CN111233433A - Slow-release antibacterial purple sand ceramic and preparation process thereof - Google Patents
Slow-release antibacterial purple sand ceramic and preparation process thereof Download PDFInfo
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Abstract
The invention relates to the technical field of antibacterial purple sand ceramics, in particular to a slow-release antibacterial purple sand ceramic and a preparation process thereof. A preparation process of a slow-release antibacterial purple sand ceramic comprises the following steps: A. adding the aged purple sand mud into a boric acid aqueous solution for pugging, sealing, aging and airing to obtain a purple sand ceramic blank; B. weighing silver nitrate and zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into deionized water to prepare an antibacterial ionic solution for later use; C. and D, carrying out crystallization water removal treatment and pre-sintering treatment on the purple sand ceramic blank prepared in the step A, and then cooling to room temperature. The invention aims to provide a slow-release antibacterial purple sand ceramic and a preparation process thereof, and the prepared slow-release antibacterial purple sand ceramic has slow-release broad-spectrum sterilization and antibacterial functions, can be applied to daily utensils and catering utensils, and has good antibacterial and bactericidal effects and stable and lasting antibacterial and bactericidal properties.
Description
Technical Field
The invention relates to the technical field of antibacterial purple sand ceramics, in particular to a slow-release antibacterial purple sand ceramic and a preparation process thereof.
Background
The purple sand mud has the characteristics of good plasticity, small drying shrinkage rate, high green strength, good air permeability, wide roasting temperature range value and the like, and the prepared purple sand ceramic has a compact structure and shows a sandy effect. The purple sand ceramic is mainly applied to the fields of daily utensils, garden pottery, sculptures and handicraft furnishings, particularly to the fields of daily utensils, has the characteristics of nature and rich trace elements, is popular with people, and plays an important role as a representative of the daily utensils, particularly tableware and drinking utensils. Nowadays, with consumers paying more attention to health elements when choosing utensils, antibacterial purple sand ceramics are produced. At present, the domestic purple sand ceramic product with sterilization and antibiosis functions is mainly formed by coating a layer of glass glaze with sterilization and antibiosis functions on the surface of a blank of purple sand ceramic, such as a blank containing divalent and tetravalent titanium ions (Ti) with photosensitive sterilization and antibiosis functions+2、Ti+4) The glaze of (2) has problems that the surface glaze is easy to fall off and the antibacterial durability is poor, and the continuous antibacterial effect cannot be achieved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation process of slow-release antibacterial purple sand ceramic, and the purple sand ceramic prepared by the preparation process can slowly release bactericidal ions to achieve a slow-release bactericidal effect, and has good, lasting and stable bactericidal and antibacterial effects.
The invention also aims to provide the slow-release antibacterial purple sand ceramic prepared by the preparation process of the slow-release antibacterial purple sand ceramic, which has the functions of slow-release broad-spectrum sterilization and antibiosis, can be applied to daily utensils and catering utensils, and has good antibacterial and bactericidal effects and stable and lasting antibacterial and bactericidal properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation process of a slow-release antibacterial purple sand ceramic comprises the following steps:
A. adding the aged purple sand mud into a boric acid aqueous solution for pugging, sealing, aging and airing to obtain a purple sand ceramic blank;
B. weighing silver nitrate and zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into deionized water to prepare an antibacterial ionic solution for later use;
C. b, carrying out crystallization water removal treatment and pre-sintering treatment on the purple sand ceramic blank prepared in the step A, and then cooling to room temperature;
D. b, putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step B for soaking, and then taking out and drying;
E. and (3) carrying out secondary sintering on the purple sand ceramic blank, and then cooling to room temperature to obtain the slow-release antibacterial purple sand ceramic.
Preferably, in the step A, the mass concentration of the boric acid aqueous solution is 4-10%, and the addition amount of the boric acid aqueous solution is 1mL of the purple sand mud per 10 g.
Preferably, in the step B, the mass concentration of silver nitrate in the antibacterial ionic solution is 5-10%, and the mass concentration of zinc nitrate in the antibacterial ionic solution is 15-25%.
Preferably, in the step C, the step of removing crystallization water includes that the purple sand ceramic blank is placed into a sintering furnace for removing crystallization water and sintering, the sintering furnace is heated from room temperature to 110 ℃ at a heating rate of 110 ℃/h, is kept at 110 ℃ for 30min, is heated to 500 ℃ at a heating rate of 50 ℃/h, and is kept at the temperature for 30 min.
