CN106348745B - A kind of preparation of 3DP technique rapid shaping YAG transparent ceramic powder material - Google Patents

Abstract

The invention discloses a method for preparing a YAG transparent ceramic powder material rapidly formed by a 3DP process. First, the YAG transparent ceramic powder is granulated to become a granulated powder with a particle size within the range of 0.1-5 μm; then, In the mixer, add according to the mass percentage, granulated YAG transparent ceramic powder: 85%~92%, zinc stearate: 0.5%~1.5%, trimellitic anhydride: 0.2%~1.0%, turn on the mixer at 300 rpm , stirred for 30 minutes, heated until the temperature reached 160~180°C, under stirring, added ABS resin: 2%~8%, thermoplastic phenolic resin: 2%~8%, and continued to stir at a speed of 350 rpm until the temperature dropped to At room temperature, laser sintering 3D printing YAG transparent ceramic powder was obtained. The material can be directly formed on a three-dimensional printing 3D printer, has high sphericity, good fluidity, high forming precision, simple preparation process, easy control of conditions, low production cost, and easy industrial production.

Description

Preparation of a 3DP process rapid prototyping YAG transparent ceramic powder material

technical field

The invention relates to a method for preparing a powder material for rapid prototyping in a three-dimensional printing (3DP) process, which belongs to the field of rapid prototyping materials, and in particular to a method for preparing a rapid prototyping YAG transparent ceramic powder material in a 3DP process and 3D printing molding .

Background technique

YAG is the abbreviation of yttrium aluminum garnet, and its chemical formula is Y ₃ Al ₅ O ₁₂ . It is a composite oxide produced by the reaction of Y ₂ O ₃ and Al ₂ O ₃ . It belongs to the cubic crystal system and has a garnet structure. The unit cell of garnet can be viewed as a linked network of dodecahedrons, octahedrons, and tetrahedra. Since Ikesue used the solid-state reaction sintering method to prepare Nd:YAG transparent ceramics in 1995 and realized continuous laser output, laser ceramics have achieved rapid development due to their short preparation cycle, easy realization of uniform and high-concentration doping, and design flexibility. It will gradually replace single crystal as the next generation laser gain material. YAG activated by various ions (such as Nd ³⁺ , Yb ³⁺ , Er ³⁺ , Ho ³⁺ , Tm ³⁺ and Cr ⁴⁺ , etc.) has become the most widely studied and the highest laser output efficiency due to its excellent physical and chemical properties. material system. The preparation of YAG-based transparent ceramics with high optical quality has become a research hotspot in the field of advanced ceramics.

Residual pores, grain boundary impurities and doping segregation in transparent ceramics are the main factors affecting their optical quality. In the process of preparing YAG transparent ceramics by solid-state reaction sintering method, direct drying of ball-milling slurry will lead to serious agglomeration and irregular shape of nano-micron powder, poor fluidity of dry powder, and high friction between particles, which is not conducive to the subsequent molding process. This phenomenon is more serious when preparing large-scale, complex shapes and composite structures, and becomes the main source of the second phase and residual pores in the ceramic sintered body, and may also lead to inconsistent shrinkage and even cracking of the ceramic body. The use of 3D printing can overcome the above shortcomings and improve the accuracy of the product.

3D printing is a technology that accumulates materials into three-dimensional products layer by layer through model design and printing equipment, also known as additive manufacturing. 3D printing integrates many cutting-edge fields such as digital modeling, electromechanical control, information technology, material science and chemistry, and is one of the core technologies of the "third industrial revolution". 3D printing technology has been gradually expanded in the fields of aerospace, biomedicine, construction, and handicraft manufacturing. Its advantages of convenience, speed, and improved material utilization continue to emerge, and it continues to promote the transformation and upgrading of traditional manufacturing industries.

