A cerium-containing modified rare earth water-retaining glaze for ceramics and a preparation method thereof

Abstract

The present invention provides a method for preparing a cerium-modified rare earth water-retaining glaze for ceramics, comprising the following steps: step 1 is to evenly mix cerium salt, polyvinyl alcohol and a dispersant, add ammonia water thereto, stir under heating conditions, and cool to room temperature after the reaction is complete to obtain a mixture; step 2 is to centrifuge the mixture to obtain an intermediate; step 3 is to dry, calcine and sand-mill the intermediate to obtain a modified additive; step 4 is to add the modified additive to the glaze, and evenly mix to obtain the cerium-modified rare earth water-retaining glaze. In the cerium-modified rare earth water-retaining glaze for ceramics described in the present invention, part of the sulfonyl groups of sodium dodecylbenzene sulfonate are converted to phenolic hydroxyl groups under alkaline conditions, fixing more cerium atoms and increasing the amount of dissolved oxygen in water. The carbon skeleton formed by high-temperature calcination of dodecyl long chains and polyvinyl alcohol is conducive to adsorbing impurity ions, stabilizing the carbon skeleton, and reducing the conductivity, thereby improving the water quality of drinking water.

Description

Technical Field

[0001] The invention belongs to the field of ceramics, and in particular relates to a cerium-containing modified rare earth water-retaining glaze for ceramics and a preparation method thereof. Background Art

[0002] The element cerium has been extensively explored in the fabrication of nanocrystals for fuel cell and catalytic applications. Their range of applications is extensible in these disciplines, and Ce has been successfully used as a host material for dopants or as a dopant for substances with unique functional purposes in optoelectronics, high energy physics, and electrochemistry. Cerium oxide has at least two stable chemical states, namely ceria (CeO2) and cerium trioxide (Ce2O3), which are often referred to as sesquioxides. Pure CeO2 has a fluorite-type structure with a special Fm3m group, especially in the temperature range from room temperature to the melting point. The phase transition of CeO22-Ce2O3 depends on the oxygen pressure and temperature in the system, and the reduction transition can be attributed to the formation and migration of oxygen vacancies and the quantum process of ionization / delocalization of cerium's 4f electrons. The close thermodynamic stability of CeO2 and Ce2O3 favors the facile and reversible transformation between the two compounds, resulting in a series of partially reduced CeO 2-x phases, which act as oxygen reservoirs by creating or eliminating oxygen vacancies.

[0003] Water is the most important compound for life on Earth, and drinking water is a major global challenge in the 21st century. Pure and unpolluted water is the basic condition for the survival of all living things. More than 71% of the Earth's surface is covered with water, but according to international standards, less than 68.1% of the water is drinkable due to different pollution. The 69 main sources of water pollution include industrial wastewater discharge, agricultural activities, urban wastewater, environment and global change. The presence of heavy metals, dyes and microorganisms, even in trace amounts, is very dangerous to human health, aquatic systems and the environment. At present, the glazes on the market are mainly used to beautify the surface of ceramics and enhance their gloss and touch, but they do not have the function of retaining water quality and cannot achieve the safety of drinking water. Summary of the invention

[0004] In view of this, the present invention aims to overcome the defects in the prior art and proposes a cerium-modified rare earth water-retaining glaze for ceramics and a preparation method thereof.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A method for preparing a cerium-modified rare earth water-retaining glaze for ceramics comprises the following steps:

[0007] Step 1 is to mix cerium salt, polyvinyl alcohol and dispersant uniformly, add ammonia water thereto, stir under heating conditions, and cool to room temperature after the reaction is complete to obtain a mixture;

[0008] Step 2 is centrifuging the mixture to obtain an intermediate;

[0009] Step 3 is to dry, calcine and sand grind the intermediate to obtain a modified additive;

[0010] Step 4 is to add the modified additive into the glaze, and mix them evenly to obtain the cerium-containing modified rare earth water-retaining glaze.

