CN108892473B - Antibacterial domestic ceramic - Google Patents
Antibacterial domestic ceramic Download PDFInfo
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- CN108892473B CN108892473B CN201811210098.8A CN201811210098A CN108892473B CN 108892473 B CN108892473 B CN 108892473B CN 201811210098 A CN201811210098 A CN 201811210098A CN 108892473 B CN108892473 B CN 108892473B
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- C04B2235/3427—Silicates other than clay, e.g. water glass
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Abstract
The invention discloses an antibacterial domestic ceramic, which relates to the technical field of porcelain, and comprises a zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent with the mass of 6-8 percent; the antibacterial daily ceramic prepared by the invention has excellent thermal shock resistance and impact strength, and meanwhile, the antibacterial effect is obvious, and the sterilization duration is long.
Description
Technical Field
The invention belongs to the technical field of porcelain, and particularly relates to an antibacterial daily ceramic.
Background
The daily-use ceramic refers to domestic porcelain used in daily life of people, and comprises tableware, tea sets, coffee sets, wine sets, rice sets and the like. The daily ceramic is widely popular among people due to the following advantages: 1) easy washing and keeping clean; 2) the heat stability is better, the heat transfer is slow; is used for containing boiling water or scalding food and is not too hot when being held. 3) The chemical property is stable and the durability is good; 4) the porcelain has few pores and low water absorption rate; the daily porcelain is used for storing food, and after the sealing is tight, the volatilization and the penetration of water in the food and the invasion of external bacteria can be prevented; 5) the colored drawing decoration is rich and colorful, especially has no lead poisoning hazards such as high-temperature glaze color, blue and white decoration and the like, can be used in a large scale, and is popular with people.
Along with the improvement of living standard of people, the functional performance of daily ceramics is required to be higher and higher, and the ceramic product with the antibacterial function can effectively avoid the invasion of various infectious diseases to human beings, particularly the sanitation prevention in public places, and is popular among people. The antibacterial ceramic product is produced through adding inorganic antiseptic to make the surface of ceramic possess antibacterial effect. The zirconium phosphate silver-loaded antibacterial agent is a commonly used inorganic antibacterial agent, but the existing zirconium phosphate silver-loaded antibacterial agent has a certain antibacterial effect, but after the zirconium phosphate silver-loaded antibacterial agent is applied to ceramics, the zirconium phosphate silver-loaded antibacterial agent does not promote the mechanical property of the ceramics, and meanwhile, when the addition amount of the zirconium phosphate silver-loaded antibacterial agent is increased for improving the antibacterial effect, the thermal shock resistance of the ceramics is reduced.
Disclosure of Invention
The invention aims to provide an antibacterial daily ceramic aiming at the existing problems.
The invention is realized by the following technical scheme:
an antibacterial daily ceramic contains 6-8% of zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent by mass.
Further, the preparation method of the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent comprises the following steps:
(1) preparing sodium alginate into 7.2% sodium alginate aqueous solution, adjusting pH of the sodium alginate aqueous solution to 8.5, then adding the n-hydroxysuccinimide into the sodium alginate aqueous solution according to the mass ratio of 1:65, stirring at 58 deg.C, adding attapulgite 40-42 wt% and stearic acid 0.1-0.15 wt% into sodium alginate water solution, stirring at 1800r/min for 1 hr, adding mercaptosuccinic acid 3.2 wt% of sodium alginate water solution, regulating temperature to 82 deg.C, ultrasonic treating for 10-12min, then stirring for 2.5 hours at the rotating speed of 350r/min, carrying out rotary evaporation drying, continuing heating to 250 ℃, preserving heat for 30min, then naturally cooling to room temperature, soaking for 10min by using deionized water, then filtering, and drying to constant weight to obtain sodium alginate modified attapulgite;
(2) compounding zirconium phosphate/sodium alginate modified attapulgite: uniformly dispersing modified attapulgite in deionized water to prepare a modified attapulgite dispersion liquid with the mass fraction of 10%, sequentially adding zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate into the modified attapulgite dispersion liquid, then adding into a reaction kettle, heating to 90 ℃, stirring at the rotating speed of 2000r/min for reaction for 3 hours, then filtering, cleaning with clear water, and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material;
(3) preparing the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent: preparing the zirconium phosphate/sodium alginate modified attapulgite composite material into an aqueous dispersion with the mass fraction of 10%, adding a silver nitrate solution into the aqueous dispersion to ensure that the mass content of silver ions in the zirconium phosphate/sodium alginate modified attapulgite composite material is 2.2%, stirring at the rotating speed of 500r/min for 30min, carrying out suction filtration, cleaning and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material.
