阅读说明：本技术 一种3d打印材料及其制备方法、3d打印方法 (3D printing material, preparation method thereof and 3D printing method ) 是由 黄灿 杨壮志 许松 杨渝昆 王远刚 王秋森 于 2020-07-10 设计创作，主要内容包括：本发明提供了一种3D打印材料及其制备方法、3D打印方法。打印材料按质量份计的39.9~47.2份二氧化锆粉末、11.4~17.7份增强粉末以及41~43份粘接剂组成。制备方法包括将二氧化锆粉末、增强粉末以粘接剂混炼得到3D打印材料。3D打印方法包括：将3D打印材料熔融后,打印出所需形状的预成形坯；对预成形坯脱脂处理后烘干,得到脱脂后烘干的预成形坯；惰性气体下,将脱脂后烘干的预成形坯烧结,得到3D打印制件。本发明的3D打印方法打印的制件成形精度高、产品性能一致性好,成型快捷；3D打印材料生物相容性和化学稳定性好。(The invention provides a 3D printing material, a preparation method thereof and a 3D printing method. The printing material comprises, by mass, 39.9-47.2 parts of zirconium dioxide powder, 11.4-17.7 parts of reinforcing powder and 41-43 parts of adhesive. The preparation method comprises the step of mixing zirconium dioxide powder and reinforcing powder with a binder to obtain the 3D printing material. The 3D printing method comprises the following steps: fusing the 3D printing material, and printing a preformed blank with a required shape; degreasing the preformed blank and then drying to obtain the degreased and dried preformed blank; and sintering the degreased and dried preform under inert gas to obtain the 3D printing part. The 3D printing method has the advantages that the formed part printed by the method is high in forming precision, good in product performance consistency and quick to form; the 3D printing material has good biocompatibility and chemical stability.)

1. The 3D printing material is characterized by comprising the following components in parts by mass:

39.9-47.2 parts of zirconium dioxide powder, 11.4-17.7 parts of reinforcing powder and 41-43 parts of adhesive.

2. The 3D printing material according to claim 1, which is composed of the following components in parts by mass:

41.2-45.7 parts of zirconium dioxide powder, 12.5-16.4 parts of reinforcing powder and 41.3-42.5 parts of adhesive.

3. The 3D printed material according to claim 1 or 2, wherein the binder consists of the following components in parts by mass:

75-80 parts of polyethylene glycol, 10-15 parts of polymethyl methacrylate, 6-8 parts of stearic acid and 3-5 parts of acrylate.

4. 3D printing material according to claim 1 or 2, characterized in that the zirconium dioxide powder and the reinforcing powder have an average particle size of 35 μ ι η to 50 μ ι η.

5. 3D printed material according to claim 1 or 2, characterized in that the strengthening powder is a mixture of aluminium oxide and silicon dioxide.

6. 3D printing material according to claim 1 or 2, characterized in that the 3D printing material further comprises yttrium oxide and/or calcium oxide, wherein the yttrium oxide content is 1.5mol% to 3.5mol% and the calcium oxide content is 1mol% to 2mol% of the zirconium dioxide powder.

7. A method for preparing a 3D printed material according to any one of claims 1 to 6, wherein the method comprises the following steps:

and uniformly mixing the zirconium dioxide powder, the reinforcing powder and the adhesive at the temperature of 67-70 ℃ to obtain the 3D printing material.

8. A3D printing method by using the 3D printing material as claimed in any one of claims 1-6, wherein the method comprises the following steps:

fusing the 3D printing material, and printing a preformed blank with a required shape;

degreasing the preformed blank and then drying to obtain the degreased and dried preformed blank;

and under the protection of inert gas, sintering the degreased and dried preform at the temperature of 1610-1630 ℃ to obtain the 3D printing part.

9. The 3D printing method according to claim 8, wherein the degreasing treatment comprises solvent degreasing at a temperature of 50 ℃ to 60 ℃.

10. The 3D printing method according to claim 8, wherein the sintering time is 1-2 hours.

Technical Field

The invention relates to the technical field of 3D printing, in particular to a 3D printing material, a preparation method thereof and a 3D printing method.

