CN115745404A - High-solid-content glaze suitable for direct-writing 3D printing and preparation method thereof - Google Patents

Abstract

The invention provides a high-solid-content glaze suitable for direct writing 3D printing, which includes raw materials for ceramic glaze, adding additives, deionizing, and mixing uniformly; the invention also provides a glaze suitable for direct writing 3D printing The preparation method of high solid content glaze is to mix the raw materials for ceramic glaze, additives, and deionized water evenly to obtain a high solid content glaze paste; after vacuuming and defoaming, the 3D printing high solid content glaze is obtained Paste: the high solid content glaze paste is added to the 3D printer, based on the set model, printed on the green body, directly written and extruded through the printing head of the 3D printer, and the high solid content glaze paste is superimposed layer by layer, Obtain 3D printing graphics on the green body, dry and sinter. The invention has the advantages of simple raw material acquisition, low cost, high solid content, uniform extrusion lines and good bonding of the green body glaze, and free graphics can be realized on the green body , and make up for the lack of ceramic direct writing 3D printing technology in glaze research.

Description

A high solid content glaze suitable for direct writing 3D printing and its preparation method

technical field

The invention relates to the technical field of 3D printing, in particular to a glaze with high solid content suitable for direct writing 3D printing and a preparation method thereof.

Background technique

Glaze is a silicate compound, which is a thin glass-like layer attached to the surface of the ceramic body after high temperature. Ceramics are generally divided into three categories: daily-use ceramics, artistic ceramics and industrial ceramics, and industrial ceramics include architectural-sanitary ceramics. According to the different types of ceramics, the glazing methods on the ceramic body are also different, including artificial glazing (glazing spraying, dipping glaze, pouring glaze, swaying glaze), screen printing, roller printing, inkjet printing, etc. Manual glazing faces problems such as high cost and long production cycle. In the production process of inkjet printing and printing technologies, inkjet printing pictures will be lost. After the pattern is printed on the base glazed body, the pattern will be lost. It becomes blurred and the layers are unclear, and sometimes due to the color of the green body, the level of the pattern cannot achieve a very ideal effect, the combination with the green body is not good, and the thickness cannot be satisfied. Chinese Patent Publication No. CN114634349A on this To solve these problems, an inkjet decorative ceramic tile, its blank and its preparation method are disclosed. This method produces a blank that can make the ink dots of inkjet more concentrated, but the production of the blank needs to be pressed after spray granulation It is made by drying, the production process is complicated, and the glaze used in inkjet printing has high requirements for its suspension stability and moisture retention performance. has certain limitations.

Direct writing 3D printing technology is a relatively new preparation method, which is developing rapidly abroad. Direct writing 3D printing technology uses pneumatic or mechanical power to extrude the slurry from the nozzle to form a linear fluid, which is printed on the substrate according to the designed three-dimensional Structural modeling begins to take shape from the first layer. Through the movement of three-dimensional space, according to the modeling path design, it moves upward in the Z-axis direction, and the overall physical shape is formed layer by layer. At present, the direct writing 3D printing technology researched by the present invention has the advantages of controlling the printing line width to 0.8mm and above, the thickness of a single layer can be controlled below 1mm, and the printing speed can be adjusted at any time. Its simple equipment structure and good slurry compatibility Personality will be better utilized in daily production, and production can be realized efficiently, quickly and individually. With the continuous update of materials, active design of multi-component raw materials can be formed. At present, there are very few researches on related glazes in the research of ceramic direct writing 3D printing in China, so this invention is based on the development and use of direct writing 3D printing technology, and prepares a kind of high solid content glaze that can be used in direct writing 3D printers material.

Contents of the invention

The purpose of the present invention is to provide a high solid content glaze suitable for direct writing 3D printing and its preparation method, which is used to solve the above problems. At the same time, the present invention has the advantages of simple raw material acquisition, low cost, and simultaneous extrusion lines with high solid content. The advantages of uniformity and good bonding of the body and glaze can realize the freedom of graphics on the body, and make up for the lack of ceramic direct writing 3D printing technology in glaze research.