Further, the particle size of the sodium alginate modified attapulgite is 1250 meshes.
Further, the ultrasonic power is 750W, and the frequency is 45 kHz.
Further, the mass ratio of the zirconium phosphate to the sodium alginate modified attapulgite in the zirconium phosphate/sodium alginate modified attapulgite composite material is 1: 2.
Further, the concentration of the silver nitrate solution is 0.5 mol/L.
Further, the antibacterial domestic ceramic is prepared from the following components in parts by weight: clay 35, mullite 11, kaolin 18, zircon 13 and albite 24.
Has the advantages that: the antibacterial daily-use ceramic prepared by the invention has excellent thermal shock resistance and impact strength, and meanwhile, the antibacterial effect is obvious, and the sterilization duration is long, the zirconium phosphate/sodium alginate modified attapulgite composite material is used as a carrier of silver ions, a large amount of experimental researches are carried out, the structural performance of attapulgite is changed by modifying the attapulgite, more active groups are endowed on the surfaces of modified attapulgite particles, then zirconium phosphate is synthesized in modified attapulgite dispersion liquid, the zirconium phosphate particles can be synthesized on the modified attapulgite particles in an attaching manner, the two are tightly combined, meanwhile, the zirconium phosphate can also have a certain coating effect on the modified attapulgite, a more stable new structural carrier is formed, and the prepared zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent can be added into the ceramic preparation to realize the tight combination of the two The organizational structure of the blank is changed, the thermal shock resistance of the blank is obviously improved, the water absorption rate is reduced, and meanwhile, the antibacterial property and the antibacterial persistence can be effectively improved.
Detailed Description
Example 1
An antibacterial daily ceramic contains 6% of zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent by mass.
Further, the preparation method of the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent comprises the following steps:
(1) preparing sodium alginate into 7.2% sodium alginate aqueous solution, adjusting pH of the sodium alginate aqueous solution to 8.5, then adding the n-hydroxysuccinimide into the sodium alginate aqueous solution according to the mass ratio of 1:65, stirring at 58 deg.C, adding attapulgite 40% and stearic acid 0.1% into sodium alginate water solution, stirring at 1800r/min for 1 hr, adding mercaptosuccinic acid 3.2 wt% of sodium alginate water solution, regulating temperature to 82 deg.C, ultrasonic treating for 10min, then stirring for 2.5 hours at the rotating speed of 350r/min, carrying out rotary evaporation drying, continuing heating to 250 ℃, preserving heat for 30min, then naturally cooling to room temperature, soaking for 10min by using deionized water, then filtering, and drying to constant weight to obtain sodium alginate modified attapulgite;
(2) compounding zirconium phosphate/sodium alginate modified attapulgite: uniformly dispersing modified attapulgite in deionized water to prepare a modified attapulgite dispersion liquid with the mass fraction of 10%, sequentially adding zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate into the modified attapulgite dispersion liquid, then adding into a reaction kettle, heating to 90 ℃, stirring at the rotating speed of 2000r/min for reaction for 3 hours, then filtering, cleaning with clear water, and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material;
(3) preparing the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent: preparing the zirconium phosphate/sodium alginate modified attapulgite composite material into an aqueous dispersion with the mass fraction of 10%, adding a silver nitrate solution into the aqueous dispersion to ensure that the mass content of silver ions in the zirconium phosphate/sodium alginate modified attapulgite composite material is 2.2%, stirring at the rotating speed of 500r/min for 30min, carrying out suction filtration, cleaning and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material.
Further, the particle size of the sodium alginate modified attapulgite is 1250 meshes.
Further, the ultrasonic power is 750W, and the frequency is 45 kHz.
Further, the mass ratio of the zirconium phosphate to the sodium alginate modified attapulgite in the zirconium phosphate/sodium alginate modified attapulgite composite material is 1: 2.
Further, the concentration of the silver nitrate solution is 0.5 mol/L.
Further, the antibacterial domestic ceramic is prepared from the following components in parts by weight: clay 35, mullite 11, kaolin 18, zircon 13 and albite 24.
Example 2
An antibacterial daily ceramic contains 8% of zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent by mass.