Preferably, in the step C, the pre-sintering treatment is to pre-sinter the purple sand ceramic blank after the crystallization water removal treatment in a sintering furnace, the sintering furnace is heated from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h, then heated at a heating rate of 100 ℃/h, and is kept at 700-800 ℃ for 30-60 min, and the porosity of the purple sand ceramic blank obtained after the crystallization water removal treatment and the pre-sintering treatment is 10-20%.
Preferably, in the step D, the soaking time of the purple sand ceramic blank in the antibacterial ion solution is 30-60 s.
Preferably, in the step E, the second sintering of the purple sand ceramic blank is to put the purple sand ceramic blank into a sintering furnace, the sintering furnace is firstly heated from room temperature to 900 ℃ at a heating rate of 250 ℃/h, is kept warm at 900 ℃ for 30min, is heated at a heating rate of 200 ℃/h, is kept warm at 1100-1150 ℃ for 30min, and is cooled to room temperature after the second sintering, so that the porosity of the slow-release antibacterial purple sand ceramic is 1.5-2.5%.
Preferably, in the step A, the aged purple sand mud is added into a boric acid water solution, the pugging temperature is 90-100 ℃, the pugging time is 1-3 hours, and the aging time for sealing and aging is 24-48 hours.
The slow-release antibacterial purple sand ceramic is prepared by using the preparation process of the slow-release antibacterial purple sand ceramic.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, boric acid is introduced into purple sand mud by adding boric acid aqueous solution for pugging, boric acid reacts with aluminosilicate to generate borate boroxy triangular vitreous body during sintering, the purple sand ceramic blank forms tiny gaps through pre-sintering treatment, and the purple sand ceramic blank soaks in the antibacterial ionic solution to sterilize Ag with broad-spectrum and antibacterial functions in the antibacterial ionic solution+And Zn2+Adsorption of Ag+And Zn2+Can be better blended into borate boron oxygen triangle glass body, simultaneously, the borate glass has certain slightly solubility to water and can be slowly dissolved in the water, thus the Ag with broad-spectrum sterilization and antibiosis functions+And Zn2+The bactericidal ions are slowly released from the borate boric oxygen triangle vitreous body in a micro-scale manner, play the role of sterilization and antibiosis with slow release effect, and stay in Ag on the surface of the purple sand ceramic when in use+And Zn2+The bactericidal ions can play the roles of sterilization and antibiosis, and Ag is used in the process of cleaning the purple sand ceramics+And Zn2+The bactericidal ions can be slowly released from the borate boric oxygen triangular vitreous body in a micro-scale manner, so that the slow-release bactericidal effect is achieved, and the bactericidal and antibacterial effects are good, lasting and stable.
Detailed Description
A preparation process of a slow-release antibacterial purple sand ceramic comprises the following steps:
A. adding the aged purple sand mud into a boric acid aqueous solution for pugging, sealing, aging and airing to obtain a purple sand ceramic blank;
B. weighing silver nitrate and zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into deionized water to prepare an antibacterial ionic solution for later use;
C. b, carrying out crystallization water removal treatment and pre-sintering treatment on the purple sand ceramic blank prepared in the step A, and then cooling to room temperature;
D. b, putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step B for soaking, and then taking out and drying;
E. and (3) carrying out secondary sintering on the purple sand ceramic blank, and then cooling to room temperature to obtain the slow-release antibacterial purple sand ceramic.
