A green and environmentally friendly ceramic clay and its manufacturing method

Abstract

This invention relates to a green and environmentally friendly ceramic clay and its manufacturing method, belonging to the field of ceramic technology. The ceramic clay comprises the following raw materials: limestone, cordierite powder, shale powder, slag, wollastonite, β-tricalcium phosphate, iron powder, starch, and phenolic resin. The addition of β-tricalcium phosphate and iron powder gives the clay a certain degree of biodegradability. Simultaneously, starch is added as a pore-forming agent, resulting in a large number of uniform, interconnected pores within the clay. This structure enhances the biodegradability of the clay. To ensure the stability of the pore structure, phenolic resin is also added to further strengthen the biodegradability of the finished clay. Furthermore, this invention selects limestone, cordierite powder, shale powder, slag, and wollastonite as the main raw materials and adjusts the proportions of each raw material in the formula to synergistically achieve outstanding flexural strength in the resulting clay.

Description

Technical Field

[0001] This invention belongs to the field of ceramic technology, specifically relating to a green and environmentally friendly ceramic clay and its manufacturing method. Background Technology

[0002] With increasing environmental awareness and the growing acceptance of sustainable development concepts, the ceramics industry is facing unprecedented challenges and opportunities. Traditional ceramic clay often suffers from poor biodegradability. In the natural environment, this type of clay is difficult to decompose on its own. The long-term accumulation of waste ceramic products made from large quantities of clay not only occupies valuable land resources but also poses potential harm to soil, water, and other ecological elements. Landfilling or incineration are also undesirable methods for disposing of ceramic products. Landfilling leads to long-term occupation of land resources and a decline in soil quality, while incineration may produce harmful gas emissions that pollute the atmosphere. Therefore, neither is a good way to degrade ceramic clay. Furthermore, the mechanical properties of ceramic clay, especially its flexural strength, play a decisive role in its practical application. During the use of ceramic products, whether for daily handling, placement, or withstanding external pressure or impact, sufficient flexural strength is required to maintain the integrity of the structure. Insufficient flexural strength makes ceramic products prone to breakage and damage, reducing their service life and safety, and further limiting their application in various fields.

[0003] Currently, most ceramic clays on the market can only meet one performance requirement: good degradation performance but low flexural strength. Therefore, providing a ceramic clay that combines excellent degradation performance and flexural strength is of great practical significance. Summary of the Invention

[0004] The purpose of this invention is to provide a green and environmentally friendly ceramic clay and its manufacturing method, which solves the problems of poor degradability and flexural strength of ceramic clay in the prior art.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A green and environmentally friendly ceramic clay, wherein the ceramic clay specifically comprises the following raw materials in parts by weight:

[0007]

[0008] As a preferred embodiment of the present invention, the limestone was purchased from Shandong Shouhua Chemical Co., Ltd.; the cordierite powder was purchased from Shijiazhuang Guangning Mineral Products Co., Ltd., item number bf011.

[0009] As a preferred embodiment of the present invention, the main chemical composition of the shale powder is as follows (wt.%): SiO2 79.73, Al2O3 9.92, Fe2O3 3.72, TiO2 0.57, CaO 0.67, MgO 2.03, K2O 0.04, Na2O 0.92, and others 2.40.

[0010] As a preferred embodiment of the present invention, the main chemical composition of the slag is as follows (wt.%): SiO2 74.90, Al2O3 11.75, Fe2O3 1.37, TiO2 0.55, CaO 2.13, MgO 0.96, K2O 5.17, Na2O 1.96, and others 1.21.

[0011] As a preferred embodiment of the present invention, the main chemical composition of the wollastonite ore is as follows (wt.%): SiO2 42.16, Al2O3 0.69, Fe2O3 0.67, TiO2 0.01, CaO 44.90, MgO 1.63, K2O 0.11, and others 9.83.

[0012] As a preferred embodiment of the present invention, the average particle size of the β-tricalcium phosphate is 360 nm; the iron content of the iron powder is 99.9%; the starch is soluble starch with an average particle size of 60 mesh, purchased from Hubei Xinrunde Chemical Co., Ltd.; the phenolic resin is thermosetting phenolic resin, model 2127, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0013] Furthermore, the ceramic blank also includes anhydrous ethanol.

