Extrusion type photocuring 3D printing glass slurry

Abstract

The invention relates to the technical field of 3D printing ink direct writing, in particular to extrusion type light-curing 3D printing glass slurry and a preparation method thereof.The extrusion type light-curing 3D printing glass slurry is prepared from 17-30 parts of HEMA resin, 5-20 parts of POE resin, 4-12 parts of TEGDA resin and 20-40 parts of ceramic powder; according to the formula design of the slurry, the printed glass material has excellent transparency, hardness and mechanical properties; in addition, the preparation method provided by the invention is simple and easy to implement, the uniformity and printability of the slurry can be ensured, and the formula design and the preparation method are combined, so that the preparation method is widely applicable to a high-precision 3D printing technology, and is particularly suitable for application in the technical field of ink direct writing.

Description

Technical Field

[0001] The present application relates to the technical field of 3D printing ink direct writing, and in particular to an extrusion-type photocurable 3D printing glass slurry. Background Art

[0002] With the development of the times, the demand for high-performance glass materials with high transparency, high hardness and good mechanical properties is increasing day by day. However, traditional glass processing technologies such as milling and polishing are often unable to cope with complex structures and high-precision requirements, and the physical and chemical changes in the processing process can easily affect the transparency and hardness of the glass.

[0003] In order to meet these challenges, 3D printing technology has gradually become an important development direction for the manufacturing industry. In 3D printing, ink direct writing technology, as an emerging printing method, has made significant progress in the manufacture of electronic devices, sensors, optoelectronic materials and other fields with its high precision and material diversity. Ink direct writing directly constructs three-dimensional objects by spraying liquid materials (such as conductive inks, photosensitive resins or metal particle suspensions) without high-temperature heating. It can accurately print complex structures and is suitable for manufacturing some temperature-sensitive or extremely high-precision products. Although ink direct writing technology has shown great potential, it still faces a series of technical bottlenecks in the printing application of glass materials.

[0004] First, the jetting performance of traditional glass ink is unstable, and it is difficult to ensure the continuity and accuracy of printing. In addition, the curing process of glass ink is very sensitive to conditions such as temperature and light. How to ensure that each layer of material is evenly cured and avoid cracks or deformation due to shrinkage or uneven curing is still a technical problem. More importantly, existing glass inks often lack good mechanical properties and transparency, which limits their application in high-performance glass products.

[0005] Therefore, how to develop a glass paste that meets the requirements of high-precision 3D printing technology has become an important issue that needs to be urgently solved in the current field of materials science. Summary of the invention

[0006] The purpose of this application is to provide an extruded light-curing 3D printing glass slurry, which improves the transparency, hardness and mechanical properties of the printed glass by reasonably designing the slurry formula to meet the needs of high-precision printing technology.

[0007] The extrusion-type light-curing 3D printing glass paste provided in this application adopts the following technical solution:

[0008] The present application provides an extrusion-type light-curing 3D printing glass paste, which adopts the following technical solution:

[0009] An extrusion-type light-curing 3D printing glass slurry comprises the following components in weight percentage: 17-30 parts of HEMA resin, 7-20 parts of POE resin, 4-12 parts of TEGDA resin, and 20-40 parts of ceramic powder.

[0010] By adopting the above technical solution, HEMA (2-hydroxyethyl methacrylate) resin is used as the main resin component to provide the structural strength and adhesion of the slurry. Its excellent adhesion and stability ensure the molding stability of the material during the printing process, avoiding the problems of poor molding or insufficient adhesion. By adjusting the proportion of HEMA resin, the hardness and viscosity of the slurry can be effectively adjusted to achieve an ideal printing effect.

