CN106966718B - A 3D printing strontium barium titanate powder material prepared by using sugar as an adhesive - Google Patents

Abstract

The invention discloses a kind of methods for preparing 3D printing barium-strontium titanate powder material with sugar for adhesive, which is characterized in that is first granulated nano barium phthalate ceramic powder, makes its partial size in 80 ~ 120 μ ms；Then it in grinder, is added by mass percentage concentration, granulation strontium-barium titanate ceramic powder: 85% ~ 92%, grinding, temperature rise to 120 ± 2 DEG C, addition stearmide: 0.5% ~ 2%, grind 30min, temperature continues to rise to 190 ± 2 DEG C, white sugar: 5% ~ 10%, melamine: 0.5% ~ 1.5%, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters: 1% ~ 3%, grinding, obtains 3D printing barium-strontium titanate powder material, acquired 3D printing barium-strontium titanate powder material.The 3D printing barium-strontium titanate powder material with it is laser sintered can straight forming, sphericity is high, good fluidity, and formed precision is high, and has simple process, and production cost is low, easy to industrialized production.

Description

A 3D printing strontium barium titanate powder material prepared by using sugar as an adhesive

technical field

The invention relates to a preparation method of laser sintering 3D printing rapid prototyping powder material, which belongs to the field of rapid prototyping materials, in particular to a method for preparing 3D printing strontium barium titanate powder material with sugar as an adhesive and laser sintering 3D printing forming.

Background technique

Sugar is refined sugar made from molasses extracted from sugarcane and beet. It is a non-reducing disaccharide formed by the dehydration condensation of one molecule each of glucose and fructose. When heated to 160°C, it melts into a thick and transparent liquid. Cooling time to recrystallize. When the heating time is prolonged, the sucrose is decomposed into glucose and anhydrofructose. At a higher temperature of 190~220°C, sucrose is dehydrated and condensed into caramel. Caramel has a strong binding effect, which can make the powder stick together and act as a binder. Sugar is used as adhesive instead of chemical adhesive to reduce environmental pollution.

Barium strontium titanate (Bax Sr1 - x TiO ₃ , referred to as BST) is a solid solution of BaTiO3 and Sr TiO3. It is an excellent heat-sensitive material, capacitor material and ferroelectric piezoelectric material, which has the characteristics of high dielectric constant, low dielectric loss, Curie temperature (TC ) changes with composition, and the nonlinear change of dielectric constant with electric field. , has broad application prospects in the fields of ultra-large-scale dynamic memory, microwave tuner, etc., and has become one of the most extensively researched materials in the field of integrated devices. The electrical properties of BST materials are closely related to the microstructure of materials such as porosity and grain size. Ultra-fine grain and highly dense BST has ideal dielectric properties, excellent physical and chemical properties of materials, and has wide application value in industry. With the development of microelectronics industry becoming more and more mature, BST ceramic materials will receive more and more attention.

Laser sintering 3D printing is a method of additive manufacturing. This process also uses the laser as the energy source, and the powder of plastic, wax, ceramic, metal or its composite is uniformly sintered on the processing plane through the laser beam. A thin layer of powder is evenly spread on the workbench as the raw material. Under the control of the computer, the laser beam scans the layered two-dimensional data at a certain speed and energy density through the scanner. After scanning by the laser beam, the powder at the corresponding position is sintered into a solid sheet with a certain thickness, and the unscanned part remains in the form of loose powder. After this layer is scanned, the next layer needs to be scanned. First, lower the working table according to the thickness of the object’s cut layer, that is, the layer thickness, and the powder spreading roller will spread the powder evenly, and a new layer of scanning can be started. Repeat this until all layers are scanned. The product can be obtained by removing excess powder and post-processing.

In the field of existing molding materials, SLS rapid prototyping technology has a wide range of applications in the field of rapid prototyping because of its advantages such as diverse sources of raw materials and short construction time of parts. But most of them are organic materials and composite materials. The Chinese invention patent CN1379061A discloses a nylon powder material used for laser sintering molding products. Through chemical synthesis and process improvement, the surface of the nylon powder material is treated and sintered Excellent performance, high strength and good toughness of molded products, which simplifies the preparation process of laser sintered nylon materials and reduces costs; Chinese invention patent CN103881371 discloses a stone-plastic composite powder for laser sintering 3D manufacturing technology and its preparation method .

