Ceramic pug for 3D printing direct-writing molding by using waste porcelain as raw material, preparation method of ceramic pug and product

Abstract

The invention discloses a ceramic pug for 3D printing direct-writing molding by using waste porcelain as a raw material, and a preparation method and a product thereof. Waste porcelain particles, Longyan kaolin, potassium feldspar, quartz, ulexite, water, a sodium silicate aqueous solution and a sodium tripolyphosphate aqueous solution are used as raw materials; the formed ceramic pug is prepared into a 3D printing direct-writing molded ceramic product through 3D printing direct-writing molding. According to the invention, the large-particle waste porcelain is used as a raw material, so that the recycling and crushing cost of the waste porcelain is reduced, the recycling proportion of the waste porcelain is increased, and the additional value of the product is increased by utilizing the unique appearance mechanism of the waste porcelain particles, so that a new technology and a new way are provided for the preparation of the ceramic pug for 3D printing direct-writing molding and the utilization of the large-particle waste porcelain.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic 3D printing, and in particular to a ceramic clay material for 3D printing direct writing molding using waste ceramics as raw materials, and a preparation method and product thereof. Background Art

[0002] 3D printing is a rapid prototyping technology in the field of additive manufacturing. It can be used to shape materials including plastics, metals, and ceramics. Compared with other molding methods, 3D printing can produce physical objects through digital modeling and direct printing, and has great advantages in the field of molding special-shaped parts. Ceramics are commonly used materials in the field of architectural decoration. Common ceramic material molding methods such as dry pressing, extrusion molding, rolling molding, and grouting molding are difficult to create more three-dimensional ceramic products. Using 3D printing technology for ceramic molding can enrich product appearance design and improve product market competitiveness and added value.

[0003] At present, the 3D printing ceramic mud technology mainly mixes ceramic powder with water-soluble organic matter to prepare a paste for 3D printing. When the ceramic powder is a barren material, such as alumina, zirconium oxide, silicon carbide, etc., the plasticity and shear thinning properties of the mud are matched mainly through the addition amount of organic matter and the formula composition, that is, the viscosity and fluidity are adapted; when the ceramic powder is a clay-type plastic raw material, such as kaolin, montmorillonite, etc., the clay-type mineral raw materials are used to provide plasticity and bonding, and the organic matter is used to provide the fluidity and lubricity of the paste to achieve the adaptation of viscosity and fluidity. However, regardless of whether the ceramic powder is a barren material or a plastic material, the 3D printing ceramic mud used in the existing technology requires the particle size of the ceramic powder to be between 0.5 and 5 μm, which is determined by the molecular chain and molecular weight of the organic matter that provides the viscosity or fluidity of the mud.

[0004] Sintered building sanitary ceramic waste is one of the typical industrial solid wastes. It has high hardness and is difficult to crush. The conventional recycling method is to ball-mill the waste porcelain to a particle size of 300-400 mesh and add it to the existing formula mud. On the one hand, the cost of ball milling is high, and on the other hand, its recycling rate is only about 20-40%. In the field of 3D printing technology, although the prior art proposes a 3D printing ceramic paste prepared from waste porcelain, about 50% of the organic binding system is added to the paste mud, and the particle diameter of the waste porcelain powder is 74-180μm. Although it can be formed by 3D printing, its low solid content leads to the defects of shrinkage, deformation, and cracking during the sintering process, and the high content of organic matter will release a large amount of CO2 during the debinding process, which is not conducive to environmental protection.

[0005] For example, using large-particle waste porcelain (greater than 500 μm) to prepare ceramic clay for 3D printing direct writing can not only reduce the cost of recycling and crushing waste porcelain and increase the recycling ratio of waste porcelain, but also use the unique appearance mechanism of waste porcelain particles to increase the added value of the product, thus providing a new way for the preparation of ceramic clay for 3D printing direct writing and the utilization of large-particle waste porcelain. There is no report on the application of large-particle waste porcelain in 3D printing clay. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a ceramic clay material for 3D printing direct writing using waste porcelain as raw materials, using waste porcelain particles, Longyan kaolin, potassium feldspar, quartz, ulexite, water, sodium silicate aqueous solution, sodium tripolyphosphate aqueous solution as raw materials to reduce the cost of recycling waste porcelain, increase the proportion of waste porcelain recycling and the added value of the product. Another purpose of the present invention is to provide a preparation method and product of the above-mentioned ceramic clay material for 3D printing direct writing using waste porcelain as raw materials.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] The invention provides a ceramic clay material for 3D printing direct writing molding using waste porcelain as a raw material. The raw material composition is as follows by weight: 50-60 parts of waste porcelain particles, 30-35 parts of Longyan kaolin, 2-4 parts of potassium feldspar, 2-4 parts of quartz, 4-12 parts of ulexite, 25-30 parts of water, 1-3 parts of a sodium silicate aqueous solution with a concentration of 5wt%, and 0.5-1.5 parts of a sodium tripolyphosphate aqueous solution with a concentration of 10wt%. The waste porcelain is obtained by crushing building ceramics and sanitary ceramics waste with a sintering temperature within the range of 1160-1220°C, and the particle size of the waste porcelain particles is 0.5-1mm.