[0011] POE (polyolefin elastomer) resin is a component that enhances the flexibility and durability of the material. It plays a role in improving impact resistance, wear resistance and long-term stability in the slurry. The addition of POE resin significantly improves the mechanical properties of the printed glass material, especially under external impact and high load, and can maintain a longer service life;

[0012] TEGDA (tetrahydroxymethylethylene glycol diacrylate) resin, as a cross-linking agent, can promote the cross-linking reaction of the slurry during heat treatment or light curing, thereby enhancing the strength, hardness and chemical stability of the printed glass. The addition of TEGDA resin makes the glass material show better hardness and heat resistance after printing, improving the comprehensive performance of the printed material.

[0013] Preferably, it comprises 20-28 parts of HEMA resin, 10-15 parts of POE resin, 6-10 parts of TEGDA resin, and 25-35 parts of ceramic powder.

[0014] Preferably, the ceramic powder is a combination of any one or more of silicon dioxide powder, aluminum oxide powder and zirconium oxide powder.

[0015] By adopting the above technical solution, silicon dioxide powder is low-cost, can provide high transparency, and enhance the hardness and chemical stability of glass; aluminum oxide powder and zirconium oxide powder can improve the hardness, strength and high temperature resistance of glass.

[0016] Preferably, the ceramic powder is silicon dioxide powder with a particle size of 50 nm-50 μm and a purity of 99-99.99%.

[0017] By adopting the above technical solution, silica powder is used as an inorganic filler with low cost, can provide the transparency and hardness required for glass printing materials, and can effectively improve the mechanical properties and durability of the printed glass. At the same time, the use of silica powder can effectively control the thermal expansion properties of the glass material, making the printed glass products more stable and durable.

[0018] Preferably, the HEMA resin has a molecular weight of 130-150 g / mol, a viscosity of 100-300 mPa·s, and a glass transition temperature of 50-60°C.

[0019] By adopting the above technical solution, the viscosity range of the selected HEMA resin is limited to ensure appropriate slurry fluidity, and the molecular weight of the resin is limited to ensure the structural stability and strength of the final product.

[0020] Preferably, the POE resin has a melt index of 2-10 g / 10 min and a glass transition temperature of -40°C to -20°C.

[0021] By adopting the above technical solution, the melt index and glass transition temperature of the selected POE resin are limited to ensure that it has sufficient flexibility and good thermal stability, thereby improving the impact resistance and long-term stability of the printed material.

[0022] Preferably, the viscosity of the TEGDA resin is 50-150 mPa·s, and the photocuring rate is 0.5-1.5 mm / min.

[0023] By adopting the above technical solution, the viscosity and photocuring rate of the selected TEGDA resin are limited to ensure that it has appropriate hardness, strength and cross-linking degree during the photocuring process, thereby enhancing the mechanical properties of the final product.

[0024] A method for preparing an extrusion-type light-curing 3D printing glass slurry comprises mixing HEMA resin, POE resin, TEGDA resin and ceramic powder according to a raw material ratio, stirring, vacuumizing and filtering to obtain a glass slurry.

[0025] In summary, the present application includes at least one of the following beneficial technical effects:

[0026] 1. HEMA resin, POE resin and TEGDA resin are the main components, which can provide the slurry with good structural strength, adhesion, flexibility and durability. Ceramic powder provides the base of glass printing materials, giving the materials excellent transparency and hardness. The combination of these raw materials makes the printed glass material have excellent transparency, which is suitable for the manufacture of optical devices and transparent structures. It also has high hardness and impact resistance, and can withstand strong external forces and wear during long-term use.

[0027] 2. The slurry formula is simple and reasonable, suitable for high-precision printing, and can stably form complex glass structures.

[0028] 3. By adjusting the ratio of resin and filler, the performance of the material can be flexibly adjusted to meet different application requirements while meeting the ink direct writing technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a physical picture of the complex structure printed in Example 1. DETAILED DESCRIPTION

[0030] The present application is further described in detail below with reference to the accompanying drawings and embodiments.

[0031] raw material

[0032] HEMA resin: molecular weight 130-150 g / mol, viscosity 100-300 mPa·s, glass transition temperature 50-60°C.

[0033] POE resin: melt index 2-10g / 10min, glass transition temperature -40℃ to -20℃.