In this application, sugar adhesive will be thermally coated onto the surface of barium strontium titanate after granulation, and the 3D printed barium strontium titanate powder material can be directly formed by laser sintering 3D printing. There is no need to spray adhesive during the molding process. The advantage is that the amount of adhesive is greatly reduced, and the adhesive used is sugar, which reduces environmental pollution and the product is of high quality. The 3D printing strontium barium titanate powder material adhesive coating prepared by the process of this application is uniform, the surface is smooth, and the fluidity is good, which is suitable for laser sintering 3D printing. In addition, the preparation method provided by the present application is simple and low in cost.

Contents of the invention

The purpose of the present invention is to provide a method for preparing 3D printing strontium barium titanate powder material with sugar as an adhesive, and the rapid prototyping strontium barium titanate powder material can be directly formed by laser scanning without spraying binder;

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

A method for preparing a 3D printing barium strontium titanate powder material using sugar as an adhesive, characterized in that the method has the following process steps:

(1) Preparation of granulated barium strontium titanate ceramic powder: In the reactor, add according to mass percentage, water: 52%~58%, water-soluble starch: 0.2%~1.0%, water-based polyurethane: 0.5%~2.0% , polyethylene glycol: 0.2%~1.0%, stir to dissolve, then add nano-barium titanate ceramic powder: 40%~45%, the sum of each component is 100%, stir vigorously, react for 6~7h, and then spray dry , to obtain granulated barium strontium titanate ceramic powder, the particle size of which is in the range of 80~120µm;

(2) Preparation of 3D printing strontium barium titanate powder material: in the grinder, add it according to the mass percentage concentration, granulate strontium barium titanate ceramic powder: 85%~92%, turn on the grinder at 500 rpm /min, grind, temperature rises to 120±2°C, add stearamide: 0.5%~2%, grind for 30min, temperature continues to rise to 190±2°C, sugar: 5%~10%, melamine: 0.5%~ 1.5%, isopropyl tris(dioctyl phosphate acyloxy) titanate: 1%~3%, the sum of each component is 100%, constant temperature, grinding at 500 rpm for 40~50 min, Cool to room temperature to obtain a 3D printed barium strontium titanate powder material, and the obtained 3D printed barium strontium titanate powder material has a particle size within the range of 100-150 μm.

In the spray drying described in step (1), the temperature of the air inlet is controlled at 110°C, the temperature of the air outlet is controlled at 90°C, and the flow rate of the air inlet is 250m ³ /h.

The polyethylene glycol described in step (1) is polyethylene glycol 200 or polyethylene glycol 400.

The white sugar described in the step (2) is edible soft white sugar or white granulated sugar.

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

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

(1) The 3D printing barium strontium titanate powder material obtained in the present invention uses sugar as an adhesive to coat the surface of the granulated barium strontium titanate, which is green and environmentally friendly, and can be directly formed under laser sintering conditions without spraying the binder.

(2) The 3D printing strontium barium titanate powder material obtained by the present invention has uniform particle size, high sphericity, good fluidity and stable properties; thin-walled models or tiny models can be manufactured from this rapid prototyping powder material. Parts, manufactured products have the characteristics of high surface gloss, good strength and high precision.

(3) The 3D printing strontium barium titanate powder material obtained in the present invention has the advantages of simple preparation process, easy control of conditions, low production cost, easy industrial production, easy storage, and no pollution.

