阅读说明：本技术 一种二氧化钛光敏树脂陶瓷浆料及其制备方法和应用 (Titanium dioxide photosensitive resin ceramic slurry and preparation method and application thereof ) 是由 杜纯 邹无有 单斌 胡镔 吴卫东 于 2020-11-20 设计创作，主要内容包括：本发明属于非金属增材制造技术领域,具体涉及一种梯度粒径二氧化钛光敏树脂陶瓷浆料及其制备方法和应用。本发明一种梯度粒径二氧化钛光敏树脂陶瓷浆料,按照体积份数,包括以下组分：低聚物25-55份、单体10-25份、活性稀释剂3-8份、分散剂3-5份、光引发剂9-18份、助剂1-3份、二氧化钛陶瓷粉末1-40份。本发明采用混合类光引发剂和混合光源,相比以往传统光固化设备为单一紫外光源,陶瓷浆料使用单一光引发剂,本发明增强陶瓷光敏树脂浆料对于光的吸收固化反应,以此抵消二氧化钛陶瓷对于光的反射,确保在单位时间内浆料固化深度达到一定尺度,缺陷少,成型效果好。(The invention belongs to the technical field of non-metal additive manufacturing, and particularly relates to a titanium dioxide photosensitive resin ceramic slurry with a gradient particle size, and a preparation method and application thereof. The invention relates to a titanium dioxide photosensitive resin ceramic slurry with gradient particle size, which comprises the following components in parts by volume: 25-55 parts of oligomer, 10-25 parts of monomer, 3-8 parts of reactive diluent, 3-5 parts of dispersant, 9-18 parts of photoinitiator, 1-3 parts of auxiliary agent and 1-40 parts of titanium dioxide ceramic powder. Compared with the traditional light curing equipment which adopts a single ultraviolet light source and uses a single photoinitiator for ceramic slurry, the mixed light source adopts a mixed photoinitiator and a mixed light source, the absorption curing reaction of the ceramic photosensitive resin slurry to light is enhanced, so that the reflection of titanium dioxide ceramic to light is counteracted, the curing depth of the slurry in unit time reaches a certain scale, the defects are few, and the forming effect is good.)

1. The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is characterized by comprising the following components in parts by volume: 25-55 parts of oligomer, 10-25 parts of monomer, 3-8 parts of reactive diluent, 3-5 parts of dispersant, 9-18 parts of photoinitiator, 1-3 parts of assistant and 1-40 parts of titanium dioxide ceramic powder, wherein the absorption wavelength peak value of the photoinitiator is 245-405nm, the titanium dioxide ceramic powder is gradient particle size titanium dioxide ceramic powder, and the gradient particle size titanium dioxide ceramic powder is formed by mixing nano-scale and micron-scale in any proportion.

2. The ceramic slurry according to claim 1, further comprising sucrose, wherein the sucrose is 1-3 parts by volume.

3. Ceramic slurry according to claim 1 or 2, characterized in that the photoinitiator is a mixture of three of 2-hydroxy-2-methylphenylacetone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.

4. The ceramic slurry according to claim 3, wherein the photoinitiator further comprises any one or a mixture of 2 or more of benzophenone, 4' -bis (dimethylamino) benzophenone, and 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone.

5. The ceramic slurry according to claim 3, wherein the oligomer is one or a mixture of any two or more of aliphatic diacrylate, aliphatic urethane acrylate, epoxy acrylate, and carboxy ethyl acrylate; the monomer is one or a mixture of any two or more of acrylic hydroxyl ester, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate and trimethylolpropane triacrylate.

6. The ceramic slurry according to claim 2, wherein the auxiliary agent is at least one of magnesium oxide, calcium oxide, copper oxide, and silicon oxide, or a mixture of any two or more of them.

7. The ceramic slurry according to claim 1, wherein the reactive diluent is a polyether modified silicone surfactant, and the dispersant is at least one of SRE-4026X, BYK-P105, Disperbyk-111, Disperbyk-168, or a mixture of any two or more thereof.