A high-solid content glaze suitable for direct writing 3D printing, including raw materials composed of the following weight percentages: 71.5%-85.75% of raw materials for ceramic glaze, 2.25%-8.5% of additives, and 12%-20% of deionized water , made after mixing evenly;

The raw materials for ceramic glaze include potassium feldspar 23%-52%, quartz 15%-27%, kaolin 13%-20%, limestone 6%-24%, talc 4%-10%, zirconium silicate 1%- 4%, after mixing evenly, wet ball mill with deionized water at a ratio of 1:1, and dry the obtained powder.

The additives include 2%-6% of binder, 0.1%-0.5% of surfactant and 0.15%-2% of dispersant.

The high solid content glaze has a solid content of 73%-80% and a particle size of 4-11 μm, which is suitable for most ceramic bisque bodies.

The binder is one or more of polyvinyl alcohol, sodium carboxymethylcellulose, and gum arabic.

The surfactant is one or more of sodium lauryl sulfate, sodium dodecylbenzenesulfonate and stearic acid.

The dispersant is one or more of 3-mercaptopropionic acid, poly-4-styrenesulfonic acid, sodium polyacrylate, and sodium hexametaphosphate.

The present invention also includes a method for preparing a high-solid content glaze suitable for direct-writing 3D printing, using the above-mentioned high-solid content glaze suitable for direct-writing 3D printing, comprising the steps of:

S1. Mix the raw materials for ceramic glaze, additives, and deionized water evenly to obtain a glaze paste with a high solid content;

S2. Put the high-solid content paste obtained in step S1 into the barrel, and obtain a 3D printing high-solid content glaze paste after vacuuming and defoaming;

S3. Add the high-solid-content glaze paste described in step S2 to a 3D printer, print on the body based on the set model, write and extrude directly through the print head of the 3D printer, and superimpose the high-solid-content glaze layer by layer Material paste, get 3D printing graphics on the green body;

S4. Drying and sintering the 3D printed graphics product described in step S3.

The direct writing forming conditions in the step S3 are as follows: the air pressure is 0.3-0.6Mpa, the diameter of the printing needle is 0.86-3mm, the printing speed is 3-12mm/s, the printing distance is 0.9-3.2mm, and the thickness of the single layer is 0.1-3mm. 0.6mm.

The green body in the step S3 is a bisque fired ceramic body.

The firing conditions in the step S4 are:

The first stage: the temperature range is from room temperature to 300°C, and the glaze firing time is 60 to 90 minutes;

The second stage: the temperature range is 300-920°C, and the glaze firing time is 120-150 minutes;

The third stage: the temperature range is 920-1050°C, and the glaze firing time is 60-80 minutes;

The fourth stage: the temperature range is 1050-1280°C, and the glaze firing time is 180-210 minutes;

The fifth stage: the temperature range is 1280 ℃ ~ room temperature, natural cooling.

The invention provides a kind of high solid content glaze suitable for direct writing 3D printing and the beneficial effects of its preparation method are:

(1) The preparation of high solid content glaze paste in the present invention mainly is to regulate and control the high solid content and rheological properties of paste by adjusting the ratio of ceramic glaze powder and binding agent, surfactant, dispersant, The extruded lines are uniform and well combined with the surface of the ceramic biscuit body, which is not easy to crack and fall off.

(2) The raw materials selected in the present invention are all common raw materials, which are easy to obtain and low in price, and do not affect the high-temperature performance in the firing process of the blank glaze. The resulting blank glaze middle layer has good bonding performance and high yield.

(3) The present invention utilizes the direct writing 3D printing technology, and the size and thickness of the pattern can be controlled through the layer-by-layer stacking principle. The printing line width can be controlled at 0.8 mm or above, the thickness of a single layer can be controlled below 1 mm, and the printing speed can be adjusted at any time, etc. Advantages, its simple equipment structure and good slurry compatibility will be more able to be used in daily production, which can realize efficient, fast and personalized production, and at the same time, the pattern style can be changed at any time through 3D modeling, so that on the blank Achieve graphic freedom. The direct writing 3D printing high-solid content glaze of the present invention makes up for the deficiency that there is no related research in China.

Description of drawings

In order to more clearly illustrate the specific implementation of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the specific implementation or description of the prior art. Obviously, the accompanying drawings in the following description The drawings show some implementations of the present invention, and those skilled in the art can obtain other drawings based on these drawings without any creative work.