[0009] Furthermore, the particle sizes of the Longyan kaolin, potassium feldspar, quartz and ulexite described in the present invention are all above 200 meshes.

[0010] Another object of the present invention is achieved by the following technical solutions:

[0011] The method for preparing the ceramic clay material for 3D printing direct writing using waste porcelain as raw material provided by the present invention comprises the following steps:

[0012] (1) dry-mixing the waste porcelain particles, Longyan kaolin, potassium feldspar, quartz, and ulexite according to a proportion to obtain a mixed dry material;

[0013] (2) stirring and mixing the water, a 5 wt % sodium silicate aqueous solution, and a 10 wt % sodium tripolyphosphate aqueous solution according to a ratio to obtain a transparent liquid;

[0014] (3) adding the transparent liquid to the mixed dry material by spraying, and performing wet kneading in a kneading machine; the obtained clay material is vacuumed to remove bubbles, and a ceramic clay material for 3D printing direct writing is obtained.

[0015] Furthermore, in the preparation method of the present invention, the stirring and mixing time in step (1) is 1 to 2 hours; the stirring and mixing time in step (2) is 5 to 10 minutes; the wet kneading time in step (3) is 0.5 to 1 hour, and the vacuum degassing time is 20 to 30 minutes.

[0016] The ceramic product provided by the present invention is based on the ceramic clay material for 3D printing direct writing molding using waste porcelain as raw materials, and the preparation method thereof has the following steps:

[0017] (1) placing the ceramic clay material in a 3D printer for direct writing molding to obtain a 3D printed ceramic body;

[0018] (2) After the 3D printed ceramic body is dried, the temperature is raised to 1200-1250° C. at 10-15° C. / min for calcination, the temperature is kept at 20-40 min, and the body is naturally cooled to obtain a 3D printed direct writing ceramic product.

[0019] In the above scheme, the process parameters of 3D printing direct writing molding in step (1) of the ceramic product of the present invention are: the printing needle diameter is 4-6 mm, the printing pressure is 0.2-0.5 MPa, the direct writing speed is 5-7 mm / s, and the layer thickness is 3-5 mm. In step (2), the 3D printed ceramic body is dried at 40-60°C for 6-12 hours and at 100-120°C for 1-2 hours.

[0020] Furthermore, the ceramic product of the present invention has a sintering volume shrinkage rate of less than 5%, a water absorption rate of less than 1%, and a flexural strength of more than 25 MPa.

[0021] The present invention has the following beneficial effects:

[0022] (1) The present invention uses waste porcelain as the main material, kaolin and other mineral raw materials as auxiliary materials, and adds water and a small amount of sodium silicate aqueous solution and sodium tripolyphosphate aqueous solution to prepare 3D printing direct writing ceramic clay, with a solid content of more than 75%. No organic plasticizer and lubricant are required to realize 3D printing direct writing of ceramic clay, and the printed blank can be obtained after conventional drying and calcination to obtain a 3D printed ceramic product. The preparation process of the ceramic clay of the present invention is simple, the recycling rate of large-particle waste porcelain is high, and the cost of recycling waste porcelain is reduced. There is no debinding of organic matter in the calcination process, which reduces carbon emissions. The product obtained by 3D printing and calcination has a low shrinkage deformation rate, and the appearance has a special particle mechanism and a three-dimensional structure, which increases the added value of the product, and provides a new technical solution and approach for the green, economical and environmentally friendly recycling of waste porcelain.