8. The method for preparing a gradient particle size titanium dioxide photosensitive resin ceramic slurry according to any one of claims 1 to 7, comprising the steps of:

(1) under the condition of keeping out of the sun, sequentially adding the oligomer, the monomer, the reactive diluent, the dispersant and the photoinitiator into a container, and uniformly mixing to obtain a semitransparent liquid;

(2) adding titanium dioxide ceramic powder, sucrose and an auxiliary agent into the obtained liquid, stirring to a uniform state under an ultrasonic heating condition, and performing ball milling for 3-5 hours to obtain slurry.

9. The use of the gradient-particle-diameter titanium dioxide photosensitive resin ceramic slurry according to any one of claims 1 to 7, wherein the use comprises curing and molding under the action of a mixed light source as a slurry for 3D printing.

10. The method as claimed in claim 9, wherein the wavelength of the mixed light source is 245-405 nm.

Technical Field

The invention belongs to the technical field of non-metal additive manufacturing, and particularly relates to a titanium dioxide photosensitive resin ceramic slurry with a gradient particle size, and a preparation method and application thereof.

Background

The 3D printing technology is also called fast molding technology (RPM for short) or additive Manufacturing technology, and includes fused deposition molding, selective laser sintering, stereolithography solidification fast molding and other technologies, wherein the stereolithography solidification fast molding technology includes DLP and SLA, both of which are obtained by ultraviolet light curing photosensitive resin layer-by-layer molding to obtain a final complete entity, and has the advantages of simple operation, fast molding speed and high molding precision. In the stereolithography curing rapid prototyping technology, photosensitive resin is the key, the quality of the photosensitive resin determines whether photocuring forming can be carried out or not and the quality of a formed part, titanium dioxide ceramics has strong light scattering performance, and the conventional photosensitive resin is difficult to be applied to photocuring 3D printing of the titanium dioxide ceramics with high solid content.

The titanium dioxide ceramic has the advantages of high photocatalytic activity, stable chemical property, no toxicity to organisms, rich raw material sources and the like, is widely applied to the fields of biomedicine, energy, environmental protection and catalysis such as sunscreen skin care products, solar cells, water pollution treatment and the like, and is the photocatalytic material with the application potential at present. At present, the ceramic part is mainly formed by modes of grouting, mould pressing, extruding and the like, but a conventional ceramic manufacturing technology needs to manufacture a mould in advance, has high preparation cost and long production period, is difficult to meet the requirement of people on quick manufacturing of personalized, refined, lightweight and complicated high-end products, and provides a brand-new possibility for solving the problems and the requirement by applying a 3D printing technology to the manufacturing of ceramic parts.

However, in order to obtain a titanium dioxide ceramic, it is necessary to prepare a ceramic photosensitive resin paste, but the preparation of the paste at present has some problems: (1) the titanium dioxide ceramic has strong reflection and other phenomena on ultraviolet light, the higher the solid content of the titanium dioxide ceramic is, the stronger the reflection on the light is, the more difficult the curing of the ceramic photosensitive resin slurry is, and the titanium dioxide ceramic photosensitive resin with high solid content is difficult to realize; (2) the higher the solid content of the titanium dioxide ceramic is, the higher the viscosity of the ceramic photosensitive resin slurry is, the more difficult the ceramic photosensitive resin slurry flows, the poorer the dispersibility is, and the photocuring printing effect is seriously influenced; (3) the ceramic photosensitive resin needs to be degreased and sintered after being subjected to photocuring forming, the sintering temperature of the ceramic is higher, energy is wasted, and the quality and the performance of photocuring forming parts are directly influenced by the degreasing and sintering effect, so that the application of the parts is directly related.

CN111348921A discloses a ceramic material for photocuring forming and an emulsion coating preparation method and application thereof, wherein the method comprises the following steps: (1) mixing photosensitive resin, an emulsifier and deionized water to form a completely dispersed coating precursor emulsion, adding ceramic powder into the coating precursor emulsion, and uniformly dispersing the ceramic powder in the coating precursor emulsion; (2) and (2) adding a photoinitiator into the mixture obtained in the step (1), irradiating by adopting ultraviolet light, carrying out a crosslinking reaction on the photosensitive resin under the irradiation of the ultraviolet light to form a gel on the surface of the ceramic powder, and uniformly coating the ceramic powder with the gel to obtain the ceramic material. However, the technical solution does not consider the influence of 3D printing, ceramic sintering and the like, and there is room for improvement.

