阅读说明：本技术 氧化锆陶瓷膏料的制备方法及其氧化锆陶瓷膏料 (Preparation method of zirconia ceramic paste and zirconia ceramic paste ) 是由 李开武 陈盛贵 李楠 叶泽荣 黄坤 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种氧化锆陶瓷膏料的制备方法及其氧化锆陶瓷膏料,其中氧化锆陶瓷膏料的制备方法的步骤包括：(1)将氧化锆粉体、高分子类分散剂和乙醇混合搅拌均匀后球磨,经过筛、干燥、粉碎制得混合粉体；(2)将混合粉体、光敏树脂、光引发剂混合搅拌得到氧化锆陶瓷膏体；(3)在搅拌状态下向氧化锆陶瓷膏体中加入触变剂,经研磨细化得到氧化锆陶瓷膏料；其中氧化锆粉体于氧化锆陶瓷膏料中的体积百分比为50～70％,通过该方法制备的氧化锆陶瓷膏料具有高固含量和高触变特性及较高的稳定性。(The invention discloses a preparation method of zirconia ceramic paste and the zirconia ceramic paste, wherein the preparation method of the zirconia ceramic paste comprises the following steps: (1) mixing and stirring zirconium oxide powder, a macromolecular dispersant and ethanol uniformly, then ball-milling, sieving, drying and crushing to obtain mixed powder; (2) mixing and stirring the mixed powder, photosensitive resin and photoinitiator to obtain zirconia ceramic paste; (3) adding a thixotropic agent into the zirconia ceramic paste under the stirring state, and grinding and refining to obtain the zirconia ceramic paste; the volume percentage of the zirconia powder in the zirconia ceramic paste is 50-70%, and the zirconia ceramic paste prepared by the method has high solid content, high thixotropic property and high stability.)

1. The preparation method of the zirconia ceramic paste is characterized by comprising the following steps:

(1) mixing and stirring zirconium oxide powder, a macromolecular dispersant and ethanol uniformly, then ball-milling, sieving, drying and crushing to obtain mixed powder;

(2) mixing and stirring the mixed powder, photosensitive resin and photoinitiator to obtain zirconia ceramic paste;

(3) adding a thixotropic agent into the zirconia ceramic paste under a stirring state, and grinding and refining to obtain a zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 50-70%.

2. The preparation method of zirconia ceramic paste according to claim 1, wherein in the step (1), the zirconia powder, the polymeric dispersant and the ethanol are mixed in a mass ratio of 100: 60: (5-3) mixing.

3. The method of preparing a zirconia ceramic paste according to claim 1, wherein the drying conditions in the step (1) are: drying for 5-12 h in a 60 ℃ forced air drying oven at constant temperature.

4. The method of claim 1, wherein the volume percentages of the polymeric dispersant, the photosensitive resin, the photoinitiator and the thixotropic agent in the zirconia ceramic paste are 5-10%, 20-40%, 0.2-1% and 2-4% in sequence.

5. The method for preparing zirconia ceramic paste according to claim 1, wherein the zirconia powder has a particle size of 50 to 1000 nm.

6. The method of preparing the zirconia ceramic paste according to claim 1, wherein the photosensitive resin is at least one of 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, bisphenol a dimethacrylate, ethoxylated bisphenol a dimethacrylate, hydroxyethyl methacrylate, polyethylene glycol 400, acryloylmorpholine, hexafunctional aliphatic urethane acrylate, tetrafunctional aliphatic urethane acrylate and difunctional aliphatic urethane acrylate.

7. The method of preparing a zirconia ceramic paste according to claim 1, wherein said polymeric dispersant is at least one of BYK-W940, BYK-145, BYK-180 and BYK-109.

8. The method of preparing a zirconia ceramic paste according to claim 1, wherein the photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.

9. The method of preparing a zirconia ceramic paste according to claim 1, wherein said thixotropic agent is at least one of BYK-420, BYK-410 and BYK-405.

10. A zirconia ceramic paste, characterized in that it is prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of zirconia ceramic materials, in particular to a preparation method of a zirconia ceramic paste and the zirconia ceramic paste.

Background

The inherent brittleness and hardness of the zirconia ceramic material cause that the zirconia ceramic material cannot be processed by high-efficiency material waiting and material reducing like metal, and the preparation and forming of a complex shape structure are limited. The zirconia ceramic additive manufacturing technology has the advantages of few processes, high speed, free forming of special-shaped parts, high precision and the like, and is particularly suitable for occasions requiring various shapes, high manufacturing speed and small-batch production. In recent years, zirconia ceramic additive manufacturing technology is increasingly applied to the development of complex structural parts, such as profiled electrolytes for solid fuel cells.