[0011] Furthermore, the dispersant in step 1 is sodium dodecylbenzene sulfonate; the cerium salt is cerium halide, and the cerium halide is at least one of CeF4•3H2O, CeCl3•6H2O, CeBr2•7H2O or CeI3•9H2O.

[0012] Furthermore, the solid-to-liquid ratio of the cerium salt, polyvinyl alcohol, dispersant and ammonia water in step 1 is 6-15g:1-3g:0.5-1g:5-12mL; and the mass concentration of the ammonia water is 2-28%.

[0013] Furthermore, the temperature of the heating step in step 1 is 70-100° C.; the time of the stirring step in step 1 is 4-8 hours.

[0014] Furthermore, the temperature of the centrifugation step in step 2 is 15-30°C, the rotation speed is 6000-12000 rpm, and the time is 0.5-2 hours.

[0015] Further, the temperature of the drying step in step 3 is 70-100°C, and the time is 1-4 hours; the temperature of the calcining step in step 3 is 600-800°C, the time is 1-4 hours, and the heating rate is 5-10°C / min; the concentration of the sand grinding step in step 3 is 20-35%, the temperature is 20-30°C, the time is 4-6 hours, and the rotation speed is 2500-3300rpm. The mass concentration of the sand grinding step in step 3 is 20-35%, the temperature is 20-30°C, the time is 4-6 hours, and the rotation speed is 2500-3300rpm.

[0016] Furthermore, the mass ratio of the modified additive to the glaze in step 4 is 1-10:100.

[0017] Furthermore, the glaze in step 4 comprises the following components in parts by weight: 10-35 parts of quartz, 5-25 parts of mica, 15-25 parts of dolomite, 15-25 parts of feldspar, 5-15 parts of talc, and 5-15 parts of barium carbonate.

[0018] A cerium-containing modified rare earth water-retaining glaze for ceramics prepared by the preparation method.

[0019] The invention discloses the use of the cerium-containing modified rare earth water-retaining glaze for ceramics and the application of the cerium-containing modified rare earth water-retaining glaze in the preparation of ceramic products.

[0020] Sodium dodecylbenzene sulfonate reacts under alkaline conditions to generate sodium dodecylphenol. Sodium dodecylphenol combines with cerium ions to have stronger electrostatic adsorption force. After high-temperature calcination, the carbon skeleton of polyvinyl alcohol combined with cerium ions is disconnected by the long chain of dodecyl, and some cerium ions are fixed on the dodecyl, which increases the specific surface area and active sites of the carbon skeleton and improves the water retention effect.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] In the cerium-modified rare earth water-retaining glaze for ceramics described in the present invention, part of the sulfonyl groups of sodium dodecylbenzene sulfonate are converted into phenolic hydroxyl groups under alkaline conditions, thereby fixing more cerium atoms and increasing the amount of dissolved oxygen in water. In addition, the carbon skeleton formed by high-temperature calcination of dodecyl long chains and polyvinyl alcohol is conducive to adsorbing impurity ions, stabilizing the carbon skeleton, and reducing electrical conductivity, thereby improving the water quality of drinking water. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A bar graph of dissolved oxygen according to an embodiment of the present invention;

[0024] Figure 2 It is a bar graph of the conductivity described in the embodiment of the present invention. DETAILED DESCRIPTION

[0025] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0026] Sodium dodecylbenzene sulfonate, hereinafter referred to as SDBS.

[0027] Polyvinyl alcohol, sodium dodecylbenzene sulfonate and ammonia water (NH3•H2O), potassium iodide, manganese sulfate tetrahydrate, sodium thiosulfate pentahydrate, sodium carbonate, and concentrated sulfuric acid were purchased from Beijing Solebow Technology Co., Ltd. Cerium nitrate hexahydrate, cerium chloride hexahydrate, cerium sulfate tetrahydrate, and cerium oxalate were purchased from Shanghai MacLean Biochemical Technology Co., Ltd. All chemicals were used without further treatment, and distilled water (ρ = 18.2 MΩ•cm, 25°C) was from a Millipore milli-Q water purification system.