CN111035802A discloses a preparation method of a hydroxyapatite/titanium dioxide composite bioceramic with a three-period minimum curved surface structure through photocuring 3D printing, wherein the composition comprises: 30 wt% of micron-sized hydroxyapatite powder, 5 wt% of titanium dioxide powder, 55 wt% of acrylated epoxy resin and a small amount of auxiliary agent. According to the technical scheme, a three-period extremely-small curved surface model with controllable polymorphic porosity is designed by using Rhino software, model slices are led out to a DLP 3D printer, slurry is prepared according to a proportion and is printed after ball milling, and a blank after printing is placed into a tube furnace to complete degreasing and sintering according to parameters. The technical scheme finally obtains the titanium dioxide composite bioceramic with controllable porosity, compact crystal grains and excellent mechanical property, but the titanium dioxide content is lower, and an improved space exists.

In summary, the prior art still lacks a photosensitive resin ceramic with high content of titanium dioxide.

Disclosure of Invention

Aiming at the defects or improvement requirements of the prior art, the invention provides the titanium dioxide photosensitive resin ceramic slurry, the mixed photoinitiator and the mixed light source are adopted, compared with the traditional light curing device which is a single ultraviolet light source, the ceramic slurry uses the single photoinitiator, the absorption curing reaction of the ceramic photosensitive resin slurry to light is enhanced, so that the reflection of the titanium dioxide ceramic to the light is counteracted, the curing depth of the slurry in unit time (10-15s) reaches a certain scale (more than 100 micrometers), and finally the high-content titanium dioxide photosensitive resin ceramic is obtained.

In order to achieve the above object, according to one aspect of the present invention, there is provided a gradient particle size titanium dioxide photosensitive resin ceramic slurry comprising the following components in parts by volume: 25-55 parts of oligomer, 10-25 parts of monomer, 3-8 parts of reactive diluent, 3-5 parts of dispersant, 9-18 parts of photoinitiator, 1-3 parts of assistant and 1-40 parts of titanium dioxide ceramic powder, wherein the absorption wavelength peak value of the photoinitiator is 245-405nm, the titanium dioxide ceramic powder is gradient particle size titanium dioxide ceramic powder, and the gradient particle size titanium dioxide ceramic powder is formed by mixing nano-scale and micron-scale in any proportion.

Oligomers, also called oligomers, generally referred to as more than dimerized, having a molecular weight of 10⁴Hereinafter referred to as oligomers.

Preferably, the food also comprises sucrose, and the volume part of the sucrose is 1-3 parts.

Preferably, the photoinitiator is a mixture of three of 2-hydroxy-2-methylphenylacetone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.

Preferably, the photoinitiator further comprises any one of benzophenone, 4' -bis (dimethylamino) benzophenone, and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, or a mixture of 2 or more thereof.

The photoinitiator used in the present invention and the absorption wavelength peak thereof are as follows.

2-hydroxy-2-methylphenylacetone, 1173 for short, absorption wavelength peak: 244. 278 nm and 322 nm.

Phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, abbreviated 819, has an absorption wavelength peak: 370. 405 nm.

(2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, abbreviated as TPO, having an absorption wavelength peak: 269. 298, 379 and 393 nm.

Benzophenone, BP for short, absorption wavelength peak: 253. 345 nm.

4, 4' -bis (dimethylamino) benzophenone, MK for short, absorption wavelength peak: 365 nm.

2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, abbreviation 907, absorption wavelength peak: 232. 307 nm.

Preferably, the oligomer is one or a mixture of any two or more of aliphatic diacrylate, aliphatic urethane acrylate, epoxy acrylate and carboxyl ethyl acrylate; the monomer is one or a mixture of any two or more of acrylic hydroxyl ester, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate and trimethylolpropane triacrylate.

Preferably, the auxiliary agent is at least one of magnesium oxide, calcium oxide, copper oxide and silicon oxide or a mixture of any two or more of the magnesium oxide, the calcium oxide, the copper oxide and the silicon oxide.

Preferably, the reactive diluent is polyether modified organic silicon surfactant, and the dispersant is at least one or a mixture of any two or more of SRE-4026X, BYK-P105, Disperbyk-111 and Disperbyk-168. The polyether modified organosilicon surfactant is SH-300 polyether modified organosilicon surfactant and SH-200 polyether modified organosilicon surfactant of Shenzhen Jipeng silicon fluorine material Limited.