3D printing materials are the material basis of 3D printing, which determine the versatility of 3D printing and are currently the bottleneck restricting the development of 3D printing. The types of 3D printing materials have expanded from the initial polymer materials (ABS, PLA, PC, PVC, photosensitive resin) to metals (various alloys, used in aerospace, medical and other high-end fields), ceramics (various inorganic non-metallic material), etc. According to the forming principle, 3D printing materials are limited to powder, filament, layer, and liquid, each of which is suitable for different 3D printing methods. 3D printing powder materials are suitable for three-dimensional printing process (3DP) and selective laser sintering (SLS). At present, there are related reports on the preparation method of powder materials for 3D printing. Chinese patent 201510125390X discloses a 3D printing zirconia powder molding The preparation method of the material; Chinese patent 2015101260246 discloses the preparation of a 3D printing rapid prototyping zirconium aluminum carbon ceramic powder material, because the inorganic non-metallic material has high strength, high hardness, high temperature resistance, low density, good chemical stability, and Corrosion and other excellent properties are widely used in aerospace, automotive, biological and other industries, and its demand in the field of 3D printing will increase rapidly. Therefore, the commercialization of selective laser sintering 3D printing inorganic non-metallic powder materials is very important. Significance and broad market.

The three-dimensional printing (3DP) process, which is today's 3D printing, was developed by Emanual Sachs of the Massachusetts Institute of Technology and others. E.M.Sachs applied for the 3DP (Three-Dimensional Printing) patent in 1989, which is one of the core patents in the field of droplet injection molding of non-shaping materials. The 3DP process is similar to the SLS process, using powder materials for forming, such as ceramic powder and metal powder. The difference is that the material powder is not connected by sintering, but the section of the part is "printed" on the material powder with an adhesive (such as silica gel) through the nozzle. Parts bonded with adhesives have low strength and require post-processing. The specific process is as follows: After the upper layer is bonded, the forming cylinder is lowered by a distance (equal to layer thickness: 0.013 ~ 0.1mm), the powder supply cylinder is raised by a certain height, and some powder is pushed out and pushed to the forming cylinder by the powder spreading roller. Paved and compacted. Under the control of the computer, the spray head selectively sprays the binder construction layer according to the forming data of the next construction section. When the powder spreading roller spreads the powder, the excess powder is collected by the powder collecting device. Such a cycle of powder feeding, powder spreading and binder spraying will finally complete the bonding of a three-dimensional powder. The place where the binder is not sprayed is dry powder, which plays a supporting role in the forming process, and is relatively easy to remove after forming. However, this molding process also has certain limitations. The amount of adhesive used is large, which is difficult to control, and the adhesive is easy to block the nozzle.

The present invention granulates the YAG transparent ceramic powder material, coats the polymer adhesive on the surface of the granulated YAG transparent ceramic powder material, and the obtained coated YAG transparent ceramic powder material can be directly molded by 3DP. There is no need to spray adhesive during the molding process, only a small amount of solvent needs to be sprayed. The advantage is that the amount of adhesive is greatly reduced, preventing nozzle clogging, reducing environmental pollution in the subsequent calcination process, and high-quality products. The powder material prepared by the process of this application has uniform particle size, high sphericity, and good fluidity, and is suitable for 3D printing and molding by 3DP process. In addition, the method provided by this patent is simple and low in cost.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a kind of preparation method of 3DP technology rapid prototyping YAG transparent ceramic powder material, rapid prototyping powder can directly three-dimensional printing rapid prototyping in spraying solvent;

The purpose of the present invention is achieved through the following technical solutions.