[0028] The present invention will be described in detail below with reference to the embodiments.

[0029] Example 1

[0030] A method for preparing a cerium-modified rare earth water-retaining glaze for ceramics comprises the following steps:

[0031] (1) 10 g of cerium chloride hexahydrate, 2 g of polyvinyl alcohol and 1 g of sodium dodecylbenzene sulfonate were mixed evenly, 10 mL of ammonia water (20%) was added thereto, and the mixture was stirred at 80° C. for 6 hours. After the reaction was complete, the mixture was cooled to room temperature to obtain a mixture;

[0032] (2) centrifuging the mixture at 10,000 rpm for 0.5 hours to obtain an intermediate;

[0033] (3) drying the intermediate at 80°C for 4 hours, and then calcining at 700°C for 3 hours at a calcination heating rate of 5°C / min. After the muffle furnace is cooled to room temperature, the calcined powder is added to water with a concentration of 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a modified additive;

[0034] (4) Add 20 parts of quartz, 20 parts of mica, 20 parts of dolomite, 20 parts of feldspar, 10 parts of talc, 5 parts of barium carbonate, and 5 parts of modifying additives into 100 parts of water, stir, and evenly apply them on the ceramic blank. Then add the glazed ceramic cup into a calcining furnace and calcine at 1200°C for 11 hours. The calcination heating rate is controlled at 10°C / min. After cooling to room temperature, a water-retaining ceramic cup (CLL) modified with cerium-containing rare earth glaze is obtained.

[0035] Comparative Example 1

[0036] A method for preparing a cerium-modified rare earth water-retaining glaze for ceramics comprises the following steps:

[0037] (1) 10 g of cerium chloride hexahydrate, 2 g of polyvinyl alcohol and 1 g of hexadecyltrimethylammonium bromide were mixed evenly, 10 mL of ammonia water (20%) was added thereto, and the mixture was stirred at 80° C. for 6 hours. After the reaction was complete, the mixture was cooled to room temperature to obtain a mixture;

[0038] (2) centrifuging the mixture at 10,000 rpm for 0.5 hours to obtain an intermediate;

[0039] (3) drying the intermediate at 80°C for 4 hours, and then calcining at 700°C for 3 hours at a calcination heating rate of 5°C / min. After the muffle furnace is cooled to room temperature, the calcined powder is added to water with a concentration of 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a modified additive;

[0040] (4) Add 20 parts of quartz, 20 parts of mica, 20 parts of dolomite, 20 parts of feldspar, 10 parts of talc, 5 parts of barium carbonate, and 5 parts of a modifying additive into 100 parts of water, stir, and evenly apply on the ceramic blank. Then add the glazed ceramic cup into a calcining furnace and calcine at 1200°C for 11 hours. The calcination heating rate is controlled at 10°C / min. After cooling to room temperature, a water-retaining ceramic cup modified with a cerium-containing rare earth glaze is obtained.

[0041] Comparative Example 2

[0042] A method for preparing a cerium-modified rare earth water-retaining glaze for ceramics comprises the following steps:

[0043] (1) 10 g of cerium chloride hexahydrate, 2 g of polyvinyl alcohol and 1 g of sodium dodecylbenzene sulfonate were mixed evenly, and the mixture was stirred at 80° C. for 6 hours. After the reaction was complete, the mixture was cooled to room temperature to obtain a mixture;

[0044] (2) centrifuging the mixture at 10,000 rpm for 0.5 hours to obtain an intermediate;

[0045] (3) drying the intermediate at 80°C for 4 hours, and then calcining at 700°C for 3 hours at a calcination heating rate of 5°C / min. After the muffle furnace is cooled to room temperature, the calcined powder is added to water with a concentration of 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a modified additive;

[0046] (4) Add 20 parts of quartz, 20 parts of mica, 20 parts of dolomite, 20 parts of feldspar, 10 parts of talc, 5 parts of barium carbonate, and 5 parts of a modifying additive into 100 parts of water, stir, and evenly apply on the ceramic blank. Then add the glazed ceramic cup into a calcining furnace and calcine at 1200°C for 11 hours. The calcination heating rate is controlled at 10°C / min. After cooling to room temperature, a water-retaining ceramic cup modified with a cerium-containing rare earth glaze is obtained.