Fig. 1 is a schematic diagram of a blank in the process of 3D printing graphic products in Embodiment 1 of the present invention.

Fig. 2 is a 3D printed graphic product in Embodiment 1 of the present invention.

Detailed ways

The technical solution of the invention will be further described below in conjunction with the accompanying drawings and examples. The following examples are only used to illustrate the technical solution of the present invention more clearly, so they are only examples and should not be used to limit the scope of protection of the present invention.

Example 1

1. Preparation of printing materials

A high-solid-content glaze suitable for direct writing 3D printing. During the preparation process, the raw materials for the glaze are mixed and ball-milled in proportion, and then additives and water are added in proportion.

a. Ball milling: in terms of weight percentage, the glaze is composed of 52% potassium feldspar, 15% quartz, 20% kaolin, 6% limestone, 4% talc and 3% zirconium silicate. Mix the above raw materials for glaze according to the ratio of material: ball stone: water = 1:2:1, mix and ball mill for 30 minutes, sieve, dry, make powder, and record it as glaze A.

b. Preparation: In terms of weight percentage, the 3D printing raw materials are composed of 85.75% of glaze A, 1.5% of polyvinyl alcohol, 0.5% of sodium carboxymethyl cellulose, 0.1% of sodium dodecylbenzenesulfonate, 3- Mercaptopropionic acid 0.15%, deionized water 12%. The above-mentioned raw materials are uniformly mixed to prepare a glaze paste with a high solid content.

2. Print graphic products

Put the high-solid content glaze paste prepared in step 1 into the barrel, remove air bubbles in a vacuum device for 2 hours, and then assemble it on the printer. Set the printing parameters: air pressure 0.3-0.6Mpa, printing needle diameter 3mm, print The speed is 12mm/s, the printing pitch is 3.2mm, and the thickness of a single layer is 0.6mm. According to the set procedure, the plain blank of the graphic product is obtained by printing.

3. Firing

The biscuit product is fired according to the following curve:

The first stage: the temperature range is from room temperature to 300°C, and the glaze firing time is 60 to 90 minutes;

The second stage: the temperature range is 300-920°C, and the glaze firing time is 120-150 minutes;

The third stage: the temperature range is 920-1050°C, and the glaze firing time is 60-80 minutes;

The fourth stage: the temperature range is 1050-1280°C, and the glaze firing time is 180-210 minutes;

The fifth stage: the temperature range is 1280 ℃ ~ room temperature, natural cooling.

In each firing stage, the free water evaporation stage is before 300°C. At this time, the temperature rise should not be too fast, and a line should be left on the kiln door to facilitate the escape of water vapor. 300-920°C is the crystallization water evaporation stage, and the heating rate slows down from 920°C to 1050°C, in order to escape the carbon-containing and sulfur-containing gases and harmful impurities, and avoid the generation of pinholes and bubbles in the finished product. During the firing process at 1050°C to 1280°C, the green body is vitrified, the glaze layer is vitrified, and the shrinkage is relatively large. It is necessary to ensure that the product is heated evenly and the high temperature reaction is consistent, so the temperature rise must be slow to promote the kiln temperature balance. After firing, it is naturally cooled, and finally a 3D printed graphic product is obtained.

Example 2

1. Preparation of printing materials

A high-solid-content glaze suitable for direct writing 3D printing. During the preparation process, the raw materials for the glaze are mixed and ball-milled in proportion, and then additives and water are added in proportion.

a. Ball milling: in terms of weight percentage, the glaze is composed of 23% potassium feldspar, 26% quartz, 13% kaolin, 24% limestone, 10% talc and 4% zirconium silicate. Mix the above raw materials for glaze according to the ratio of material: ball stone: water = 1:2:1, mix and ball mill for 30 minutes, sieve, dry, make powder, and record it as glaze A.

b. Preparation: In terms of weight percentage, the 3D printing raw materials are composed of 71.5% of glaze A, 2% of gum arabic, 4% of sodium carboxymethyl cellulose, 0.5% of sodium dodecylbenzene sulfate, and 2% of sodium polyacrylate. %, deionized water 20%. The above-mentioned raw materials are uniformly mixed to prepare a glaze paste with a high solid content.