Background

Zirconium dioxide is a high melting point metal oxide with the molecular formula of ZrO₂The relative molecular weight is 123.22, the boiling point is 4300 ℃, the softening point is 2390-2500 ℃, the melting point is 2715 ℃, and the high-hardness wear-resistant high-temperature heat-resistant rubber has high hardness, high wear resistance, good high-temperature thermal stability and thermal shock resistance; and is insoluble in water, sulfuric acid, hydrochloric acid and nitric acid, and slightly soluble in hydrofluoric acid and concentrated sulfuric acid when heated. Pure zirconium dioxide is an insulator at normal temperature, and when a stabilizer is added, the conductivity increases and ionic conductivity is exhibited at high temperature.

With the rapid development of economy and the improvement of scientific research capability, the application field of the zirconium dioxide ceramic material has been greatly changed, the zirconium dioxide ceramic material is mainly applied to the fields of refractory materials and the like in the past, the zirconium dioxide ceramic material is now changed to the fields of structural ceramics, biological ceramics, electronic functional ceramics and the like, and the zirconium dioxide ceramic material is actively applied to high and new technical fields such as aerospace, aviation, nuclear industry and the like. Particularly, with the development of 3D printing technology, the shape and structure which are difficult to realize by the traditional process are directly formed by utilizing metal powder, so that a feasible way is provided for the development of the manufacturing process of the zirconium dioxide material.

Research on 3D printing of zirconia materials mainly focuses on stereolithography (SLA or SL) technology, but the technology has not been applied industrially. Moreover, in the existing 3D printing application process, especially for the photo-curing molding technology, there are several problems in the following aspects:

(1) the photocuring molding technology has strict requirements on printing materials, and low-viscosity slurry needs to be obtained by using powder with low specific surface area and nearly spherical shape, so that the cost of the printing materials is high;

(2) the powder slurry prepared from the conventional zirconium dioxide powder is easy to have the layering phenomenon, and the powder needs to be modified, so that the process is complex;

(3) slurry residue is easy to generate in products printed by the photocuring molding technology;

(4) 3D printing devices are expensive, often millions, and cost prohibitive to use and maintain;

(5) the light curing molding equipment is precise equipment, and a software system is complex to operate and high in operation difficulty.

Disclosure of Invention

In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, it is an object of the present invention to provide a 3D printing method that is low cost and non-toxic.

One aspect of the present invention provides a 3D printing material, which may be composed of the following components in parts by mass: 39.9-47.2 parts of zirconium dioxide powder, 11.4-17.7 parts of reinforcing powder and 41-43 parts of adhesive.

Another aspect of the present invention provides a method for preparing a 3D printing material, which may include the steps of: and uniformly mixing the zirconium dioxide powder, the reinforcing powder and the adhesive at the temperature of 67-70 ℃ to obtain the 3D printing material.

The invention also provides a 3D printing method, which comprises the steps of melting the 3D printing material or the 3D printing material prepared by the 3D printing material preparation method, printing a preform, degreasing the preform, and drying to obtain a degreased and dried preform; and under the protection of inert gas, sintering the degreased and dried preform at the temperature of 1610-1630 ℃ to obtain the 3D printing part.

Compared with the prior art, the beneficial effects of the invention at least comprise at least one of the following:

(1) the 3D printing material disclosed by the invention does not need to be provided with expensive 3D printing equipment and corresponding dies, is wide in application field, low in production cost, fast in production and good in biocompatibility and chemical stability;

(2) compared with photocuring molding printing, the 3D printing method has no residue, does not need powder with low specific surface area and nearly spherical shape, and does not need to prepare slurry; moreover, the sintering temperature is lower than the melting point of zirconium dioxide, so that the 3D printing material cannot be melted in the printing process, nontoxic production can be realized, and the printing ink is green and environment-friendly;

(3) the product printed by the 3D printing method provided by the invention has the advantages of high forming precision, good product performance consistency and quick forming.

Detailed Description

Hereinafter, a 3D printing material, a method of manufacturing the same, and a 3D printing method according to the present invention will be described in detail with reference to exemplary embodiments.

An aspect of the present invention provides a 3D printing material. In an exemplary embodiment of the 3D printed material of the present invention, the 3D printed material may be composed of the following components in parts by mass:

39.9-47.2 parts of zirconium dioxide powder, 11.4-17.7 parts of reinforcing powder and 41-43 parts of adhesive. In the case where the content of the reinforcing powder exceeds the upper limit of the above-mentioned range, the reinforcing effect is deteriorated; below the lower limit of the above-mentioned setting range, the reinforcing effect may be insignificant, and therefore, the provision of the reinforcing powder in the above-mentioned content has a good reinforcing effect. The adhesive within the above range has a good adhesion effect and does not cause excessive volume shrinkage. The bonding agent is too little, so that the bonding between the zirconium dioxide powder and the reinforcing powder is not firm; too much adhesive is wasted and increases the cost, and too much adhesive is easy to cause more volume shrinkage due to degreasing, and shrinkage gaps may be caused.