[0023] (2) The 3D printing ceramic clay provided by the present invention uses large-particle waste porcelain particles as the main raw material, and sodium silicate and sodium tripolyphosphate are added in small amounts as degumming agents to achieve the degumming and dispersion of Longyan kaolin with excellent plasticity and viscosity. If the waste porcelain particles are too large, it will increase the cracking and stratification defects between the waste porcelain and clay materials such as kaolin. If the particles are too small, the waste porcelain will move, crack and stratify during the drying and shrinkage of the kaolin clay. The present invention uses large waste porcelain particles of 0.5 to 1 mm as a dispersed phase distributed in the fine-particle clay material mainly composed of Longyan kaolin, which not only improves the fluidity of the clay material under low water content conditions, but also reduces the shrinkage, deformation and cracking defects caused by the drying of Longyan kaolin.

[0024] (3) The present invention dissolves and disperses the high-plasticity and high-viscosity Longyan kaolin, replacing the addition of organic matter to adjust the fluidity and viscosity of the mud. Waste porcelain and mineral materials of appropriate particle size provide the fluidity of the mud through the dissolution and dispersion of clay at a relatively low moisture content. The uniform stacking of the mud is achieved by controlling the low-pressure and slow direct writing molding of the 3D printer, thereby reducing the collapse and drying cracking defects of the mud. The dissolution and dispersion does not affect the viscosity of the Longyan kaolin after drying. Therefore, the 3D printed mud blank has a higher green strength after drying, which is convenient for the subsequent glazing and blank movement process. Sodium borate calcium calcium is used to adjust the calcination temperature of the product, and potassium feldspar and quartz are used to adjust the high-temperature viscosity of the product and prevent the product from calcining and deformation, ultimately obtaining a low-cost, high-performance, high-value-added 3D printed ceramic product. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings:

[0026] Figure 1 This is a process flow chart of the preparation of ceramic clay material and ceramic products for 3D printing direct writing molding according to an embodiment of the present invention;

[0027] Figure 2 This is an appearance diagram of a 3D printed direct writing ceramic product prepared in Example 1 of the present invention;

[0028] Figure 3 This is an appearance diagram of a 3D printed direct writing ceramic product prepared in Example 2 of the present invention. DETAILED DESCRIPTION

[0029] Embodiment 1:

[0030] 1. In this embodiment, a ceramic clay material for 3D printing direct writing using waste porcelain as a raw material is used. The raw material composition is as follows by weight: 53 parts of waste porcelain particles, 30 parts of Longyan kaolin (produced in Longyan, Fujian Province, the same below), 3 parts of potassium feldspar, 2 parts of quartz, 12 parts of ulexite, 25 parts of water, 1 part of a sodium silicate aqueous solution with a concentration of 5wt%, and 1.5 parts of a sodium tripolyphosphate aqueous solution with a concentration of 10wt%; the waste porcelain is obtained by crushing architectural ceramics and sanitary ceramic waste with a sintering temperature within the range of 1160 to 1220°C, and the particle size of the waste porcelain particles is 0.5 to 1mm; the particle sizes of Longyan kaolin, potassium feldspar, quartz, and ulexite are all above 200 mesh.

[0031] 2. The method for preparing ceramic clay material for 3D printing direct writing molding using waste porcelain as raw material in this embodiment is as follows: Figure 1 As shown, the steps are as follows:

[0032] (1) adding the above-mentioned waste porcelain particles, Longyan kaolin, potassium feldspar, quartz, and ulexite according to the proportion into a kneader and dry-mixing for 1 hour to obtain a mixed dry material;

[0033] (2) stirring and mixing the water, a 5 wt % sodium silicate aqueous solution, and a 10 wt % sodium tripolyphosphate aqueous solution according to a certain ratio for 10 minutes to obtain a transparent liquid;

[0034] (3) The transparent liquid is added to the mixed dry material by spraying, and wet kneading is performed in a kneading machine for 0.8 h. The obtained clay is vacuumed and degassed for 30 min to obtain a ceramic clay for 3D printing direct writing.

[0035] 3. This embodiment is based on the 3D printing direct writing of the above ceramic mud to form a ceramic product, such as Figure 1 As shown, the steps of its preparation method are as follows:

[0036] (1) placing the ceramic clay material in a 3D printer for direct writing to obtain a 3D printed ceramic body; the process parameters of the 3D printing direct writing are: the printing needle diameter is 4 mm, the printing pressure is 0.25 MPa, the direct writing speed is 5 mm / s, and the layer thickness is 5 mm;

[0037] (2) The 3D printed ceramic body was dried at 60°C for 6 h and 120°C for 1 h, then heated to 1200°C at 15°C / min for calcination, kept at this temperature for 20 min, and cooled naturally to obtain a 3D printed direct writing ceramic product (see Figure 2 ).