[0014] A green and environmentally friendly method for manufacturing ceramic clay includes the following steps:

[0015] S1. Limestone, cordierite powder, shale powder, slag, wollastonite ore, and iron powder are ball-milled using a planetary ball mill, sieved, and dried under controlled temperature to obtain a dried mixture; anhydrous ethanol and phenolic resin are stirred evenly to obtain a mixed material.

[0016] S2. Mix the dry mixture, β-tricalcium phosphate and starch evenly, grind, sieve, add anhydrous ethanol, stir evenly and shake, then add the mixture and stir in a temperature-controlled water bath until the anhydrous ethanol evaporates, dry at a controlled temperature to obtain intermediate ceramic blank clay.

[0017] S3. Place the intermediate ceramic blank in the mold, flatten it, heat the mold, control the pressure, hot press and maintain the pressure, and then sinter it under nitrogen protection to obtain the finished ceramic blank.

[0018] As a preferred embodiment of the present invention, in the planetary ball mill described in step S1, the ratio of material:ball:water is 1:1.2-2:1, and the ball milling time is 30-60 min; the ratio of anhydrous ethanol to phenolic resin is 2 mL:1-1.5 g.

[0019] As a preferred embodiment of the present invention, the sieving in step S1 is sieving through a 50-mesh sieve; the temperature of the temperature-controlled drying is 95-100℃.

[0020] As a preferred embodiment of the present invention, the amount of anhydrous ethanol added in step S2 is 1.4-1.8 times the total mass of the dried mixture, β-tricalcium phosphate and starch.

[0021] As a preferred embodiment of the present invention, the sieving in step S2 is sieving through an 80-mesh sieve; the temperature of the temperature-controlled water bath stirring is 80-85℃; and the temperature of the temperature-controlled drying is 85-90℃.

[0022] As a preferred technical solution of the present invention, step S3 involves heating the mold to 145-150°C; the pressure for controlled hot pressing and holding the pressure is 16-18 MPa, and the time is 30-35 min.

[0023] The beneficial effects of this invention are:

[0024] (1) This invention incorporates β-tricalcium phosphate and iron powder. The good biodegradability, biocompatibility, and non-toxicity of β-tricalcium phosphate, along with the good processability, biodegradability, and biocompatibility of iron powder, work synergistically to make the clay body biodegradable to a certain extent. At the same time, starch is added as a pore-forming agent, resulting in a large number of uniform and interconnected pore structures inside the clay body. This structure in the system improves the biodegradability of the clay body. In addition, to ensure the stability of the pore structure, this invention also incorporates phenolic resin. During the continuous heating process, the glassy carbon network generated by the phenolic resin provides good support for the pore structure of the finished clay body, thereby enhancing the biodegradability of the finished clay body.

[0025] (2) This invention uses limestone, cordierite powder, shale powder, slag, and wollastonite as the main raw materials and adjusts the proportions of each raw material in the formula to obtain a ceramic clay with excellent degradation performance. At the same time, the ceramic clay also has outstanding flexural strength. Specifically, limestone is used to strengthen the skeleton, cordierite powder is used to improve the density and strength of the ceramic, and shale powder introduces more silica, which forms a multi-element eutectic compound with the other raw materials in the system at high temperature, which is conducive to the nucleation and growth of crystals in the liquid phase. Slag and wollastonite introduce alkali metal oxides to promote the liquid phase sintering process. Therefore, the five elements work synergistically to give the obtained clay outstanding flexural strength. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] The limestone used in this embodiment of the invention was purchased from Shandong Shouhua Chemical Co., Ltd.; the cordierite powder used was purchased from Shijiazhuang Guangning Mineral Products Co., Ltd., item number bf011; the starch used was soluble starch with an average particle size of 60 mesh, purchased from Hubei Xinrunde Chemical Co., Ltd.; the phenolic resin used was thermosetting phenolic resin, model 2127, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0028] The main chemical composition (wt.%) of the shale powder used is: SiO2 79.73, Al2O3 9.92, Fe2O3 3.72, TiO2 0.57, CaO 0.67, MgO 2.03, K2O 0.04, Na2O 0.92, and others 2.40. The main chemical composition (wt.%) of the slag used is: SiO2 74.90, Al2O3 11.75, Fe2O3 1.37, TiO2 0.55, CaO 2.13, MgO 0.96, K2O 5.17, Na2O 1.96, and others 1.21. The main chemical composition (wt.%) of the wollastonite used is: SiO2 42.16, Al2O3 0.69, Fe2O3 0.67, TiO2 0.01, CaO 44.90, and MgO 0.67. 1.63, K2O 0.11, others 9.83;