Detailed ways

Example 1

(1) Preparation of granulated barium strontium titanate ceramic powder: In the reactor, add water: 540mL, water-soluble starch: 5g, water-based polyurethane: 10g, polyethylene glycol: 5g, stir to dissolve, and then add nano-titanium Barium oxide ceramic powder: 400g, vigorously stirred, reacted for 6.5h, and then spray-dried to obtain granulated barium strontium titanate ceramic powder with a particle size in the range of 80-120µm;

(2) Preparation of 3D printing strontium barium titanate powder material: In the grinder, add separately, granulate strontium barium titanate ceramic powder: 88g, turn on the grinder at a speed of 500 rpm, grind, and the temperature rises to 120±2℃, add stearamide: 1g, grind for 30min, continue to increase the temperature to 190±2℃, white sugar: 8g, melamine: 1g, isopropyl tri(dioctyl phosphate acyloxy) titanate: 2g, constant temperature, grinding at a speed of 500 rpm for 45 min, and cooling to room temperature to obtain a 3D printing strontium barium titanate powder material. The obtained 3D printing strontium barium titanate powder material has a particle size of 100~ 150μm range.

Example 2

(1) Preparation of granulated barium strontium titanate ceramic powder: In the reactor, add water: 1040mL, water-soluble starch: 4g, water-based polyurethane: 36g, polyethylene glycol: 20g, stir to dissolve, and then add nano-titanium Barium oxide ceramic powder: 900g, vigorously stirred, reacted for 6h, and then spray-dried to obtain granulated barium strontium titanate ceramic powder, the particle size of which was in the range of 80~120µm;

(2) Preparation of 3D printing strontium barium titanate powder material: In the grinder, add separately, granulate strontium barium titanate ceramic powder: 920g, turn on the grinder at a speed of 500 rpm, grind, and the temperature rises to 120±2℃, add stearamide: 5g, grind for 30min, the temperature continues to rise to 190±2℃, white sugar: 50g, melamine: 15g, isopropyl tri(dioctyl phosphate acyloxy) titanate: 10g, constant temperature, grinding at a speed of 500 rpm for 40 min, and cooling to room temperature to obtain a 3D printing strontium barium titanate powder material, the obtained 3D printing strontium barium titanate powder material has a particle size of 100~ 150μm range.

Example 3

(1) Preparation of granulated barium strontium titanate ceramic powder: In the reactor, add water: 1160mL, water-soluble starch: 20g, water-based polyurethane: 16g, polyethylene glycol: 4g, stir to dissolve, and then add nano-titanium Barium oxide ceramic powder: 800g, vigorously stirred, reacted for 7 hours, and then spray-dried to obtain granulated barium strontium titanate ceramic powder with a particle size in the range of 80-120µm;

(2) Preparation of 3D printing strontium barium titanate powder material: In the grinder, add separately, granulate strontium barium titanate ceramic powder: 850g, turn on the grinder at a speed of 500 rpm, grind, and the temperature rises to 120±2°C, add stearamide: 20g, grind for 30min, continue to increase the temperature to 190±2°C, white sugar: 100g, melamine: 12g, isopropyl tri(dioctyl phosphate acyloxy) titanate: 18g, constant temperature, grinding at a speed of 500 rpm for 50 minutes, and cooling to room temperature to obtain a 3D printing strontium barium titanate powder material. The obtained 3D printing strontium barium titanate powder material has a particle size of 100~150 μm In the range.

Example 4

(1) Preparation of granulated barium strontium titanate ceramic powder: In the reactor, add water: 1100mL, water-soluble starch: 14g, water-based polyurethane: 20g, polyethylene glycol: 16g, stir to dissolve, and then add nano-titanium Barium oxide ceramic powder: 840g, vigorously stirred, reacted for 6.5h, and then spray-dried to obtain granulated barium strontium titanate ceramic powder, the particle size of which was in the range of 80~120µm;

(2) Preparation of 3D printing strontium barium titanate powder material: In the grinder, add separately, granulate strontium barium titanate ceramic powder: 880g, turn on the grinder at a speed of 500 rpm, grind, and the temperature rises to 120±2°C, add stearamide: 15g, grind for 30min, continue to increase the temperature to 190±2°C, white sugar: 70g, melamine: 5g, isopropyl tri(dioctyl phosphate acyloxy) titanate: 30g, constant temperature, grinding at a speed of 500 rpm for 45 min, and cooling to room temperature to obtain a 3D printed strontium barium titanate powder material. The obtained 3D printed strontium barium titanate powder material has a particle size of 100~ 150μm range.