2. Print graphic products

Put the high-solid content glaze paste prepared in step 1 into the barrel, remove air bubbles in a vacuum device for 2 hours, and then assemble it on the printer. Set the printing parameters: air pressure 0.3-0.6Mpa, printing needle diameter 0.86mm, The printing speed is 3mm/s, the printing distance is 0.9mm, and the thickness of a single layer is 0.1mm. According to the set procedure, the plain blank of the graphic product is obtained by printing.

3. Firing

The biscuit product is fired according to the following curve:

The first stage: the temperature range is from room temperature to 300°C, and the glaze firing time is 60 to 90 minutes;

The second stage: the temperature range is 300-920°C, and the glaze firing time is 120-150 minutes;

The third stage: the temperature range is 920-1050°C, and the glaze firing time is 60-80 minutes;

The fourth stage: the temperature range is 1050-1280°C, and the glaze firing time is 180-210 minutes;

The fifth stage: the temperature range is 1280 ℃ ~ room temperature, natural cooling.

In each firing stage, the free water evaporation stage is before 300°C. At this time, the temperature rise should not be too fast, and a line should be left on the kiln door to facilitate the escape of water vapor. 300-920°C is the crystallization water evaporation stage, and the heating rate slows down from 920°C to 1050°C, in order to escape the carbon-containing and sulfur-containing gases and harmful impurities, and avoid the generation of pinholes and bubbles in the finished product. During the firing process at 1050°C to 1280°C, the green body is vitrified, the glaze layer is vitrified, and the shrinkage is relatively large. It is necessary to ensure that the product is heated evenly and the high temperature reaction is consistent, so the temperature rise must be slow to promote the kiln temperature balance. After firing, it is naturally cooled, and finally a 3D printed graphic product is obtained.

Example 3

1. Preparation of printing materials

A high-solid-content glaze suitable for direct writing 3D printing. During the preparation process, the raw materials for the glaze are mixed and ball-milled in proportion, and then additives and water are added in proportion.

a. Ball milling: in terms of weight percentage, the glaze is composed of 45% potassium feldspar, 20% quartz, 15% kaolin, 13% limestone, 6% talc and 1% zirconium silicate. Mix the above raw materials for glaze according to the ratio of material: ball stone: water = 1:2:1, mix and ball mill for 30 minutes, sieve, dry, make powder, and record it as glaze A.

b. Preparation: In terms of weight percentage, the 3D printing raw materials are composed of 76.26% of glaze A, 4% of sodium carboxymethyl cellulose, 0.4% of stearic acid, 0.04% of poly-4-styrenesulfonic acid, and hexametaphosphoric acid Sodium 1.3%, deionized water 18%. The above-mentioned raw materials are uniformly mixed to prepare a glaze paste with a high solid content.

2. Print graphic products

Put the high-solid content glaze paste prepared in step 1 into the barrel, remove air bubbles in a vacuum device for 2 hours, and then assemble it on the printer. Set the printing parameters: air pressure 0.3-0.6Mpa, printing needle diameter 1.26mm, The printing speed is 5mm/s, the printing pitch is 1.32mm, and the single layer thickness is 0.2mm. According to the set procedure, the plain blank of the graphic product is obtained by printing.

3. Firing

Put the biscuit product in an electric kiln, and the firing system (heating curve) is as follows:

The first stage: the temperature range is from room temperature to 300°C, and the glaze firing time is 60 to 90 minutes;

The second stage: the temperature range is 300-920°C, and the glaze firing time is 120-150 minutes;

The third stage: the temperature range is 920-1050°C, and the glaze firing time is 60-80 minutes;

The fourth stage: the temperature range is 1050-1280°C, and the glaze firing time is 180-210 minutes;

The fifth stage: the temperature range is 1280 ℃ ~ room temperature, natural cooling.