[0029] The average particle size of the β-tricalcium phosphate used was 360 nm; the iron content of the iron powder used was 99.9%.

[0030] The above will not be repeated hereafter.

[0031] Example 1

[0032] A green and environmentally friendly ceramic clay, wherein the ceramic clay specifically comprises the following raw materials in parts by weight:

[0033]

[0034] The ceramic blank also includes anhydrous ethanol.

[0035] The method for manufacturing the green and environmentally friendly ceramic clay body specifically includes the following steps:

[0036] S1. Limestone, cordierite powder, shale powder, slag, wollastonite ore and iron powder are ball-milled in a planetary ball mill for 30 minutes, passed through a 50-mesh sieve, and dried at 100℃ to obtain a dried mixture; anhydrous ethanol and phenolic resin are stirred evenly to obtain a mixture.

[0037] In the planetary ball mill, the ratio of material:balls:water is 1:1.2:1; the ratio of anhydrous ethanol to phenolic resin is 2 mL:1.3 g.

[0038] S2. Mix the dried mixture, β-tricalcium phosphate and starch evenly, grind, pass through an 80-mesh sieve, add anhydrous ethanol, stir evenly and shake, then add the mixture and stir in a water bath at 85°C until the anhydrous ethanol evaporates, then dry at 85°C to obtain intermediate ceramic blank clay.

[0039] The amount of anhydrous ethanol added is 1.4 times the total mass of the dried mixture, β-tricalcium phosphate, and starch;

[0040] S3. Place the intermediate ceramic blank in the mold, flatten it, heat the mold to 145°C, hot press it at 16 MPa and hold the pressure for 35 minutes, and then sinter it under nitrogen protection to obtain the finished ceramic blank.

[0041] Example 2

[0042] A green and environmentally friendly ceramic clay, wherein the ceramic clay specifically comprises the following raw materials in parts by weight:

[0043]

[0044] The ceramic blank also includes anhydrous ethanol.

[0045] The method for manufacturing the green and environmentally friendly ceramic clay body specifically includes the following steps:

[0046] S1. Limestone, cordierite powder, shale powder, slag, wollastonite ore and iron powder are ball-milled in a planetary ball mill for 45 minutes, passed through a 50-mesh sieve, and dried at 95℃ to obtain a dried mixture; anhydrous ethanol and phenolic resin are stirred evenly to obtain a mixture.

[0047] In the planetary ball mill, the ratio of material:ball:water is 1:2:1; the ratio of anhydrous ethanol to phenolic resin is 2mL:1g.

[0048] S2. Mix the dried mixture, β-tricalcium phosphate and starch evenly, grind, pass through an 80-mesh sieve, add anhydrous ethanol, stir evenly and shake, then add the mixture and stir in a water bath at 80℃ until the anhydrous ethanol evaporates, then dry at 90℃ to obtain intermediate ceramic blank clay.

[0049] The amount of anhydrous ethanol added is 1.6 times the total mass of the dried mixture, β-tricalcium phosphate, and starch;

[0050] S3. Place the intermediate ceramic blank in the mold, flatten it, heat the mold to 150°C, hot press it at 17 MPa and hold the pressure for 33 minutes, and then sinter it under nitrogen protection to obtain the finished ceramic blank.

[0051] Example 3

[0052] A green and environmentally friendly ceramic clay, wherein the ceramic clay specifically comprises the following raw materials in parts by weight:

[0053]

[0054] The ceramic blank also includes anhydrous ethanol.