Example 5

(1) Preparation of granulated barium strontium titanate ceramic powder: In the reactor, add water: 1120mL, water-soluble starch: 20g, water-based polyurethane: 10g, polyethylene glycol: 10g, stir to dissolve, and then add nano-titanium Barium oxide ceramic powder: 860g, vigorously stirred, reacted for 6.5h, and then spray-dried to obtain granulated barium strontium titanate ceramic powder, the particle size of which was in the range of 80~120µm;

(2) Preparation of 3D printing strontium barium titanate powder material: In the grinder, add separately, granulate strontium barium titanate ceramic powder: 900g, turn on the grinder at a speed of 500 rpm, grind, and the temperature rises to 120±2℃, add stearamide: 10g, grind for 30min, continue to increase the temperature to 190±2℃, white sugar: 60g, melamine: 10g, isopropyl tri(dioctyl phosphate acyloxy) titanate: 20g, constant temperature, grinding at a speed of 500 rpm for 45 min, and cooling to room temperature to obtain a 3D printing strontium barium titanate powder material. The obtained 3D printing strontium barium titanate powder material has a particle size of 100~ 150μm range.

How to use: Add the 3D printed barium strontium titanate powder material into the powder supply cylinder of the selective laser sintering molding machine, the powder spreading roller spreads the powder material evenly on the processing plane and is heated to the processing temperature, the laser emits laser light, The computer controls the switch of the laser and the angle of the scanner so that the laser beam scans on the processing plane according to the shape of the corresponding two-dimensional sheet. , and so on, to obtain laser sintered parts; where the laser beam scans on the processing plane in a sub-area scanning manner, the laser power is 80~100W, the scanning speed is 1500mm/s, the scanning distance is 0.1~0.15mm, and the layer thickness is 0.10~0.2mm, preheating temperature: 100℃, processing temperature: 200~210℃.

Claims (4)

1. A method for preparing 3D printing barium strontium titanate powder material with sugar as adhesive, is characterized in that, the method has the following processing steps: (1) Preparation of granulated barium strontium titanate ceramic powder: In the reactor, add water: 52% to 58%, water-soluble starch: 0.2% to 1.0%, water-based polyurethane: 0.5% to 2.0% , polyethylene glycol: 0.2% ~ 1.0%, stir to dissolve, then add nano barium titanate ceramic powder: 40% ~ 45%, the sum of each component is 100%, stir vigorously, react for 6 ~ 7h, and then spray dry , to obtain granulated barium strontium titanate ceramic powder, the particle size of which is in the range of 80-120 μm; (2) Preparation of 3D printing strontium barium titanate powder material: in the grinder, add it according to the mass percentage concentration, granulate strontium barium titanate ceramic powder: 85% ~ 92%, turn on the grinder at 500 rpm Grinding, the temperature rises to 120±2°C, add stearamide: 0.5%~2%, grind for 30min, the temperature continues to rise to 190±2°C, sugar: 5%~10%, melamine: 0.5%~ 1.5%, isopropyl tris (dioctyl phosphate acyloxy) titanate: 1% ~ 3%, the sum of each component is 100%, constant temperature, grinding at 500 rpm for 40 ~ 50min, cold to room temperature to obtain a 3D printed strontium barium titanate powder material, and the obtained 3D printed strontium barium titanate powder material has a particle size within the range of 100-150 μm. 2. A method for preparing 3D printing strontium barium titanate powder material with sugar as an adhesive according to claim 1, characterized in that, in the spray drying described in step (1), the air inlet temperature is controlled at 110°C , the air outlet temperature is controlled at 90°C, and the air inlet flow rate is 250m ³ /h. 3. a kind of method according to claim 1 is that adhesive preparation 3D prints strontium barium titanate powder material with sugar, it is characterized in that, the polyethylene glycol described in step (1) is polyethylene glycol 200 or macrogol 400. 4. The 3D printing strontium barium titanate powder material prepared by a method for preparing a 3D printing strontium barium titanate powder material using sugar as an adhesive according to claim 1.