A kind of preparation method of YAG transparent ceramic powder material of rapid prototyping by 3DP technology, it is characterized in that, this method has following processing steps:

(1) YAG transparent ceramic powder pretreatment: YAG transparent ceramic powder is dried, ground, sieved, and the particle size is controlled within the range of 0.1-5 μm to obtain pretreated YAG transparent ceramic powder;

(2) Preparation of granulated YAG transparent ceramic powder: In the reactor, add water: 52%~56%, water-soluble urea-formaldehyde resin: 0.2%~1.5%, soluble starch: 0.2%~1.5%, Heat to dissolve, sodium hexametaphosphate: 0.1%~1.0%, stir to dissolve, then add pretreated YAG transparent ceramic powder: 42%~46%, the sum of each component is 100%, stir vigorously, react for 5~7h, then Spray drying to obtain granulated YAG transparent ceramic powder with a particle size in the range of 40-100 µm;

(3) Preparation of YAG transparent ceramic powder formed by laser sintering 3D printing: in the mixer, add according to the mass percentage, granulate YAG transparent ceramic powder: 85%~92%, zinc stearate: 0.5%~1.5%, Trimellitic anhydride: 0.2%~1.0%, turn on the mixer at 300 rpm, stir for 30 minutes, heat to make the temperature reach 160~180°C, add ABS resin: 2%~8%, thermoplastic phenolic resin: 2%~ 8%, the sum of each component is 100%, continue to stir at a speed of 350 rpm until the temperature drops to room temperature, and obtain a laser sintered 3D printed YAG transparent ceramic powder, and the obtained laser sintered 3D printed YAG transparent ceramic The particle size of the powder is in the range of 40-120 μm.

In the spray drying described in step (2), the temperature of the air inlet is controlled at 100°C, the temperature of the air outlet is controlled at 90°C, and the flow rate of the air inlet is 200m ³ /h.

The mass ratio of water-soluble urea-formaldehyde resin to soluble starch in step (2) is optimal between 1:0.8~1.2.

The mass ratio of water-soluble urea-formaldehyde resin to sodium hexametaphosphate described in step (2) is optimal between 1:0.09~0.11

The mass ratio of ABS resin to thermoplastic phenolic resin described in step (3) is optimal between 1:0.9~1.1.

The mass ratio of thermoplastic phenolic resin to trimellitic anhydride in step (3) is optimal between 1:0.09~0.11.

The particle size test method of the present invention is the particle size equivalent diameter measured by a laser particle size analyzer.

Another object of the present invention is to provide the application of YAG transparent ceramic powder material formed by laser sintering 3D printing on a 3D printer. The solvent N,N-dimethylformamide is loaded inside. The specific process is as follows: the nozzle sprays N,N-dimethylformamide on the YAG transparent ceramic powder material formed by laser sintering 3D printing, and the adhesive on the surface of the material dissolves to make it bond. After the upper layer is bonded, the forming cylinder Descending a distance (equal to layer thickness: 0.010~0.1mm), the powder supply cylinder rises to a certain height, pushes out some powder, and is pushed to the forming cylinder by the powder spreading roller, paved and compacted. Under the control of the computer, the spray head selectively sprays the solvent N,N-dimethylformamide to build the layer according to the forming data of the next build section. When the powder spreading roller spreads the powder, the excess powder is collected by the powder collecting device. Such a cycle of powder feeding, powder spreading and spraying of N,N-dimethylformamide will finally complete the bonding of a three-dimensional powder. The place where N,N-dimethylformamide is not sprayed is dry powder, which plays a supporting role in the forming process, and is relatively easy to remove after forming.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The YAG transparent ceramic powder material obtained by laser sintering and 3D printing in the present invention does not need to be sprayed with a binder, and the nozzle can be directly formed by spraying only a solvent, which greatly reduces the amount of adhesive, improves the quality of the product, and prevents the nozzle from clogging .

(2) The laser sintering 3D printing YAG transparent ceramic powder material obtained in the present invention has uniform particle size, high sphericity, and good fluidity, and is suitable for 3D printing in 3DP technology; this rapid prototyping powder The material can be used to manufacture thin-walled models or tiny parts and handicrafts, and the manufactured products have the characteristics of high surface gloss and high precision.

(3) The laser sintering 3D printing YAG transparent ceramic powder material obtained in the present invention has the advantages of simple preparation process, easy control of conditions, low production cost, easy industrial production, and low-carbon environmental protection and energy saving. .