[0055] The method for manufacturing the green and environmentally friendly ceramic clay body specifically includes the following steps:

[0056] S1. Limestone, cordierite powder, shale powder, slag, wollastonite ore and iron powder are ball-milled in a planetary ball mill for 60 minutes, passed through a 50-mesh sieve, and dried at a controlled temperature of 97.5℃ to obtain a dried mixture; anhydrous ethanol and phenolic resin are stirred evenly to obtain a mixture.

[0057] In the planetary ball mill, the ratio of material:balls:water is 1:1.6:1; the ratio of anhydrous ethanol to phenolic resin is 2 mL:1.5 g.

[0058] S2. Mix the dried mixture, β-tricalcium phosphate and starch evenly, grind, pass through an 80-mesh sieve, add anhydrous ethanol, stir evenly and shake, then add the mixture and stir in a water bath at 82.5℃ until the anhydrous ethanol evaporates, then dry at 87.5℃ to obtain intermediate ceramic blank clay.

[0059] The amount of anhydrous ethanol added is 1.8 times the total mass of the dried mixture, β-tricalcium phosphate, and starch;

[0060] S3. Place the intermediate ceramic blank in the mold, flatten it, heat the mold to 147.5℃, hot press it at 18Mpa and hold the pressure for 30 minutes, and then sinter it under nitrogen protection to obtain the finished ceramic blank.

[0061] Comparative Example 1

[0062] Compared with Example 3, the difference is that Comparative Example 1 does not add β-tricalcium phosphate, but uses an equal amount of iron powder instead, while the other operation steps and parameters are the same.

[0063] Comparative Example 2

[0064] Compared with Example 3, the difference is that iron powder was not added in Comparative Example 2, but was replaced with an equal weight of β-tricalcium phosphate. All other operating steps and parameters were the same.

[0065] Comparative Example 3

[0066] Compared with Example 3, the difference is that no starch was added in Comparative Example 3, but the other operation steps and parameters are the same.

[0067] Comparative Example 4

[0068] Compared with Example 3, the difference is that no phenolic resin was added in Comparative Example 4, while the other operation steps and parameters were the same.

[0069] Comparative Example 5

[0070] Compared with Example 3, the difference is that Comparative Example 5 does not add limestone, but instead uses cordierite powder, shale powder, slag and wollastonite ore in 1 / 4 weight of limestone respectively. The other operation steps and parameters are the same.

[0071] Comparative Example 6

[0072] Compared with Example 3, the difference is that Comparative Example 6 does not add cordierite powder, but instead uses limestone, shale powder, slag and wollastonite ore with 1 / 4 part by weight of cordierite powder respectively. The other operation steps and parameters are the same.

[0073] Comparative Example 7

[0074] Compared with Example 3, the difference is that Comparative Example 7 does not add shale powder, but instead uses limestone, cordierite powder, slag and wollastonite ore in 1 / 4 weight of shale powder respectively. The other operation steps and parameters are the same.

[0075] Comparative Example 8

[0076] Compared with Example 3, the difference is that Comparative Example 8 does not add slag, but uses limestone, cordierite powder, shale powder and wollastonite ore with 1 / 4 part by weight of slag respectively. The other operation steps and parameters are the same.

[0077] Comparative Example 9

[0078] Compared with Example 3, the difference is that Comparative Example 9 does not add wollastonite ore, but instead uses 1 / 4 part by weight of limestone, cordierite powder, shale powder and slag, respectively. The other operation steps and parameters are the same.

[0079] Test Example 1

[0080] Degradability test: The method for determining the weight loss rate is as follows: The ceramic clay prepared in Examples 1-3 and Comparative Examples 1-4 were weighed and immersed in 1 mol / L hydrochloric acid aqueous solution at room temperature for 144 h. After being taken out and dried, they were weighed again and the weight loss rate was calculated. The results are shown in Table 1.

[0081] Table 1

[0082] Weight loss rate (%) Example 1 12.5 Example 2 12.2 Example 3 12.6 Comparative Example 1 6.2 Comparative Example 2 7.0 Comparative Example 3 7.3 Comparative Example 4 8.4

[0083] As can be seen from Table 1, the finished clay product obtained by the present invention has excellent degradability.

