifugal stirring is 1400-2000 r/min, and the time is 60-120 s, and the method specifically comprises the following steps:
subjecting the pretreated Al2O3And adding ceramic powder and a thickening agent into the resin mixed solution, and carrying out two-stage centrifugal stirring to obtain the 3D printing ceramic paste, wherein the rotating speed of the first-stage centrifugal stirring is 1300r/min for 30s, the rotating speed of the second-stage centrifugal stirring is 1700r/min for 60 s.
3. The method of preparing a 3D printed ceramic paste according to claim 1, wherein the applying comprises applying a pasteDispersant pair Al2O3Ball-milling pretreatment is carried out on the ceramic powder to obtain pretreated Al2O3The ceramic powder comprises the following steps:
al by using dispersant and absolute ethyl alcohol2O3And performing ball milling and drying pretreatment on the ceramic powder, wherein the ball milling rotation speed is 180-230 r/min, and the time is 1.5-3 h.
4. The method of preparing a 3D printing ceramic paste according to claim 3, wherein the Al is printed using a dispersant and absolute ethanol2O3Ball milling and drying pretreatment are carried out on the ceramic powder, the ball milling rotating speed is 180-230 r/min, and the time is 1.5-3 h, and the method specifically comprises the following steps:
by using dispersant and absolute ethyl alcohol to Al2O3Ball milling and drying pretreatment are carried out on the ceramic powder, the ball milling rotating speed is 200r/min, the time is 2h, and the drying temperature is 60 ℃.
5. The preparation method of the 3D printing ceramic paste according to claim 1, wherein the resin, the dispersant, the defoamer, the plasticizer and the photoinitiator are added into a reaction container for centrifugal stirring to obtain a resin mixed solution, wherein the step of centrifugal rotation speed of 600-1000 r/min for 20-60 s specifically comprises the following steps:
adding resin, a dispersing agent, a defoaming agent, a plasticizer and a photoinitiator into a reaction container, and carrying out centrifugal stirring to obtain a resin mixed solution, wherein the centrifugal rotation speed is 800r/min, and the time is 20 s.
6. The method of preparing a 3D printing ceramic paste of claim 1, wherein the Al is2O3Purity of ceramic powder>99.7%, a particle diameter of 0.5 to 2 μm, and a BET specific surface area of 1 to 15m2/g。
7. 3D printing ceramic paste, which is characterized in that the 3D printing ceramic paste is prepared by the preparation method of the 3D printing ceramic paste according to any one of claims 1-6.
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