Zirconia ceramic stereolithography is an additive manufacturing technique based on the principle of photopolymerization, typically with an ultraviolet beam provided by a laser positioned above a shaping stage. Firstly, mixing ceramic powder and liquid resin, preparing photosensitive resin slurry with certain solid phase content and viscosity, then controlling ultraviolet laser to scan the surface of the slurry to initiate photopolymerization reaction and layering and curing to obtain a blank body of polymer-coated powder particles, and finally degreasing and sintering to obtain the required part. At present, most of zirconia ceramic resin materials reported in documents are slurry materials with good fluidity, the solid content is mostly lower than 50 vol.%, the solid content is low, the precision forming on printing equipment is not facilitated, but the dispersion of ceramic materials in the resin materials is not facilitated due to the high solid content, so that the existing ceramic slurry also has the defects of easiness in layering and incapability of long-term storage, the printing effect on a sink printing equipment is influenced due to the poor thixotropy of the existing ceramic slurry, and the quality of printed products is finally influenced.

Therefore, a zirconia ceramic paste or a preparation method thereof is needed to solve the defects of the prior art.

Disclosure of Invention

The invention aims to provide a preparation method of a zirconia ceramic paste, and the zirconia ceramic paste prepared by the method has high solid content, high thixotropic property and high stability.

It is another object of the present invention to provide a zirconia ceramic paste having high printing fineness obtained by the above-mentioned preparation method.

In order to achieve the above object, the present invention provides a method for preparing zirconia ceramic paste, comprising the steps of:

(1) mixing and stirring zirconium oxide powder, a macromolecular dispersant and ethanol uniformly, then ball-milling, sieving, drying and crushing to obtain mixed powder;

(2) mixing and stirring the mixed powder, photosensitive resin and photoinitiator to obtain zirconia ceramic paste;

(3) adding a thixotropic agent into the zirconia ceramic paste under the stirring state, and grinding and refining to obtain the zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 50-70%.

Compared with the prior art, the preparation method of the zirconia ceramic paste material of the invention mixes and stirs the high solid content zirconia powder, the macromolecular dispersant and the ethanol to ensure that the dispersant is evenly distributed on the surface of the zirconia powder, and simultaneously, the volatilization of the solvent in the drying process after ball milling can promote that the dispersant is evenly anchored on the surface of the zirconia powder, thereby ensuring that the zirconia powder is not easy to cause agglomeration, which is beneficial to the dispersion of the zirconia powder in photosensitive resin, and further ensuring that the prepared zirconia ceramic paste material has better stability, in addition, the macromolecular dispersant anchored on the surface of the zirconia powder and the added thixotropic agent can generate synergistic action, thereby not only further improving the thixotropy of the zirconia ceramic paste material, but also effectively inhibiting the flow of the zirconia ceramic paste material caused by gravity in a static state, therefore, the zirconia ceramic paste material of the invention has better printing stability and storage stability, the printing success rate is high and the product does not settle after being placed for a long time; meanwhile, the acting force of the zirconia ceramic paste anchored by the macromolecular dispersant is greatly reduced after shearing, so that the zirconia ceramic paste has a smooth and fine paving effect after being paved on a platform by a scraper, and the zirconia ceramic paste also has higher printing fineness.

Preferably, the ball milling speed in step (1) of the invention is 100 and 400rpm, and the ball milling time is 2-24 h.

Preferably, the screen sieved in the step (1) of the invention is 100-200 meshes.

Preferably, the drying conditions in step (1) of the present invention are: drying for 5-12 h in a 60 ℃ forced air drying oven at constant temperature; the temperature makes the solvent have moderate volatilization speed, and promotes the dispersant to be evenly anchored on the surface of the zirconia powder.

Preferably, in step (1) of the present invention, a pulverizer is used for pulverization.

Preferably, in the step (1) of the present invention, the mass ratio of the zirconia powder, the polymeric dispersant, and the ethanol is 100: 60: (5-3) mixing.

Preferably, the volume percentages of the macromolecular dispersant, the photosensitive resin, the photoinitiator and the thixotropic agent in the zirconia ceramic paste are 5-10%, 20-40%, 0.2-1% and 2-4% in sequence. Wherein the volume percentage (V) of the zirconia powder in the zirconia ceramic paste is calculated by the following formula:

in the formula, m_z、ρ_zThe mass and density (5.9 g.cm) of the zirconia powder, respectively^-3)，m_r、ρ_rRespectively, the mass and density (1.1 g.cm.) of the photosensitive resin^-3)，m_d、ρ_dThe mass and density (1.1 g.cm) of the polymer dispersant^-3)，m_c、ρ_cMass and density of the thixotropic agent (1.1 g.cm), respectively^-3)，m_i、ρ_iRespectively, the mass and density of the photoinitiator (1.2 g.cm)^-3) (ii) a The volume percentage of other substances in the zirconia ceramic paste, i.e. the solid content of other substances, is calculated according to the mass and density of each substance.