[0034] TEGDA resin: viscosity 50-150mPa·s, photocuring rate 0.5-1.5mm / min.

[0035] Ceramic powder: In this application, silicon dioxide powder is taken as an example, with a particle size of 50nm-50μm and a purity of 99-99.99%.

[0036] Example

[0037] Embodiment 1, 2

[0038] Examples 1 and 2 use the same preparation process, but have different specific component ratios, as shown in Table 1.

[0039] Table 1 Specific raw material ratio table of Examples 1 and 2

[0040]

[0041] Preparation process:

[0042] 1) Add HEMA resin, POE resin and TEGDA resin into a premixing container according to the proportion, use a low-speed stirrer for preliminary mixing at a speed of 80 r / min and stir for 10 min to ensure that the components are evenly dispersed to obtain a mixture A.

[0043] 2) Slowly add ceramic powder to mixture A according to the raw material ratio, gradually increase the stirring speed to 180r / min, and continue stirring for 15min to ensure that the ceramic powder is fully dispersed and evenly mixed with other ingredients to obtain mixture B.

[0044] 3) Place mixture B in a vacuum degassing machine, set the vacuum degree to -0.1 MPa, and evacuate for 15 minutes to obtain a slurry to be treated.

[0045] 4) The slurry to be treated is taken out from the vacuum degassing machine, added into a premixing container, and preliminarily mixed with a low-speed agitator at a speed of 50 r / min for 5 minutes. After the stirring is completed, it is allowed to stand at room temperature for 30 minutes to obtain the slurry to be filtered.

[0046] 5) Filter the slurry to be filtered using a 200-mesh sieve to obtain a finished slurry.

[0047] The slurry of Example 1 was 3D printed by ink direct writing technology, and the finished product is shown in the figure Figure 1 shown.

[0048] Comparative Example

[0049] Comparative Example 1

[0050] Comparative Example 1 and Example 1 use the same preparation process, but the specific composition ratio is different, and the specific composition ratio is shown in Table 2.

[0051] Table 2 Specific raw material ratio table of comparative example 1

[0052]

[0053] Comparative Example 2

[0054] Comparative Example 2 uses the same preparation process as Example 1, but the raw materials are different. In Comparative Example 2, 25 parts of acrylic resin, 13 parts of POE resin, 9 parts of TEGDA resin, and 30 parts of ceramic powder are used.

[0055] Comparative Example 3

[0056] Comparative Example 3 uses commercially available light-cured 3D printing glass slurry.

[0057] Performance testing

[0058] In order to further study the influence of each component on the performance of the finished product, the slurries of each embodiment and the comparative example were 3D printed into finished products by ink direct writing technology. For the finished products, the present application further carried out the following example verification.

[0059] Transparency detection

[0060]

[0061] The test data of Examples 1 and 2 and Comparative Examples 1-3 are shown in Table 3.

[0062] Table 3 Transparency test data table

[0063]

[0064] The results of the study showed that:

[0065] 1) By comparing the data of Example 1 and Example 2, it can be seen that within the range of the glass paste raw material ratio proposed in the present application, the transparency of the product can be effectively improved.

[0066] 2) By comparing the data of Example 1 with Comparative Examples 1 and 2, it can be seen that the present solution optimizes the curing process and optical properties of the resin by carefully selecting and adjusting the types and ratios of raw materials, thereby obtaining higher transparency; in this ratio, HEMA resin can provide better optical properties than conventional acrylic resin.

[0067] 3) The data of Example 1 is better than that of Comparative Example 3 because HEMA resin has good optical properties and mechanical strength and is a key component for improving transparency. POE resin, as a toughening agent, can improve the flexibility and impact resistance of the material while having little effect on transparency. TEGDA resin, as a cross-linking agent, can enhance the curing performance and stability of the material.