Detailed ways

Example 1

(1) YAG transparent ceramic powder pretreatment: YAG transparent ceramic powder is dried, ground, sieved, and the particle size is controlled within the range of 0.1-5 μm to obtain pretreated YAG transparent ceramic powder;

(2) Preparation of granulated YAG transparent ceramic powder: In the reactor, add water: 5400mL, water-soluble urea-formaldehyde resin: 50g, soluble starch: 50g, heat to dissolve, sodium hexametaphosphate: 20g, stir to dissolve, and then Add pretreated YAG transparent ceramic powder: 4500g, stir vigorously, react for 6h, and then spray dry to obtain granulated YAG transparent ceramic powder, the particle size of which is in the range of 40~100µm;

(3) Preparation of YAG transparent ceramic powder formed by laser sintering and 3D printing: In the mixer, add and granulate YAG transparent ceramic powder: 880g, zinc stearate: 6g, trimellitic anhydride: 4g, and turn on the mixer at 300 rpm /min, stirring for 30min, heating until the temperature reaches 160~180℃, under stirring, add ABS resin: 50g, thermoplastic phenolic resin: 60g, continue stirring at 350 rpm until the temperature drops to room temperature, and obtain laser sintering 3D printing YAG transparent ceramic powder, the particle size of the obtained laser sintered 3D printing YAG transparent ceramic powder is in the range of 40-120 μm.

Example 2

(1) YAG transparent ceramic powder pretreatment: YAG transparent ceramic powder is dried, ground, sieved, and the particle size is controlled within the range of 0.1-5 μm to obtain pretreated YAG transparent ceramic powder;

(2) Preparation of granulated YAG transparent ceramic powder: In the reactor, add water: 5200mL, water-soluble urea-formaldehyde resin: 100g, soluble starch: 100g, heat to dissolve, sodium hexametaphosphate: 40g, stir to dissolve, and then Add pre-treated YAG transparent ceramic powder: 4600g, stir vigorously, react for 5h, and then spray dry to obtain granulated YAG transparent ceramic powder, the particle size of which is in the range of 40~100µm;

(3) Preparation of YAG transparent ceramic powder formed by laser sintering and 3D printing: In a blender, respectively add and granulate YAG transparent ceramic powder: 90g, zinc stearate: 0.5g, trimellitic anhydride: 0.5g, and turn on the mixer at a speed of 300 rev/min, stirring for 30 min, heating until the temperature reaches 160~180°C, under stirring, add ABS resin: 4g, thermoplastic phenolic resin: 5g, continue stirring at 350 rev/min until the temperature drops to room temperature, and get Laser sintering 3D printing forms YAG transparent ceramic powder, and the particle size of the obtained laser sintering 3D printing forming YAG transparent ceramic powder is in the range of 40-120 μm.

Example 3

(1) YAG transparent ceramic powder pretreatment: YAG transparent ceramic powder is dried, ground, sieved, and the particle size is controlled within the range of 0.1-5 μm to obtain pretreated YAG transparent ceramic powder;

(2) Preparation of granulated YAG transparent ceramic powder: In the reactor, add water: 5600mL, water-soluble urea-formaldehyde resin: 80g, soluble starch: 80g, heat to dissolve, sodium hexametaphosphate: 10g, stir to dissolve, and then Add pretreated YAG transparent ceramic powder: 4300g, stir vigorously, react for 7 hours, and then spray dry to obtain granulated YAG transparent ceramic powder, the particle size of which is in the range of 40~100μm;

(3) Preparation of YAG transparent ceramic powder formed by laser sintering and 3D printing: In a blender, add and granulate YAG transparent ceramic powder: 170g, zinc stearate: 3g, trimellitic anhydride: 3g, and turn on the mixer at 300 rpm /min, stirring for 30min, heating until the temperature reaches 160~180°C, under stirring, add ABS resin: 12g, thermoplastic phenolic resin: 12g, continue stirring at 350 rpm until the temperature drops to room temperature, and obtain laser sintering 3D printing YAG transparent ceramic powder, the particle size of the obtained laser sintered 3D printing YAG transparent ceramic powder is in the range of 40-120 μm.