Preferably, the particle size of the zirconia powder is 50-1000 nm.

Preferably, the vessel used for mixing and stirring in step (2) of the present invention is a planetary mixer or a homomixer.

Preferably, the stirring speed in step (2) of the present invention is 50 to 150rpm, and the stirring time is 10 to 12 hours.

Preferably, the stirring speed in step (3) of the present invention is 50 to 150rpm, and the stirring time is 2 to 4 hours.

Preferably, a three-roll grinder is adopted in the step (3) of the invention to grind and refine the materials at a roll spacing of 1-5 μm.

Preferably, the photosensitive resin of the present invention is at least one of 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, bisphenol a dimethacrylate, ethoxylated bisphenol a dimethacrylate, hydroxyethyl methacrylate, polyethylene glycol 400, acryloylmorpholine, hexafunctional aliphatic urethane acrylate, tetrafunctional aliphatic urethane acrylate, and difunctional aliphatic urethane acrylate.

Preferably, the macromolecular dispersant is at least one of BYK-W940, BYK-145, BYK-180 and BYK-109.

Preferably, the photoinitiator of the present invention is at least one of 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.

Preferably, the thixotropic agent of the present invention is at least one of BYK-420, BYK-410 and BYK-405.

In order to achieve the purpose, the invention also provides a zirconia ceramic paste, and the zirconia ceramic paste is prepared by the preparation method of the zirconia ceramic paste.

Compared with the prior art, the dispersing agent can be uniformly anchored on the surface of the zirconia powder in the preparation process of the zirconia ceramic paste, and the dispersing agent anchored on the surface of the zirconia powder and the added thixotropic agent can generate a synergistic effect, so that the thixotropy of the zirconia ceramic paste can be further improved, and the flow of the zirconia ceramic paste in a static state due to gravity can be effectively inhibited, so that the zirconia ceramic paste has better stability and does not settle after being placed for a long time; meanwhile, the acting force of the zirconia ceramic paste is greatly reduced after the zirconia ceramic paste is sheared, so that the zirconia ceramic paste has a smooth and fine paving effect after being sheared and paved on a platform, and the zirconia ceramic paste also has higher printing fineness.

Drawings

FIG. 1 is a stacking view of the zirconia ceramic paste of example 1.

FIG. 2 is a plan view of a zirconia ceramic paste of the present invention cut by a machine blade and laid on a platform.

FIG. 3 shows a test piece printed with the zirconia ceramic paste of example 1 after sintering.

FIG. 4 is a microscopic size of the aperture of the test piece of FIG. 3.

Detailed Description

In order to explain the technical contents of the present invention and the technical effects achieved in the present invention in detail, the following description will be given with reference to the embodiments. All reagents in the examples and comparative examples are commercially available.

Example 1

A preparation method of zirconia ceramic paste comprises the following steps:

(1) mixing and stirring 1000g of zirconium oxide powder (D50 ═ 100nm), 35g of BYK-145 and 600g of ethanol uniformly, then putting the mixture into a ball milling tank, ball milling the mixture for 3 hours at the rotating speed of 200rpm, sieving the mixture through a 150-mesh screen, drying the mixture for 12 hours in a 60 ℃ forced air drying oven at constant temperature, and crushing the dried mixture by using a crusher to obtain mixed powder;

(2) adding 62.5g of 1, 6-hexanediol diacrylate, 62.5g of trimethylolpropane triacrylate, 1.25g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and the mixed powder into a planetary stirrer, and stirring at the rotating speed of 50rpm for 12 hours to obtain a zirconium oxide ceramic paste;

(3) adding 9g of BYK-410 into the zirconia ceramic paste under stirring at the rotating speed of 70rpm, stirring for 2 hours, and grinding and refining by a three-roll grinder at a roll spacing of 1 mu m to obtain zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 52.28 percent.