In each firing stage, the free water evaporation stage is before 300°C. At this time, the temperature rise should not be too fast, and a line should be left on the kiln door to facilitate the escape of water vapor. 300-920°C is the crystallization water evaporation stage, and the heating rate slows down from 920°C to 1050°C, in order to escape the carbon-containing and sulfur-containing gases and harmful impurities, and avoid the generation of pinholes and bubbles in the finished product. During the firing process at 1050°C to 1280°C, the green body is vitrified, the glaze layer is vitrified, and the shrinkage is relatively large. It is necessary to ensure that the product is heated evenly and the high temperature reaction is consistent, so the temperature rise must be slow to promote the kiln temperature balance. After firing, it is naturally cooled, and finally a 3D printed graphic product is obtained.

The specific embodiments described above have further described the technical problems, technical solutions and beneficial effects solved by the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. The high-solid-content glaze suitable for direct-writing 3D printing is characterized by comprising the following raw materials in percentage by weight: 71.5 to 85.75 percent of raw material for ceramic glaze, 2.25 to 8.5 percent of additive and 12 to 20 percent of deionized water are evenly mixed to prepare the ceramic glaze;

the raw materials for the ceramic glaze comprise 23-52% of potash feldspar, 15-27% of quartz, 13-20% of kaolin, 6-24% of limestone, 4-10% of talcum and 1-4% of zirconium silicate, and the raw materials are uniformly mixed, subjected to wet ball milling with deionized water according to the proportion of 1.

2. The high-solid-content glaze suitable for direct-write 3D printing according to claim 1, wherein the additive comprises 2% -6% of binder, 0.1% -0.5% of surfactant and 0.15% -2% of dispersant.

3. The high solid content glaze suitable for direct-write 3D printing according to claim 1 or 2, wherein the high solid content glaze has a solid content of 73-80% and a particle size of 4-11 μm.

4. The high-solid-content glaze suitable for direct-writing 3D printing according to claim 2, wherein the binder is one or more of polyvinyl alcohol, sodium carboxymethylcellulose and acacia gum.

5. The high-solid-content glaze suitable for direct-writing 3D printing according to claim 4, wherein the surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and stearic acid.

6. The high-solid-content glaze suitable for direct-writing 3D printing according to claim 5, wherein the dispersant is one or more of 3-mercaptopropionic acid, poly-4-styrenesulfonic acid, sodium polyacrylate and sodium hexametaphosphate.

7. A method of preparing a high solids glaze suitable for direct write 3D printing using a high solids glaze suitable for direct write 3D printing as claimed in any one of claims 1 to 7, comprising the steps of:

s1, uniformly mixing a raw material for ceramic glaze, an additive and deionized water to obtain a high-solid-content glaze paste;

s2, filling the high-solid-content paste obtained in the step S1 into a charging barrel, and performing vacuumizing and defoaming treatment to obtain a 3D printing high-solid-content glaze paste;

s3, adding the high-solid-content glaze paste body obtained in the step S2 into a 3D printer, printing on the blank body based on a set model, directly writing and extruding through a printing head of the 3D printer, overlapping the high-solid-content glaze paste body layer by layer, and obtaining a 3D printing graph on the blank body;

and S4, drying and sintering the 3D printing graphic product obtained in the step S3.

8. The method for preparing high solid content glaze suitable for direct-write 3D printing according to claim 7, wherein the direct-write molding conditions in step S3 are as follows: the air pressure is 0.3-0.6Mpa, the diameter of the printing needle is 0.86-3mm, the printing speed is 3-12mm/s, the printing interval is 0.9-3.2mm, and the single-layer thickness is 0.1-0.6mm.

9. The method for preparing a high solid content glaze suitable for direct-write 3D printing according to claim 8, wherein the blank in step S3 is a ceramic bisque-fired blank.

10. The method for preparing a high solid content glaze suitable for direct-write 3D printing according to claim 9, wherein the firing conditions in the step S4 are as follows:

the first stage is as follows: the temperature interval is normal temperature to 300 ℃, and the glaze firing time is 60 to 90 minutes;

and a second stage: the temperature interval is 300-920 ℃, and the glaze firing time is 120-150 minutes;

and a third stage: the temperature interval is 920-1050 ℃, and the glaze firing time is 60-80 minutes;

a fourth stage: the temperature interval is 1050-1280 ℃, and the glaze firing time is 180-210 minutes;

the fifth stage: the temperature range is 1280 ℃ to normal temperature, and the natural cooling is carried out.

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