[0038] Embodiment 2:

[0039] 1. The present embodiment uses waste porcelain as a raw material for 3D printing direct writing ceramic clay, and its raw material composition is as follows by weight: 55 parts of waste porcelain particles, 33 parts of Longyan kaolin, 2 parts of potassium feldspar, 4 parts of quartz, 6 parts of ulexite, 28 parts of water, 2 parts of 5wt% sodium silicate aqueous solution, and 1 part of 10wt% sodium tripolyphosphate aqueous solution; the waste porcelain is obtained by crushing building ceramics and sanitary ceramics waste with a sintering temperature in the range of 1160 to 1220°C, and the particle size of the waste porcelain particles is 0.5 to 1mm; the particle sizes of Longyan kaolin, potassium feldspar, quartz, and ulexite are all above 200 mesh.

[0040] 2. The method for preparing ceramic clay material for 3D printing direct writing molding using waste porcelain as raw material in this embodiment is as follows: Figure 1 As shown, the steps are as follows:

[0041] (1) adding the above-mentioned waste porcelain particles, Longyan kaolin, potassium feldspar, quartz, and ulexite according to the proportion into a kneader and dry-mixing for 1.5 hours to obtain a mixed dry material;

[0042] (2) stirring and mixing the water, a 5 wt % sodium silicate aqueous solution, and a 10 wt % sodium tripolyphosphate aqueous solution according to a certain ratio for 10 minutes to obtain a transparent liquid;

[0043] (3) The transparent liquid is added to the mixed dry material by spraying, and wet kneading is performed in a kneading machine for 0.8 h. The obtained clay is vacuumed and degassed for 25 min to obtain a ceramic clay for 3D printing direct writing.

[0044] 3. This embodiment is based on the 3D printing direct writing of the above ceramic mud to form a ceramic product, such as Figure 1 As shown, the steps of its preparation method are as follows:

[0045] (1) placing the ceramic clay material in a 3D printer for direct writing to obtain a 3D printed ceramic body; the process parameters of the 3D printing direct writing are: the printing needle diameter is 4 mm, the printing pressure is 0.35 MPa, the direct writing speed is 6 mm / s, and the layer thickness is 4 mm;

[0046] (2) The 3D printed ceramic body was dried at 50°C for 6 h and 100°C for 1 h, then heated to 1230°C at 12°C / min for calcination, kept at this temperature for 40 min, and cooled naturally to obtain a 3D printed direct writing ceramic product (see Figure 3 ).

[0047] Embodiment three:

[0048] 1. In this embodiment, a ceramic clay material for 3D printing direct writing using waste porcelain as a raw material is used. The raw material composition is as follows by weight: 57 parts of waste porcelain particles, 35 parts of Longyan kaolin, 2 parts of potassium feldspar, 2 parts of quartz, 4 parts of ulexite, 30 parts of water, 3 parts of a sodium silicate aqueous solution with a concentration of 5wt%, and 1.5 parts of a sodium tripolyphosphate aqueous solution with a concentration of 10wt%; the waste porcelain is obtained by crushing architectural ceramics and sanitary ceramic waste with a sintering temperature within the range of 1160 to 1220°C, and the particle size of the waste porcelain particles is 0.5 to 1mm; the particle sizes of Longyan kaolin, potassium feldspar, quartz, and ulexite are all above 200 mesh.

[0049] 2. The method for preparing ceramic clay material for 3D printing direct writing molding using waste porcelain as raw material in this embodiment is as follows: Figure 1 As shown, the steps are as follows:

[0050] (1) adding the above-mentioned waste porcelain particles, Longyan kaolin, potassium feldspar, quartz, and ulexite according to the proportion into a kneader and dry-mixing for 2 hours to obtain a mixed dry material;

[0051] (2) stirring and mixing the water, a 5 wt % sodium silicate aqueous solution, and a 10 wt % sodium tripolyphosphate aqueous solution according to a certain ratio for 10 minutes to obtain a transparent liquid;

[0052] (3) The transparent liquid is added to the mixed dry material by spraying, and wet kneading is performed in a kneading machine for 1 hour. The obtained clay is vacuumed and degassed for 30 minutes to obtain a ceramic clay for 3D printing direct writing.