Example 4

(1) YAG transparent ceramic powder pretreatment: YAG transparent ceramic powder is dried, ground, sieved, and the particle size is controlled within the range of 0.1-5 μm to obtain pretreated YAG transparent ceramic powder;

(2) Preparation of granulated YAG transparent ceramic powder: In the reactor, add water: 5000mL, water-soluble urea-formaldehyde resin: 60g, soluble starch: 60g, heat to dissolve, sodium hexametaphosphate: 60g, stir to dissolve, and then Add pretreated YAG transparent ceramic powder: 4800g, stir vigorously, react for 6.5h, and then spray dry to obtain granulated YAG transparent ceramic powder, the particle size of which is in the range of 40~100µm;

(3) Preparation of YAG transparent ceramic powder formed by laser sintering and 3D printing: In the mixer, add and granulate YAG transparent ceramic powder: 860g, zinc stearate: 10g, trimellitic anhydride: 10g, and turn on the mixer at 300 rpm /min, stir for 30min, heat until the temperature reaches 160~180℃, under stirring, add ABS resin: 50g, thermoplastic phenolic resin: 70g, continue stirring at 350 rpm until the temperature drops to room temperature, and obtain laser sintering 3D printing YAG transparent ceramic powder, the particle size of the obtained laser sintered 3D printing YAG transparent ceramic powder is in the range of 40-120 μm.

Example 5

(1) YAG transparent ceramic powder pretreatment: YAG transparent ceramic powder is dried, ground, sieved, and the particle size is controlled within the range of 0.1-5 μm to obtain pretreated YAG transparent ceramic powder;

(2) Preparation of granulated YAG transparent ceramic powder: In the reactor, add water: 25000mL, water-soluble urea-formaldehyde resin: 300g, soluble starch: 300g, heat to dissolve, sodium hexametaphosphate: 100g, stir to dissolve, and then Add pretreated YAG transparent ceramic powder: 25000g, vigorously stir, react for 5.5h, and then spray dry to obtain granulated YAG transparent ceramic powder, the particle size of which is in the range of 40~100µm;

(3) Preparation of YAG transparent ceramic powder formed by laser sintering 3D printing: In the mixer, add respectively, granulate YAG transparent ceramic powder: 450g, zinc stearate: 2.5g, trimellitic anhydride: 3.0g, turn on the mixer at 300 rev/min, stirring for 30 min, heating until the temperature reaches 160~180°C, under stirring, add ABS resin: 35g, thermoplastic phenolic resin: 15g, continue stirring at 350 rev/min until the temperature drops to room temperature, and get Laser sintering 3D printing forms YAG transparent ceramic powder, and the particle size of the obtained laser sintering 3D printing forming YAG transparent ceramic powder is in the range of 40-120 μm.

Example 6

How to use: Add the YAG transparent ceramic powder material formed by laser sintering 3D printing into the powder supply tank of the 3D printing 3D printer, and add N,N-dimethylformamide into the nozzle. The specific process is as follows: the solvent N,N-dimethylformamide is sprayed from the nozzle to dissolve the adhesive on the surface of the powder material, so that the powder is bonded together. After the upper layer is bonded, the forming cylinder is lowered for a distance ( Equal to the thickness of the layer: 0.010~0.1mm), the powder supply cylinder rises to a certain height, pushes out some powder, and is pushed to the forming cylinder by the powder spreading roller, paved and compacted. Under the control of the computer, the spray head selectively sprays the solvent N,N-dimethylformamide to build the layer according to the forming data of the next build section. When the powder spreading roller spreads the powder, the excess powder is collected by the powder collecting device. Such a cycle of powder feeding, powder spreading and spraying of N,N-dimethylformamide will finally complete the bonding of a three-dimensional powder. The place where N,N-dimethylformamide is not sprayed is dry powder, which plays a supporting role in the forming process and is easy to remove after forming.