Further, the preparation method of the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent comprises the following steps:
(1) preparing sodium alginate into 7.2% sodium alginate aqueous solution, adjusting pH of the sodium alginate aqueous solution to 8.5, then adding the n-hydroxysuccinimide into the sodium alginate aqueous solution according to the mass ratio of 1:65, stirring at 58 deg.C, adding 42% attapulgite and 0.15% stearic acid into sodium alginate water solution, stirring at 1800r/min for 1 hr, adding mercaptosuccinic acid 3.2 wt% of sodium alginate water solution, regulating temperature to 82 deg.C, ultrasonic treating for 12min, then stirring for 2.5 hours at the rotating speed of 350r/min, carrying out rotary evaporation drying, continuing heating to 250 ℃, preserving heat for 30min, then naturally cooling to room temperature, soaking for 10min by using deionized water, then filtering, and drying to constant weight to obtain sodium alginate modified attapulgite;
(2) compounding zirconium phosphate/sodium alginate modified attapulgite: uniformly dispersing modified attapulgite in deionized water to prepare a modified attapulgite dispersion liquid with the mass fraction of 10%, sequentially adding zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate into the modified attapulgite dispersion liquid, then adding into a reaction kettle, heating to 90 ℃, stirring at the rotating speed of 2000r/min for reaction for 3 hours, then filtering, cleaning with clear water, and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material;
(3) preparing the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent: preparing the zirconium phosphate/sodium alginate modified attapulgite composite material into an aqueous dispersion with the mass fraction of 10%, adding a silver nitrate solution into the aqueous dispersion to ensure that the mass content of silver ions in the zirconium phosphate/sodium alginate modified attapulgite composite material is 2.2%, stirring at the rotating speed of 500r/min for 30min, carrying out suction filtration, cleaning and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material.
Further, the particle size of the sodium alginate modified attapulgite is 1250 meshes.
Further, the ultrasonic power is 750W, and the frequency is 45 kHz.
Further, the mass ratio of the zirconium phosphate to the sodium alginate modified attapulgite in the zirconium phosphate/sodium alginate modified attapulgite composite material is 1: 2.
Further, the concentration of the silver nitrate solution is 0.5 mol/L.
Further, the antibacterial domestic ceramic is prepared from the following components in parts by weight: clay 35, mullite 11, kaolin 18, zircon 13 and albite 24.
Example 3
An antibacterial daily ceramic contains 7% of zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent by mass.
Further, the preparation method of the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent comprises the following steps:
(1) preparing sodium alginate into 7.2% sodium alginate aqueous solution, adjusting pH of the sodium alginate aqueous solution to 8.5, then adding the n-hydroxysuccinimide into the sodium alginate aqueous solution according to the mass ratio of 1:65, stirring at 58 deg.C, adding attapulgite 41 wt% and stearic acid 0.12 wt% into sodium alginate water solution, stirring at 1800r/min for 1 hr, adding mercaptosuccinic acid 3.2 wt% of sodium alginate water solution, regulating temperature to 82 deg.C, ultrasonic treating for 11min, then stirring for 2.5 hours at the rotating speed of 350r/min, carrying out rotary evaporation drying, continuing heating to 250 ℃, preserving heat for 30min, then naturally cooling to room temperature, soaking for 10min by using deionized water, then filtering, and drying to constant weight to obtain sodium alginate modified attapulgite;
(2) compounding zirconium phosphate/sodium alginate modified attapulgite: uniformly dispersing modified attapulgite in deionized water to prepare a modified attapulgite dispersion liquid with the mass fraction of 10%, sequentially adding zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate into the modified attapulgite dispersion liquid, then adding into a reaction kettle, heating to 90 ℃, stirring at the rotating speed of 2000r/min for reaction for 3 hours, then filtering, cleaning with clear water, and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material;
(3) preparing the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent: preparing the zirconium phosphate/sodium alginate modified attapulgite composite material into an aqueous dispersion with the mass fraction of 10%, adding a silver nitrate solution into the aqueous dispersion to ensure that the mass content of silver ions in the zirconium phosphate/sodium alginate modified attapulgite composite material is 2.2%, stirring at the rotating speed of 500r/min for 30min, carrying out suction filtration, cleaning and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material.
Further, the particle size of the sodium alginate modified attapulgite is 1250 meshes.
Further, the ultrasonic power is 750W, and the frequency is 45 kHz.
Further, the mass ratio of the zirconium phosphate to the sodium alginate modified attapulgite in the zirconium phosphate/sodium alginate modified attapulgite composite material is 1: 2.
Further, the concentration of the silver nitrate solution is 0.5 mol/L.
Further, the antibacterial domestic ceramic is prepared from the following components in parts by weight: clay 35, mullite 11, kaolin 18, zircon 13 and albite 24.
Comparative example 1: the difference from the example 1 is only that the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent is replaced by the zirconium phosphate silver-loaded antibacterial agent.