[0053] 3. This embodiment is based on the 3D printing direct writing of the above ceramic mud to form a ceramic product, such as Figure 1 As shown, the steps of its preparation method are as follows:

[0054] (1) placing the ceramic clay material in a 3D printer for direct writing to obtain a 3D printed ceramic body; the process parameters of the 3D printing direct writing are: the printing needle diameter is 6 mm, the printing pressure is 0.5 MPa, the direct writing speed is 7 mm / s, and the layer thickness is 5 mm;

[0055] (2) The 3D printed ceramic body was dried at 40°C for 6 h and 120°C for 1 h, and then heated to 1250°C at a rate of 10°C / min for calcination, kept at that temperature for 40 min, and naturally cooled to obtain a 3D printed direct writing ceramic product.

[0056] The performance indicators of the 3D printed direct writing ceramic product prepared in the embodiment of the present invention are shown in Table 1.

[0057] Table 1 Performance indicators of 3D printing direct writing ceramic products prepared in the embodiments of the present invention

[0058]

Claims

1. A ceramic clay material for 3D printing direct writing using waste porcelain as raw material, characterized in that The raw materials are composed of 50-60 parts by weight of waste porcelain particles, 30-35 parts of Longyan kaolin, 2-4 parts of potassium feldspar, 2-4 parts of quartz, 4-12 parts of ulexite, 25-30 parts of water, 1-3 parts of 5wt% sodium silicate aqueous solution, and 0.5-1.5 parts of 10wt% sodium tripolyphosphate aqueous solution; the waste porcelain is obtained by crushing building ceramics and sanitary ceramics waste with a sintering temperature within the range of 1160-1220°C, and the particle size of the waste porcelain particles is 0.5-1mm.

2. The ceramic clay material for 3D printing direct writing using waste porcelain as raw material according to claim 1, characterized in that: The particle sizes of the Longyan kaolin, potassium feldspar, quartz and ulexite are all above 200 meshes.

3. The method for preparing ceramic clay material for 3D printing direct writing using waste porcelain as raw material according to claim 1 or 2, characterized in that The following steps are involved: (1) dry-mixing the waste porcelain particles, Longyan kaolin, potassium feldspar, quartz, and ulexite according to a proportion to obtain a mixed dry material; (2) stirring and mixing the water, a 5 wt % sodium silicate aqueous solution, and a 10 wt % sodium tripolyphosphate aqueous solution according to a ratio to obtain a transparent liquid; (3) adding the transparent liquid to the mixed dry material by spraying, and performing wet kneading in a kneading machine; the obtained clay material is vacuumed to remove bubbles, and a ceramic clay material for 3D printing direct writing is obtained.

4. The method for preparing ceramic clay material for 3D printing direct writing using waste porcelain as raw material according to claim 3, characterized in that: The stirring and mixing time in step (1) is 1 to 2 hours; the stirring and mixing time in step (2) is 5 to 10 minutes; the wet kneading time in step (3) is 0.5 to 1 hour, and the vacuum degassing time is 20 to 30 minutes.

5. A ceramic product based on the ceramic clay material for 3D printing direct writing molding using waste porcelain as raw material as claimed in claim 1, characterized in that The steps of the preparation method are as follows: (1) placing the ceramic clay material in a 3D printer for direct writing molding to obtain a 3D printed ceramic body; (2) After the 3D printed ceramic body is dried, the temperature is raised to 1200-1250° C. at 10-15° C. / min for calcination, the temperature is kept at 20-40 min, and the body is naturally cooled to obtain a 3D printed direct writing ceramic product.

6. The ceramic product according to claim 5, characterized in that: The process parameters of the 3D printing direct writing molding in the step (1) are: the printing needle diameter is 4 to 6 mm, the printing pressure is 0.2 to 0.5 MPa, the direct writing speed is 5 to 7 mm / s, and the layer thickness is 3 to 5 mm.

7. The ceramic product according to claim 5, characterized in that: In the step (2), the 3D printed ceramic body is dried at 40-60° C. for 6-12 hours and at 100-120° C. for 1-2 hours.

8. The ceramic product according to claim 5, characterized in that: The ceramic product has a sintering volume shrinkage rate of less than 5%, a water absorption rate of less than 1%, and a flexural strength of more than 25 MPa.

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