[0068] At the same time, in this scheme, the proportions of various raw materials have been carefully adjusted to ensure that they can work synergistically to jointly improve the performance of the material. The appropriate amount of POE resin and TEGDA resin form a good interpenetrating network structure with the HEMA resin, thereby improving the transparency and mechanical properties of the material;

[0069] Moreover, ink direct writing 3D printing technology has high requirements on the fluidity and curing speed of the slurry. The ratio of this solution is more suitable for the specific application field of ink direct writing 3D printing. Domestic manufacturers pay less attention to this field. Commercially available glass slurry may pay more attention to cost control and production efficiency. Therefore, certain compromises are made in raw material selection and ratio, which affects the performance of the final product.

[0070] Hardness testing

[0071]

[0072] The test data of Example 1 and Comparative Examples 1 and 3 are shown in Table 4.

[0073] Table 4 Hardness test data table

[0074]

[0075] The results of the study showed that:

[0076] 1) By comparing Example 1 with Comparative Example 3, it can be seen that the present solution is superior; however, the hardness of Comparative Example 1 is less than that of Comparative Example 3. This may be because HEMA resin has good optical properties and mechanical strength and is one of the key components for improving the hardness of the material. However, excessive HEMA resin may cause an uneven internal structure of the material, making the finished product brittle and reducing the hardness. At the same time, less silica powder may also cause the hardness of the finished product to decrease.

[0077] Durability testing

[0078]

[0079] The test data of Example 1 and Comparative Example 3 are shown in Table 5.

[0080] Table 5 Durability test data table

[0081]

[0082]

[0083] The results of the study showed that:

[0084] 1) During the entire test period, the special formula and carefully selected material components of Example 1 provide excellent weather resistance and UV resistance. Compared with Comparative Example 3, the surface change of Example 1 is smaller, gradually transitioning from no change to slight color change;

[0085] This may be because, in this specific ratio, the microstructure is evenly distributed, there are very few peripheral defects in the material, and there is an interface interaction between the ceramic powder and the resin. Good interface bonding can effectively transfer stress and reduce weaknesses at the interface, thereby improving the mechanical strength and durability of the material; at the same time, there is an intermolecular force between HEMA, POE and TEGDA resins, which is crucial to maintaining the stability of the material and resisting the influence of external environmental factors.

[0086] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. An extrusion-type light-curing 3D printing glass slurry, characterized in that: It includes 17-30 parts of HEMA resin, 7-20 parts of POE resin, 4-12 parts of TEGDA resin and 20-40 parts of ceramic powder.

2. The extrusion-type light-curing 3D printing glass paste according to claim 1, characterized in that: It includes 20-28 parts of HEMA resin, 10-15 parts of POE resin, 6-10 parts of TEGDA resin and 25-35 parts of ceramic powder.

3. The extrusion-type light-curing 3D printing glass paste according to claim 1, characterized in that: The ceramic powder is any one or more of a combination of silicon dioxide powder, aluminum oxide powder and zirconium oxide powder.

4. The extrusion-type light-curing 3D printing glass paste according to claim 3, characterized in that: The ceramic powder is silicon dioxide powder with a particle size of 50nm-50μm and a purity of 99-99.99%.

5. The extrusion-type light-curing 3D printing glass paste according to claim 1, characterized in that: The HEMA resin has a molecular weight of 130-150 g / mol, a viscosity of 100-300 mPa·s, and a glass transition temperature of 50-60°C.

6. The extrusion-type light-curing 3D printing glass paste according to claim 1, characterized in that: The POE resin has a melt index of 2-10 g / 10 min and a glass transition temperature of -40°C to -20°C.

7. The extrusion-type light-curing 3D printing glass paste according to claim 1, characterized in that: The viscosity of the TEGDA resin is 50-150 mPa·s, and the photocuring rate is 0.5-1.5 mm / min.

8. A method for preparing an extrusion-type light-curing 3D printing glass paste, characterized in that: HEMA resin, POE resin, TEGDA resin and ceramic powder are mixed according to the raw material ratio, stirred, vacuumed and filtered to obtain glass slurry.

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