According to another aspect of the present invention, there is provided a method for preparing a graded-particle-diameter titanium dioxide photosensitive resin ceramic slurry, comprising the steps of:

(1) under the condition of keeping out of the sun, sequentially adding the oligomer, the monomer, the reactive diluent, the dispersant and the photoinitiator into a container, and uniformly mixing to obtain a semitransparent liquid;

(2) adding titanium dioxide ceramic powder, sucrose and an auxiliary agent into the obtained liquid, stirring to a uniform state under an ultrasonic heating condition, and performing ball milling for 3-5 hours to obtain slurry.

According to another aspect of the invention, the application of the gradient-particle-size titanium dioxide photosensitive resin ceramic slurry is provided, and the application comprises that the slurry serving as 3D printing is cured and molded under the action of a mixed light source.

Preferably, the wavelength of the mixed light source is 245-405 nm.

The invention has the following beneficial effects:

(1) compared with the traditional light curing equipment which adopts a single ultraviolet light source and uses a single photoinitiator for ceramic slurry, the mixed light source adopts a mixed photoinitiator and a mixed light source, the absorption curing reaction of the ceramic photosensitive resin slurry to light is enhanced, so that the reflection of titanium dioxide ceramic to light is counteracted, the curing depth of the slurry in unit time reaches a certain scale, the defects are few, and the forming effect is good.

(2) The invention uses titanium dioxide with gradient particle size, and for titanium dioxide ceramics with different particle sizes and different solid contents, such as nano, micron and the like, the addition of the mixed photoinitiator and the use of the mixed light source can effectively offset the light scattering of the titanium dioxide, improve the light curing depth and speed of the photosensitive resin and powerfully ensure the light curing molding of the photosensitive resin.

(3) The invention uses the cane sugar to improve the sintering quality, adds the auxiliary agent to reduce the sintering temperature, adds the surface active diluent and the dispersing agent to improve the dispersibility and the fluidity of the slurry, and further enhances the dispersibility of the slurry by stirring and preparing the slurry under the ultrasonic heating condition.

(4) The photosensitive resin ceramic slurry can be suitable for photocuring 3D printing of titanium dioxide ceramics with different particle sizes and different solid contents, and can print high-solid-content titanium dioxide ceramics with volume fraction of more than 40%.

(5) The preparation method is simple in preparation process, and can be directly applied to the manufacture of complex structural components in the fields of catalytic carriers, biological models, artware and the like.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

Example 1

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X, 9.5 ml of photoinitiator TPO, 11739.5 ml of photoinitiator and 8199.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, uniformly stirring under an ultrasonic heating condition, wherein the ultrasonic frequency is 40KHZ, the ultrasonic input power is 200W, the ultrasonic heating temperature is 40 ℃, and performing ultrasonic milling for 5 hours after half an hour to obtain the slurry.

Example 2

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 60 ml of aliphatic diacrylate, 20 ml of aliphatic polyurethane acrylic resin, 33 ml of dipropylene glycol diacrylate, SH-30010.5 ml of surfactant diluent, SRE-4026X 7 ml of dispersant, 8.5 ml of photoinitiator TPO, 11738.5 ml of photoinitiator and 8198.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 40 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Example 3

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 48 ml of aliphatic diacrylate, 20.5 ml of aliphatic polyurethane acrylic resin, 30 ml of dipropylene glycol diacrylate, SH-3009 ml of surface active diluent, 6 ml of dispersing agent SRE-4026X, 7.5 ml of photoinitiator TPO, 11737.5 ml of photoinitiator and 8197.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 60 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Example 4

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 42.5 ml of aliphatic diacrylate, 16 ml of aliphatic polyurethane acrylic resin, 25 ml of dipropylene glycol diacrylate, SH-3008 ml of surface active diluent, 5 ml of dispersing agent SRE-4026X, 6.5 ml of photoinitiator TPO, 11736.5 ml of photoinitiator and 8196.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 80 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Comparative example 1

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 9.5 ml of photoinitiator TPO, 11739.5 ml of photoinitiator and 8199.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain translucent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Comparative example 2

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X, 9.5 ml of photoinitiator TPO, 11739.5 ml of photoinitiator and 8199.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, performing ultrasonic heating at the temperature of 40 ℃ under the ultrasonic frequency of 40KHZ and the ultrasonic input power of 200W, performing ultrasonic milling for 5 hours after half an hour, and thus obtaining the slurry.