Further, the 3D printing material may be composed of the following components in parts by mass:

41.2-45.7 parts of zirconium dioxide powder, 12.5-16.4 parts of reinforcing powder and 41.3-42.5 parts of adhesive. For example, the 3D printing material may consist of the following components in parts by mass: 43.5 parts of zirconium dioxide powder, 13.6 parts of reinforcing powder and 42.9 parts of binder.

Further, the adhesive can be composed of the following components in parts by mass: 75-80 parts of polyethylene glycol, 10-15 parts of polymethyl methacrylate, 6-8 parts of stearic acid and 3-5 parts of acrylate. The adhesive with the components and the proportion has good adhesive strength, and can better adhere zirconium dioxide powder and reinforced powder. Further, the adhesive may be composed of the following components in parts by mass: 78 parts of polyethylene glycol, 11 parts of polymethyl methacrylate, 8 parts of stearic acid and 3 parts of stearic acid.

Further, the zirconia powder may have an average particle diameter of 35 μm to 50 μm. For example, the zirconia powder may have an average particle diameter of 42 μm or 48 μm.

Further, the reinforcing powder may be a mixture of alumina and silica. Further, the molar ratio of alumina to silica can be (2.5-4): 1-2, for example, the molar ratio of alumina to silica can be 3.2: 1.5. By using the mixture of aluminum oxide and silicon dioxide in the molar ratio in the range as the reinforcing powder, the fracture toughness of the zirconium dioxide can be greatly improved, and the fracture toughness can be improved by more than 30%. The reinforced powder aluminum oxide has the function of stabilizing tetragonal and cubic crystal forms of zirconia, when the content of the aluminum oxide is too high, the effect of enhancing the performance of the printing material cannot be achieved, the hardness of the printing material is lower, and the printed part has lower density and higher porosity due to too high content. When the content of the aluminum oxide is too low, the fracture toughness of the printing material cannot be enhanced well.

Further, to enhance the stability of the zirconium dioxide, the 3D printing material may further comprise yttrium oxide and/or calcium oxide. The content of yttrium oxide can be 1.5mol% to 3.5mol% of zirconium dioxide. The content of calcium oxide can be 1-2 mol% of zirconium dioxide powder. Preferably, the 3D printing material comprises both 3.0mol% yttria and 2.0mol% calcia, where the stability of the zirconia powder can be optimized and the hardness value of the material can reach 1010.23 HV. The addition of the aluminum oxide and the silicon dioxide can be matched with yttrium oxide and calcium oxide, and the fracture toughness value can be further improved to more than 35% under the synergistic effect. For example, when the molar ratio of alumina to silica is 3:2, and the 3D printing material contains 14.5wt% of the reinforcing powder, the fracture toughness of the 3D printing material containing 3mol% of yttria and 2mol% of calcia-stabilized zirconia can be improved better, and the improvement range can be as high as 45% or more compared with that of alumina and silica without adding the above ratio.

Furthermore, more than 98% of zirconium dioxide in the 3D printing material is tetragonal phase zirconium dioxide.

Further, the zirconium dioxide powder and the reinforcing powder are pure compound powders.

The invention further provides a preparation method of the 3D printing material. In one exemplary embodiment of the 3D printing material preparation method of the present invention, the preparation method may include:

and mixing 39.9-47.2 parts by mass of zirconium dioxide powder, 11.4-17.7 parts by mass of reinforcing powder and 41-43 parts by mass of adhesive at the temperature of 67-70 ℃ to obtain the 3D printing material. For example, the zirconium dioxide powder, the reinforcing powder and the binder in the above proportions are kneaded on a rubber mixer for 2 to 2.5 hours at a powder loading of 66 to 68vo1% to obtain a 3D printing material. The mixing temperature is set to enable the raw materials to be well mixed and uniformly mixed. The temperature of mixing may be 69 ℃.

Further, the preparation method comprises the step of melting and uniformly mixing 75-80 parts by mass of polyethylene glycol, 10-15 parts by mass of polymethyl methacrylate, 6-8 parts by mass of stearic acid and 3-5 parts by mass of acrylic acid to obtain the adhesive. For example, the uniform mixing may be uniform mixing under stirring.