Comparative example 2: the difference from example 1 is only that the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent is replaced by a physical mixture of the zirconium phosphate silver-loaded antibacterial agent and the attapulgite.
The ceramic products with the same specification are processed and prepared by the embodiment and the comparative example by the same process, and the thermal shock resistance, the impact strength, the antibacterial property and the like of the ceramic products of the embodiment and the comparative example are tested, and the results are shown in table 1;
the thermal shock resistance is a characteristic index showing the capability of the ceramic product to resist the rapid change of the external temperature without cracks or breakage, and is an important service performance index. The thermal shock resistance of the domestic ceramic product is tested according to GBT3298-2008, the standard is that whether the domestic ceramic product has defects such as cracks and damages or not is observed after one-time cold and hot circulation, and the domestic ceramic product is rechecked after standing for 24 hours. According to the standard test method, a sample is heated to 250 ℃ in a heating furnace, and then put into a water tank at 20 +/-2 ℃ to observe whether the sample has defects such as cracks, damages and the like; performing the cooling and heating cycle for 3 times to obtain a result;
the sterilization efficiency of the ceramic product in the sunlight for 1 hour is detected, and the sterilization efficiency of the ceramic product in the sunlight for 1 hour after 8 months of continuous use is as follows:
TABLE 1
As can be seen from Table 1, the antibacterial daily ceramic prepared by the invention has excellent thermal shock resistance and impact strength, and meanwhile, the antibacterial effect is remarkable, and the sterilization duration is long;
water absorption test:
TABLE 2
As can be seen from Table 2, the domestic ceramics prepared by the invention has lower water absorption.
Claims (6)
1. An antibacterial domestic ceramic is characterized in that the antibacterial domestic ceramic contains a zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent with the mass of 6-8%; the preparation method of the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent comprises the following steps:
(1) preparing sodium alginate into 7.2% sodium alginate aqueous solution, adjusting pH of the sodium alginate aqueous solution to 8.5, then adding the n-hydroxysuccinimide into the sodium alginate aqueous solution according to the mass ratio of 1:65, stirring at 58 deg.C, adding attapulgite 40-42 wt% and stearic acid 0.1-0.15 wt% into sodium alginate water solution, stirring at 1800r/min for 1 hr, adding mercaptosuccinic acid 3.2 wt% of sodium alginate water solution, regulating temperature to 82 deg.C, ultrasonic treating for 10-12min, then stirring for 2.5 hours at the rotating speed of 350r/min, carrying out rotary evaporation drying, continuing heating to 250 ℃, preserving heat for 30min, then naturally cooling to room temperature, soaking for 10min by using deionized water, then filtering, and drying to constant weight to obtain sodium alginate modified attapulgite;
(2) compounding zirconium phosphate/sodium alginate modified attapulgite: uniformly dispersing modified attapulgite in deionized water to prepare a modified attapulgite dispersion liquid with the mass fraction of 10%, sequentially adding zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate into the modified attapulgite dispersion liquid, then adding into a reaction kettle, heating to 90 ℃, stirring at the rotating speed of 2000r/min for reaction for 3 hours, then filtering, cleaning with clear water, and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material;
(3) preparing the zirconium phosphate/sodium alginate modified attapulgite composite silver-loaded antibacterial agent: preparing the zirconium phosphate/sodium alginate modified attapulgite composite material into an aqueous dispersion with the mass fraction of 10%, adding a silver nitrate solution into the aqueous dispersion to ensure that the mass content of silver ions in the zirconium phosphate/sodium alginate modified attapulgite composite material is 2.2%, stirring at the rotating speed of 500r/min for 30min, carrying out suction filtration, cleaning and drying to obtain the zirconium phosphate/sodium alginate modified attapulgite composite material.
2. The antibacterial domestic ceramic of claim 1, wherein the particle size of the sodium alginate-modified attapulgite is 1250 mesh.
3. An antibacterial domestic ceramic according to claim 1 wherein the ultrasonic power is 750W and the frequency is 45 kHz.
4. The antibacterial domestic ceramic of claim 1, wherein the mass ratio of zirconium phosphate to sodium alginate-modified attapulgite in the zirconium phosphate/sodium alginate-modified attapulgite composite material is 1: 2.
5. An antibacterial domestic ceramic as claimed in claim 1 wherein said silver nitrate solution is at a concentration of 0.5 mol/L.
6. The antibacterial domestic ceramic of claim 1, further comprising the following components in parts by weight: clay 35, mullite 11, kaolin 18, zircon 13 and albite 24.
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