[0084] Test Example 2

[0085] Flexural strength test: The flexural strength of the ceramic blanks prepared in Examples 1-3 and Comparative Examples 5-9 was tested according to GB / T 4741-1999, and the results are shown in Table 2.

[0086] Table 2

[0087] Flexural strength (MPa) Example 1 1.47 Example 2 1.43 Example 3 1.53 Comparative Example 5 1.18 Comparative Example 6 1.23 Comparative Example 7 1.20 Comparative Example 8 1.02 Comparative Example 9 1.07

[0088] As can be seen from Table 2, the finished clay body obtained by this invention has outstanding flexural strength. Specifically, this is because the present invention selects limestone, cordierite powder, shale powder, slag, and wollastonite as the main raw materials and adjusts the proportions of each raw material in the formula. Limestone strengthens the skeleton, cordierite powder improves the density and strength of the ceramic, shale powder facilitates crystal nucleation and growth in the liquid phase, and slag and wollastonite introduce alkali metal oxides to promote the liquid phase sintering process. Therefore, the five elements work synergistically to give the finished clay body outstanding flexural strength.

[0089] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0090] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A green and environmentally friendly ceramic clay, characterized in that, The ceramic clay specifically comprises the following raw materials in parts by weight:

2. The green and environmentally friendly ceramic clay according to claim 1, characterized in that, The average particle size of the β-tricalcium phosphate is 360 nm; the starch is soluble starch with an average particle size of 60 mesh; and the phenolic resin is a thermosetting phenolic resin.

3. The green and environmentally friendly ceramic clay according to claim 1, characterized in that, The ceramic blank also includes anhydrous ethanol.

4. A method for manufacturing green and environmentally friendly ceramic clay as described in claim 3, characterized in that, Specifically, the steps include the following: S1. Limestone, cordierite powder, shale powder, slag, wollastonite ore, and iron powder are ball-milled using a planetary ball mill, sieved, and dried under controlled temperature to obtain a dried mixture; anhydrous ethanol and phenolic resin are stirred evenly to obtain a mixed material. S2. Mix the dry mixture, β-tricalcium phosphate and starch evenly, grind, sieve, add anhydrous ethanol, stir evenly and shake, then add the mixture and stir in a temperature-controlled water bath until the anhydrous ethanol evaporates, dry at a controlled temperature to obtain intermediate ceramic blank clay. S3. Place the intermediate ceramic blank in the mold, flatten it, heat the mold, control the pressure, hot press and maintain the pressure, and then sinter it under nitrogen protection to obtain the finished ceramic blank.

5. The method for manufacturing green and environmentally friendly ceramic clay according to claim 4, characterized in that, In the planetary ball mill described in step S1, the ratio of material:ball:water is 1:1.2-2:1, and the ball milling time is 30-60 min; the ratio of anhydrous ethanol to phenolic resin is 2 mL: 1-1.5 g.

6. The method for manufacturing green and environmentally friendly ceramic clay according to claim 4, characterized in that, The sieving in step S1 is through a 50-mesh sieve; the temperature for temperature-controlled drying is 95-100℃.

7. The method for manufacturing green and environmentally friendly ceramic clay according to claim 4, characterized in that, The amount of anhydrous ethanol added in step S2 is 1.4-1.8 times the total mass of the dried mixture, β-tricalcium phosphate, and starch.

8. The method for manufacturing green and environmentally friendly ceramic clay according to claim 4, characterized in that, The sieving in step S2 is through an 80-mesh sieve; the temperature of the temperature-controlled water bath stirring is 80-85℃; and the temperature of the temperature-controlled drying is 85-90℃.

9. The method for manufacturing green and environmentally friendly ceramic clay according to claim 4, characterized in that, Step S3 involves heating the mold to 145-150°C.

10. The method for manufacturing green and environmentally friendly ceramic clay according to claim 4, characterized in that, The pressure for controlled hot pressing and holding in step S3 is 16-18 MPa, and the time is 30-35 min.

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