[0047] Comparative Example 3

[0048] A method for preparing a cerium-modified rare earth water-retaining glaze for ceramics comprises the following steps:

[0049] (1) 10 g Ce(NO3)3•6H2O, 2 g polyvinyl alcohol and 1 g sodium dodecylbenzene sulfonate were mixed evenly, 10 mL ammonia water (20%) was added thereto, and the mixture was stirred at 80°C for 6 hours. After the reaction was complete, the mixture was cooled to room temperature to obtain a mixture;

[0050] (2) centrifuging the mixture at 10,000 rpm for 0.5 hours to obtain an intermediate;

[0051] (3) drying the intermediate at 80°C for 4 hours, and then calcining at 700°C for 3 hours at a calcination heating rate of 5°C / min. After the muffle furnace is cooled to room temperature, the calcined powder is added to water with a concentration of 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a modified additive;

[0052] (4) Add 20 parts of quartz, 20 parts of mica, 20 parts of dolomite, 20 parts of feldspar, 10 parts of talc, 5 parts of barium carbonate, and 5 parts of a modifying additive into 100 parts of water, stir, and evenly apply on the ceramic blank. Then add the glazed ceramic cup into a calcining furnace and calcine at 1200°C for 11 hours. The calcination heating rate is controlled at 10°C / min. After cooling to room temperature, a water-retaining ceramic cup modified with a cerium-containing rare earth glaze is obtained.

[0053] The ceramic cups obtained in Example 1 and Comparative Examples 1-3 were tested for dissolved oxygen content in water. The blank control was a ceramic cup using glaze without adding a modifying additive. The test method was iodine titration. The test method was as follows:

[0054] Adjust the drinking water switch to slow flow, and use the ceramic cup to be tested to connect it to about half to one third of the overflow container. Be careful not to create bubbles in the water, and ensure that the ceramic cup is left to stand still after adding drinking water to prevent oxygen from entering the ceramic cup. Use a pipette to draw 1mL of MnSO4 solution (36g of manganese sulfate tetrahydrate is diluted to 100mL with water), insert it into the bottom of the ceramic cup and add it to the drinking water. In the same way, add 2mL of alkaline potassium iodide solution (500g of sodium hydroxide is dissolved in 300mL of water, and another 150g of potassium iodide is dissolved in 200mL of water. The two solutions are mixed and diluted to 1L). When the precipitate sinks to the bottom, use a pipette to insert 2mL of concentrated sulfuric acid (98%) into the bottom layer of the solution. When the precipitate disappears completely, use a pipette to draw 100mL of the above liquid, add it to a 250mL conical flask, and titrate it with sodium thiosulfate solution (6.2g of sodium thiosulfate pentahydrate is added to 1L of boiling water, and then 0.2g of sodium carbonate is added). Titrate until the solution turns light yellow, add 1mL of 1% starch solution, and continue to titrate the sodium thiosulfate solution until the blue color just disappears and start calculating the dosage. Calculate by the amount of sodium thiosulfate used.

[0055] like Figure 1 As shown, compared with hexadecyltrimethylammonium bromide, no ammonia water, other cerium salts and blank ceramic cups, the CCL ceramic cup showed the highest dissolved oxygen content, proving that the enamel contained in the CCL ceramic cup has a strong oxygen evolution effect. At the same time, sodium dodecylbenzene sulfonate promotes the increase of Ce active sites under alkaline conditions, and trivalent cerium and tetravalent cerium in the Ce-containing ceramic glaze are converted into each other, which increases the dissolved oxygen content of the ceramic cup.