Comparative example 3

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, 8 ml of dispersing agent SRE-4026X, 9.5 ml of photoinitiator TPO, 11739.5 ml of photoinitiator and 8199.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Comparative example 4

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X and 28.5 ml of photoinitiator TPO into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Comparative example 5

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X and 117328.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Comparative example 6

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X and 81928.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Comparative example 7

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X, 9.5 ml of photoinitiator TPO, 11739.5 ml of photoinitiator and 8199.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of magnesium oxide and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, performing ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, performing ultrasonic treatment for half an hour, and performing ball milling for 5 hours to obtain slurry.

Comparative example 8

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X, 9.5 ml of photoinitiator TPO, 11739.5 ml of photoinitiator and 8199.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar, 2 ml of magnesium oxide and 20 ml of micron-sized titanium dioxide ceramic powder into the liquid, carrying out ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, carrying out ultrasonic treatment for half an hour, and carrying out ball milling for 5 hours to obtain the slurry.

Comparative example 9

The photosensitive resin ceramic slurry of titanium dioxide with the gradient particle size is prepared by the following method:

(1) under the condition of keeping out of the sun, adding 63 ml of aliphatic diacrylate, 24.5 ml of aliphatic polyurethane acrylic resin, 40 ml of dipropylene glycol diacrylate, SH-30012 ml of surface active diluent, 8 ml of dispersing agent SRE-4026X, 9.5 ml of photoinitiator TPO, 11739.5 ml of photoinitiator and 8199.5 ml of photoinitiator into a 250 ml beaker, and uniformly mixing to obtain a semitransparent liquid;

(2) adding 2 ml of cane sugar and 20 ml of micron-sized nano-grade mixed titanium dioxide ceramic powder into the liquid, performing ultrasonic heating under the conditions of ultrasonic frequency of 40KHZ, ultrasonic input power of 200W and ultrasonic heating temperature of 40 ℃, performing ultrasonic treatment for half an hour, and performing ball milling for 5 hours to obtain the slurry.

The slurries obtained in examples 1 to 4 and comparative examples 1 to 9 were 3D printed, cured and molded under a mixed light source with a wavelength of 245-.

Examples 1-4 all printed successfully. It was tested that the photocuring depth of example 1 was 211 microns, that of example 2 was 157 microns, that of example 3 was 125 microns, and that of example 4 was 102 microns. Furthermore, the sintered quality of the molded articles of example 1 is clearly superior to that of comparative examples 7 and 8, with few defects. The light curing depth is measured by fixing a small number of layers of ceramics (each layer is fixed for 10-15s) by manual exposure or curing with a device, such as one layer or ten layers, and then measuring the thickness of the ceramics, and dividing the thickness by the number of layers to obtain the light curing depth. The comprehensive mechanical properties of the products in the embodiments 1 to 4 meet the use requirements, the mechanical properties of the printed products are measured by a universal testing machine testing device, the tensile strength exceeds 40MPa, and the engineering application requirements are met.

In comparative example 1, no dispersant is added, and the titanium dioxide ceramic powder is seriously agglomerated and obviously layered, so that the photocuring 3D printing cannot be performed.

Comparative example 2 was not stirred under ultrasonic heating conditions, and the titanium dioxide ceramic powder was partially agglomerated and could not be photocured for 3D printing.

Comparative example 3 in which no surface active diluent was added, the photosensitive resin had a large viscosity and poor flowability, and the molded article had a large amount of defects and poor quality.

Comparative examples 4 to 6 the photosensitive resin was not photo-curable using a single photoinitiator.

In comparative example 7, sucrose was not added, and printing was successful, but defects such as warpage, delamination, cracks and the like were present in the molded article after sintering.

Comparative example 8, which used pure micron-sized titanium dioxide ceramic powder, was successfully printed, but the sintered molded part had a few defects.

In comparative example 9, no sintering aid is added, the sintering temperature of the formed part is required to be above 1350 ℃, and in examples 1 and 2, the formed part can be sintered only at the sintering temperature of 1150 ℃.

It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.