Further, the preparation method also comprises the following steps: and (4) granulating the 3D printing material. For example, the 3D printing material is pelletized on a mixing extruder to further homogenize the feed to obtain a pelletized 3D printing material.

Further, the preparation method comprises adding yttrium oxide and/or calcium oxide to the zirconium dioxide powder before mixing. The content of yttrium oxide is 1.5-3.5 mol% of zirconium dioxide powder, and the content of calcium oxide is 1-2 mol% of zirconium dioxide powder.

Further, the zirconia powder may have an average particle diameter of 35 μm to 50 μm. For example, the zirconia powder may have an average particle diameter of 42 μm or 48 μm.

Further, the reinforcing powder may be a mixture of alumina and silica.

In an exemplary embodiment of the 3D printing method of the present invention, the printing method may include:

and S100, fusing the 3D printing material or the 3D printing material prepared by the 3D printing material preparation method, and printing a preform. For example, the 3D printing material is melted and then transported to a 3D printer to print out a preform. The melting temperature here may be 68 ℃ to 72 ℃, for example, 70 ℃.

And S200, degreasing the preform, and drying to obtain the degreased preform. For example, the preform may be immersed in deionized water to perform a solvent degreasing process to obtain a degreased preform. The degreasing temperature can be 50-60 ℃, and the degreasing time can be 8-10 hours. For example, the degreasing temperature may be 55 ℃ and the degreasing time may be 9 hours.

S300, sintering the degreased and dried preform at the temperature of 1610-1630 ℃ under the protection of inert gas to obtain the 3D printing part. The time period may be 1 to 2 hours. For example, the degreased and dried preform may be sintered in a sintering furnace, and then sintered at 1620 ℃ for 1 to 2 hours under a high-purity argon atmosphere. Under the sintering temperature of 1610 ℃ to 1630 ℃, incomplete sintering temperature caused by too low sintering temperature can be avoided, and crystal grains can not become coarse and the performance of the product can not be reduced because of too high sintering temperature.

Further, the sintering may be laser sintering.

In the 3D printing method, the zirconia powder is bonded by using the adhesive provided by the invention in the printing process, a preformed blank is printed, and the steps of degreasing, sintering and forming are carried out, so that the extremely harsh requirement on the required materials in the 3D printing process by using the 3D printing material is met. The invention can use conventional powder, does not need expensive 3D equipment and has low cost; moreover, as the melting point of the zirconium dioxide is not reached, the zirconium dioxide can not be melted in the printing process, the nontoxic and green production is realized, the forming precision of a workpiece is high, the consistency of product performance is good, no residue is generated, and the biocompatibility and the chemical stability are good.

In order that the above-described exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.

Example 1

Preparation of 3D printing material

(1) 80g of polyethylene glycol, 10g of polymethyl methacrylate vinegar, 6g of stearic acid and 4g of acrylate are melted and uniformly mixed to obtain the adhesive.

(2) 40.3g of zirconium dioxide powder (containing 2.178g of yttrium oxide and 0.18g of calcium oxide), 17.7g of reinforcing powder (containing 12.714g of aluminum oxide and 4.986g of silicon dioxide) and 42g of binder were mixed for 2.5 hours on a rubber mixing mill according to a powder loading of 66vo1% at a mixing temperature of 67 ℃, and the average particle diameter of the zirconium dioxide powder and the aluminum oxide powder was controlled to 35 um.

(3) And granulating the mixed mixture on a mixing extruder to ensure that the feeding is further uniform, thereby obtaining the granulated 3D printing material.

Preparation of two-dimensional and 3D printing part

(1) And heating and melting the granular 3D printing material, conveying the material to 3D printing, and printing a preformed blank with a required shape.

(2) And soaking the preform in deionized water, carrying out solvent degreasing for 8 hours at the degreasing temperature of 59 ℃, and taking out the preform after degreasing is finished and drying the preform.

(3) And sintering the dried preform in a sintering furnace, adopting high-purity argon atmosphere for protection, and preserving heat at 1610 ℃ for 1.5 hours to obtain the 3D printing part.

3D printed part (ZrO) prepared in this example₂-Al₂O₃Composite component) has a hardness of 973.84HV and a fracture toughness value of 5.054 MPa.m^1/2。

Example 2

Preparation of 3D printing material

(1) 78g of polyethylene glycol, 11g of polymethyl methacrylate vinegar, 8g of stearic acid and 3g of acrylate are melted and uniformly mixed to obtain the adhesive.