Claims (8)

1. a kind of preparation method of 3DP technology rapid prototyping YAG transparent ceramic powder material, it is characterized in that, the method has following processing steps: (1) YAG transparent ceramic powder pretreatment: dry the YAG transparent ceramic powder, grind, sieve, and control the particle size within the range of 0.1-5 μm to obtain the pretreated YAG transparent ceramic powder; (2) Preparation of granulated YAG transparent ceramic powder: In the reactor, add water: 52% to 56%, water-soluble urea-formaldehyde resin: 0.2% to 1.5%, soluble starch: 0.2% to 1.5%, Heat to dissolve, sodium hexametaphosphate: 0.1%~1.0%, stir to dissolve, then add pretreated YAG transparent ceramic powder: 42%~46%, the sum of each component is 100%, stir vigorously, react for 5~7h, then Spray drying to obtain granulated YAG transparent ceramic powder, the particle size of which is in the range of 40-100 μm; (3) Preparation of YAG transparent ceramic powder for rapid prototyping by 3DP process: in a blender, add according to mass percentage, granulate YAG transparent ceramic powder: 85% to 92%, zinc stearate: 0.5% to 1.5%, trimellitic anhydride : 0.2% ~ 1.0%, turn on the mixer at 300 rpm, stir for 30 minutes, heat up to 160 ~ 180 ° C, under stirring, add ABS resin: 2% ~ 8%, thermoplastic phenolic resin: 2% ~ 8 %, the sum of each component is 100%, continue to stir until the temperature drops to room temperature at a speed of 350 rpm, and obtain a 3DP technology rapid molding YAG transparent ceramic powder, and the obtained 3DP technology rapid molding YAG transparent ceramic powder The particle size is in the range of 40-120 μm. 2. the preparation method of a kind of 3DP technology rapid prototyping YAG transparent ceramic powder material according to claim 1, is characterized in that, the spray drying described in step (2), air inlet temperature is controlled at 100 ℃, and air outlet The temperature is controlled at 90°C, and the air intake flow rate is 200m ³ /h. 3. the preparation method of a kind of 3DP process rapid prototyping YAG transparent ceramic powder material according to claim 1, is characterized in that, the mass ratio of water-soluble urea-formaldehyde resin described in step (2) and soluble starch is at 1: Between 0.8 and 1.2. 4. the preparation method of a kind of 3DP process rapid prototyping YAG transparent ceramic powder material according to claim 1, is characterized in that, the mass ratio of water-soluble urea-formaldehyde resin described in step (2) and sodium hexametaphosphate is in 1: Between 0.09 and 0.11. 5. the preparation method of a kind of 3DP process rapid prototyping YAG transparent ceramic powder material according to claim 1, is characterized in that, the mass ratio of ABS resin described in step (3) and thermoplastic phenolic resin is at 1:0.9 ~1.1. 6. The preparation method of a kind of 3DP process rapid prototyping YAG transparent ceramic powder material according to claim 1, is characterized in that, the mass ratio of thermoplastic phenolic resin described in step (3) and trimellitic anhydride is in 1:0.09～ between 0.11. 7. the YAG transparent ceramic powder material prepared by the preparation method of a kind of 3DP process rapid prototyping YAG transparent ceramic powder material according to claim 1, is characterized in that, described rapid prototyping YAG transparent ceramic powder material is in During 3D molding conditions on a 3D printing printer, the solvent N,N-dimethylformamide is sprayed from the nozzle. 8. The YAG transparent ceramic powder material prepared by the preparation method of a kind of 3DP process rapid prototyping YAG transparent ceramic powder material according to claim 1.