Example 2

A preparation method of zirconia ceramic paste comprises the following steps:

(1) mixing and stirring 700g of zirconium oxide powder (D50 is 100nm), 300g of zirconium oxide powder (D50 is 1000nm), 30g of BYK-180 and 600g of ethanol uniformly, then putting the mixture into a ball milling tank, ball milling the mixture for 8 hours at the rotating speed of 100rpm, sieving the mixture through a 100-mesh sieve, drying the mixture for 8 hours in a 60-DEG C forced air drying oven at constant temperature, and crushing the dried mixture by a crusher to obtain mixed powder;

(2) adding 85.5g of 1, 6-hexanediol diacrylate, 40.5g of difunctional aliphatic urethane acrylate, 0.75g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 0.5g of 1-hydroxycyclohexyl phenyl ketone and the mixed powder into a homogenizing and dispersing machine, and stirring at the rotating speed of 120rpm for 10 hours to obtain a zirconium oxide ceramic paste;

(3) adding 8g of BYK-420 into the zirconia ceramic paste under stirring at the rotating speed of 100rpm, stirring for 3 hours, and grinding and refining by a three-roll grinder at a roll spacing of 3 mu m to obtain zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 53.09%.

Example 3

A preparation method of zirconia ceramic paste comprises the following steps:

(1) mixing and stirring 600g of zirconium oxide powder (D50 ═ 200nm), 400g of zirconium oxide powder (D50 ═ 500nm), 8g of BYK-W940, 8g of BYK-180 and 600g of ethanol uniformly, then putting the mixture into a ball milling tank to ball mill for 15 hours at the rotating speed of 400rpm, firstly sieving the mixture through a 200-mesh sieve, then drying the mixture for 10 hours in a 60 ℃ forced air drying oven at constant temperature, and crushing the dried mixture by a crusher to obtain mixed powder;

(2) adding 75g of hydroxyethyl methacrylate, 40g of tetrafunctional aliphatic polyurethane acrylate, 0.6g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 0.6g of 1-hydroxycyclohexyl phenyl ketone and the mixed powder into a planetary stirrer, and stirring at the rotating speed of 70rpm for 10 hours to obtain a zirconium oxide ceramic paste;

(3) adding 10g of BYK-405 into the zirconia ceramic paste under stirring at the rotating speed of 140rpm, stirring for 4 hours, and grinding and refining by a three-roll grinder at a roll spacing of 3 mu m to obtain zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 56.74%.

Example 4

A preparation method of zirconia ceramic paste comprises the following steps:

(1) mixing and stirring 1000g of zirconium oxide powder (D50 ═ 100nm), 35g of BYK-145 and 600g of ethanol uniformly, then putting the mixture into a ball milling tank to ball mill for 3 hours at the rotating speed of 200rpm, firstly sieving the mixture through a 150-mesh sieve, then drying the mixture for 12 hours in a vacuum drying oven at the temperature of 60 ℃, and crushing the dried mixture by using a crusher to prepare mixed powder;

(2) adding 62.5g of 1, 6-hexanediol diacrylate, 62.5g of trimethylolpropane triacrylate, 1.25g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and the mixed powder into a planetary stirrer, and stirring at the rotating speed of 50rpm for 12 hours to obtain a zirconium oxide ceramic paste;

(3) adding 9g of BYK-410 into the zirconia ceramic paste under stirring at the rotating speed of 70rpm, stirring for 2 hours, and grinding and refining by a three-roll grinder at a roll spacing of 1 mu m to obtain zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 52.28 percent.

Comparative example 1

A preparation method of zirconia ceramic paste comprises the following steps:

(1) mixing and stirring 1000g of zirconium oxide powder (D50 ═ 100nm), 35g of BYK-145 and 600g of ethanol uniformly, then putting the mixture into a ball milling tank, ball milling the mixture for 3 hours at the rotating speed of 200rpm, sieving the mixture through a 150-mesh screen, drying the mixture for 12 hours in a 60 ℃ forced air drying oven at constant temperature, and crushing the dried mixture by using a crusher to obtain mixed powder;

(2) adding 62.5g of 1, 6-hexanediol diacrylate, 62.5g of trimethylolpropane triacrylate, 1.25g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and the mixed powder into a planetary stirrer, stirring at the rotating speed of 50rpm for 12 hours to obtain a zirconium oxide ceramic paste, and grinding and refining by a three-roll grinder at the roll spacing of 1 mu m to obtain the zirconium oxide ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 53.63%.

Comparative example 2

A preparation method of zirconia ceramic paste comprises the following steps:

(1) adding 1000g of zirconium oxide powder (D50 is 100nm), 35g of BYK-145, 62.5g of 1, 6-hexanediol diacrylate, 62.5g of trimethylolpropane triacrylate and 1.25g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide into a planetary stirrer, and stirring at the rotating speed of 50rpm for 12 hours to obtain a zirconium oxide ceramic paste;

(2) adding 9g of BYK-410 into the zirconia ceramic paste under stirring at the rotating speed of 70rpm, stirring for 2 hours, and grinding and refining by a three-roll grinder at a roll spacing of 1 mu m to obtain zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 52.28 percent.