[0056] The ceramic cups obtained in Example 1 and Comparative Examples 1-3 were tested for water conductivity. The blank control was a ceramic cup using glaze without adding a modifying additive. The test method was tested using a Mik-TDS210-B conductivity detector:

[0057] Fill the ceramic cup to be tested with pure water to two-thirds of the cup, and then let it stand for 2 hours. Then put the probe into the water in the ceramic cup, keep it for 30 seconds, read the value and record it.

[0058] like Figure 2 As shown, CCL has the lowest conductivity, which also proves that sodium dodecylbenzene sulfonate can better fix Ce atoms and polyvinyl alcohol, reduce the ion concentration in water, and also adsorb other impurity ions to improve the quality of drinking water.

[0059] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a cerium-modified rare earth water-retaining glaze for ceramics, characterized in that: The steps include: Step 1 is to mix cerium salt, polyvinyl alcohol and dispersant uniformly, add ammonia water thereto, stir under heating conditions, and cool to room temperature after the reaction is complete to obtain a mixture; Step 2 is centrifuging the mixture to obtain an intermediate; Step 3 is to dry, calcine and sand grind the intermediate to obtain a modified additive; Step 4 is to add the modified additive to the glaze, and mix them evenly to obtain the cerium-containing modified rare earth water-retaining glaze; The dispersant in step 1 is sodium dodecylbenzene sulfonate; the solid-liquid ratio of cerium salt, polyvinyl alcohol, dispersant and ammonia water in step 1 is 6-15g: 1-3g: 0.5-1g: 5-12mL; the temperature of the heating step in step 1 is 70-100°C; The mass concentration of the ammonia water is 2-28%.

2. The method for preparing the cerium-modified rare earth water-retaining glaze for ceramics according to claim 1, characterized in that: The cerium salt is a cerium halide, and the cerium halide is at least one of CeF4•3H2O, CeCl3•6H2O, CeBr3•7H2O or CeI3•9H2O.

3. The method for preparing the cerium-modified rare earth water-retaining glaze for ceramics according to claim 1, characterized in that: The stirring step in step 1 is performed for 4-8 hours.

4. The method for preparing the cerium-modified rare earth water-retaining glaze for ceramics according to claim 1, characterized in that: The temperature of the centrifugation step in step 2 is 15-30°C, the rotation speed is 6000-12000rpm, and the time is 0.5-2 hours.

5. The method for preparing the cerium-modified rare earth water-retaining glaze for ceramics according to claim 1, characterized in that: The temperature of the drying step in step 3 is 70-100°C, the time is 1-4 hours; the temperature of the calcining step in step 3 is 600-800°C, the time is 1-4 hours, and the heating rate is 5-10°C / min; the mass concentration of the sand grinding step in step 3 is 20-35%, the temperature is 20-30°C, the time is 4-6 hours, and the rotation speed is 2500-3300rpm.

6. The method for preparing the cerium-modified rare earth water-retaining glaze for ceramics according to claim 1, characterized in that: The mass ratio of the modified additive to the glaze in step 4 is 1-10:

100.

7. The method for preparing the cerium-modified rare earth water-retaining glaze for ceramics according to claim 1, characterized in that: The glaze in step 4 comprises the following components in parts by weight: 10-35 parts of quartz, 5-25 parts of mica, 15-25 parts of dolomite, 15-25 parts of feldspar, 5-15 parts of talc, and 5-15 parts of barium carbonate.

8. A cerium-containing modified rare earth water-retaining glaze for ceramics prepared by the preparation method according to any one of claims 1 to 7.

9. The use of the cerium-modified rare earth water-retaining glaze for ceramics according to claim 8, characterized in that: The application of the cerium-containing modified rare earth water-retaining glaze in the preparation of ceramic products.

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