(2) 42.5g of zirconium dioxide powder (containing 2.297g of yttrium oxide and 0.19g of calcium oxide), 15.5g of reinforcing powder (containing 11.134g of aluminum oxide and 4.366g of silicon dioxide) and 42g of adhesive are mixed on a rubber mixing mill for 2 hours at the mixing temperature of 68 ℃ according to the powder loading of 66vo1%, and the average particle size of the zirconium dioxide powder and the aluminum oxide powder is controlled to be 50 um.

(3) And granulating the mixed mixture on a mixing extruder to ensure that the feeding is further uniform, thereby obtaining the granulated 3D printing material.

Preparation of two-dimensional and 3D printing part

(1) And heating and melting the granular 3D printing material, conveying the material to 3D printing, and printing a preformed blank with a required shape.

(2) And soaking the preform in deionized water for solvent degreasing for 9 hours, wherein the degreasing temperature is 52 ℃, and taking out the preform after degreasing is finished and drying the preform.

(3) And sintering the dried preform in a sintering furnace, adopting high-purity argon atmosphere for protection, and preserving the heat at the temperature of 1615 ℃ for 2 hours to obtain the 3D printing part.

3D printed part (ZrO) prepared in this example₂-Al₂O₃Composite part) has a hardness of 987.41HV and a fracture toughness value of 5.56MPa^1/2。

Example 3

Preparation of 3D printing material

(1) And melting 76g of polyethylene glycol, 12g of polymethyl methacrylate vinegar, 7g of stearic acid and 5g of acrylate, and uniformly mixing to obtain the adhesive.

(2) 44g of zirconium dioxide powder (containing 2.391g of yttrium oxide and 0.395g of calcium oxide), 13g of reinforcing powder (containing 9.338g of aluminum oxide and 3.662g of silicon dioxide) and 43g of adhesive are mixed on a rubber mixing mill for 2.5 hours according to the powder loading of 68vo1%, the mixing temperature is 68 ℃, and the average particle diameter of the zirconium dioxide powder and the aluminum oxide powder is controlled to be 35 um.

(3) And granulating the mixed mixture on a mixing extruder to ensure that the feeding is further uniform, thereby obtaining the granulated 3D printing material.

Preparation of two-dimensional and 3D printing part

(1) And heating and melting the granular 3D printing material, conveying the material to 3D printing, and printing a preformed blank with a required shape.

(2) And soaking the preform in deionized water, carrying out solvent degreasing for 8 hours at the degreasing temperature of 59 ℃, and taking out the preform after degreasing is finished and drying the preform.

(3) And sintering the dried preform in a sintering furnace, adopting high-purity argon atmosphere for protection, and preserving the heat at 1620 ℃ for 1.5 hours to obtain the 3D printing part.

3D printed part (ZrO) prepared in this example₂-Al₂O₃Composite part) has a hardness of 996.21HV and a fracture toughness value of 6.395MPa^1/2。

Example 4

Preparation of 3D printing material

(1) 75g of polyethylene glycol, 15g of polymethyl methacrylate vinegar, 7g of stearic acid and 3g of acrylate are melted and uniformly mixed to obtain the adhesive.

(2) 47.2g of zirconium dioxide powder (containing 2.565g of yttrium oxide and 0.424g of calcium oxide), 11.8g of reinforcing powder (containing 8.476g of aluminum oxide and 3.324g of silicon dioxide) and 41g of binder were mixed on a rubber mixing mill for 2 hours at a mixing temperature of 70 ℃ according to a powder loading of 68vo1%, and the average particle diameter of the zirconium dioxide powder and the aluminum oxide powder was controlled to 50 μm.

(3) And granulating the mixed mixture on a mixing extruder to ensure that the feeding is further uniform, thereby obtaining the granulated 3D printing material.

Preparation of two-dimensional and 3D printing part

(1) And heating and melting the granular 3D printing material, conveying the material to 3D printing, and printing a preformed blank with a required shape.

(2) And soaking the preform in deionized water for solvent degreasing for 9 hours, wherein the degreasing temperature is 52 ℃, and taking out the preform after degreasing is finished and drying the preform.

(3) And sintering the dried preform in a sintering furnace, adopting high-purity argon atmosphere for protection, and preserving heat at 1630 ℃ for 1 hour to obtain the 3D printing part.

3D printed part (ZrO) prepared in this example₂-Al₂O₃Composite part) has a hardness of 1010.23HV and a fracture toughness value of 4.756MPa^1/2。

Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.