Comparative example 3

A preparation method of zirconia ceramic paste comprises the following steps:

(1) mixing and stirring 1000g of zirconia powder (D50 is 100nm), 35g of polyether polyol oligomer and 600g of ethanol uniformly, then putting the mixture into a ball milling tank, ball milling the mixture for 3 hours at the rotating speed of 200rpm, sieving the mixture through a 150-mesh screen, drying the mixture for 12 hours in a 60 ℃ forced air drying oven at constant temperature, and crushing the dried mixture by using a crusher to obtain mixed powder;

(2) adding 62.5g of 1, 6-hexanediol diacrylate, 62.5g of trimethylolpropane triacrylate, 1.25g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and the mixed powder into a planetary stirrer, and stirring at the rotating speed of 50rpm for 12 hours to obtain a zirconium oxide ceramic paste;

(3) adding 9g of BYK-410 into the zirconia ceramic paste under stirring at the rotating speed of 70rpm, stirring for 2 hours, and grinding and refining by a three-roll grinder at a roll spacing of 1 mu m to obtain zirconia ceramic paste;

wherein the volume percentage of the zirconia powder in the zirconia ceramic paste is 52.28 percent.

The solid contents of the zirconia powder of examples 1 to 4 were 52.28 vol.%, 53.09 vol.%, 56.74 vol.%, and 52.28 vol.%, and the zirconia ceramic paste prepared in examples 1 to 4 had a high solid content. The zirconia ceramic paste obtained in example 1 was deposited, and the paste did not flow after deposition, and the paste could maintain the shape of the deposit shown in fig. 1, and the zirconia ceramic paste obtained in examples 2 to 4 was deposited, and the paste did not flow after deposition. The zirconia ceramic pastes obtained in examples 1 to 4 and comparative examples 1 to 3 were allowed to stand for 30 days, 90 days and 150 days, respectively, and then tested for sedimentation amount, and the results are shown in the following Table 1:

TABLE 1 results of sedimentation amount test of zirconia ceramic pastes obtained in examples 1 to 4 and comparative examples 1 to 3

Comparing example 1 with comparative example 1, the result shows that the stability of the zirconia ceramic paste of example 1 is better than that of comparative example 1, which is probably because the dispersant anchored on the surface of the zirconia powder and the added thixotropic agent generate a synergistic effect, and can effectively inhibit the flow of the zirconia ceramic paste in a static state caused by gravity, so that the stability of the zirconia ceramic paste is better.

Comparing example 1 with comparative example 2, the result shows that the stability of the zirconia ceramic paste of example 1 is better than that of comparative example 2, which indicates whether the polymeric dispersant is uniformly anchored on the surface of the zirconia powder, which will affect the synergistic effect between the dispersant anchored on the surface of the zirconia powder and the thixotropic agent, and further affect the stability of the zirconia ceramic paste.

Comparing example 1 with comparative example 3, the results show that the stability of the zirconia ceramic paste of example 1 is superior to that of comparative example 3, probably because the small molecular dispersant has poor compatibility with the photosensitive resin, and thus precipitates in a large amount to cause poor stability of the zirconia ceramic paste.

The zirconia ceramic pastes prepared in examples 1-4 were sheared using a machine blade to enable spreading on a platform as shown in fig. 2, and the minimum blade speed at which they could be spread was recorded, with a larger value indicating that the zirconia ceramic paste was harder to shear and spread, and too fast a blade operation causing greater pressure on the underlying paste during spreading resulting in unstable prints, as shown in table 2 below.

TABLE 2 minimum doctor blade rate required for leveling of zirconia ceramic pastes obtained in examples 1-4

The zirconia ceramic paste prepared in example 1 was printed on a sunken SLA printer and then sintered, and the sintered test piece had a higher fineness, as shown in FIGS. 3 to 4. Therefore, the zirconia ceramic paste system has better stability and printing fineness in the printing stage.

Comparing example 1 with example 4, the results show that the zirconia ceramic paste of example 4 is relatively difficult to shear-flatten, probably because the vacuum condition affects the uniform anchoring of the dispersant to the zirconia powder surface, which in turn affects the synergistic effect between the dispersant and the thixotropic agent anchored to the zirconia powder surface, resulting in relatively slightly poor thixotropy of the zirconia ceramic paste of example 4.

The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.