The chemical structure of silver determines that the silver has higher catalytic capability, and the reducibility of the silver in a high oxidation state is extremely high enough to generate atomic oxygen in the surrounding space. Atomic oxygen has strong oxidizing property and thus can be sterilized, so Ag+Can strongly attract sulfhydryl (-SH) on protease in bacterial body, rapidly combine with it to inactivate protease and cause bacterial death, Ag+And Zn2+Can destroy the activity of cell membrane or cell protoplasm active enzyme of bacteria at very low mass concentration, when the bacteria are coated with Ag+And Zn2+After killing, Ag+And Zn2+And the bacterial colonies are dissociated and contacted with other bacterial colonies, and the processes are repeatedly carried out, so that a new round of antibacterial and bactericidal effects are achieved. Because the main component of the purple sand mud is kaolin and the main component of the kaolin is aluminosilicate, when the purple sand mud is mixed, boric acid aqueous solution is added for pugging, boric acid is introduced into the purple sand mud, the sintering temperature of the boric acid can be reduced when the purple sand ceramic is sintered, and the boric acid reacts with the aluminosilicate to generate borate boroxy triangular vitreous body, at the moment, the purple sand ceramic blank is subjected to crystallization water removal treatment and presintering treatment, the purple sand ceramic blank forms a plurality of tiny gaps through the presintering treatment, then the purple sand ceramic blank is put into the antibacterial ionic solution for soaking, and the purple sand ceramic blank is subjected to ultraviolet irradiation treatmentMicro gaps formed after pre-sintering treatment of the sand ceramic blank are used for carrying out broad-spectrum sterilization and antibacterial on Ag in the antibacterial ion solution+And Zn2+The adsorption is carried out because the borate boron oxygen triangle glass body is good Ag+And Zn2+Ionophores, Ag+And Zn2 +The bactericidal ions can be better blended into the borate boron oxygen triangular glass body, and simultaneously, the borate glass has certain slightly solubility to water and can be slowly dissolved in the water, so that the Ag with broad-spectrum bactericidal and antibacterial functions+And Zn2+The bactericidal ions are slowly released from the borate boric oxygen triangle vitreous body in a micro-scale manner, play the role of sterilization and antibiosis with slow release effect, and stay in Ag on the surface of the purple sand ceramic when in use+And Zn2+The bactericidal ions can play the roles of sterilization and antibiosis, and Ag is used in the process of cleaning the purple sand ceramics+And Zn2+The bactericidal ions can be slowly released from the borate boric oxygen triangular vitreous body in a micro-scale manner, so that the slow-release bactericidal effect is achieved, and the bactericidal and antibacterial effects are good, lasting and stable.
Preferably, in the step A, the mass concentration of the boric acid aqueous solution is 4-10%, and the addition amount of the boric acid aqueous solution is 1mL of the purple sand mud per 10 g.
Boric acid enters a glass state, and two glass bodies are provided, wherein one glass body is a borate boron-oxygen tetrahedral glass body which is a cubic structure, has high chemical stability and is not easy to dissolve by aqueous solution; the other is borate boron oxygen triangular glass body which has poor chemical stability and is characterized in that the sterilization metal ions can be stably kept in the borate boron oxygen triangular glass body, and the borate boron oxygen triangular glass body can be slowly dissolved in water and can slowly release the sterilization metal ions. K in the purple sand ceramic blank during sintering2O、Na2The partial alkali and alkaline earth metal oxides such as O, CaO, MgO, etc. take part in vitrification reaction to provide partial oxygen atoms for the boron-oxygen vitreous body to form borate boron-oxygen tetrahedral vitreous body, the rest forms borate boron-oxygen triangular vitreous body, Ag is formed during sintering+And Zn2+Mainly enriched in boric acidAnd when the mass concentration of the boric acid aqueous solution is more than 10% or the dosage is too much, vitrification is only carried out on the particle surfaces of the purple sand ceramic blank due to low sintering temperature, and the redundant boric acid does not participate in vitrification at the moment.
Preferably, in the step B, the mass concentration of silver nitrate in the antibacterial ionic solution is 5-10%, and the mass concentration of zinc nitrate in the antibacterial ionic solution is 15-25%.
Ag+And Zn2+Can destroy the activity of cell membrane or cell protoplasm active enzyme of bacteria at very low mass concentration, when the bacteria are coated with Ag+And Zn2+After killing, Ag+And Zn2+And the bacterial colonies are dissociated and contacted with other bacterial colonies, and the processes are repeatedly carried out, so that a new round of antibacterial and bactericidal effects are achieved. Limiting the mass concentration of silver nitrate and zinc nitrate in the antibacterial ion solution, and controlling Ag in the antibacterial ion solution adsorbed by the purple sand ceramic blank+And Zn2+Content to thereby control Ag+And Zn2+The effective content in the purple sand ceramic blank ensures the sterilization effect, and if the addition amount is too low, the sterilization effect is poor, the addition amount is too high, and excessive Ag is contained+And Zn2+The purple sand ceramic blank is remained in the solution after the adsorption of the purple sand ceramic blank to ions reaches saturation, so that waste is caused, and in addition, the mass concentration of zinc nitrate in the antibacterial ion solution is higher than that of silver nitrate because part of Zn2+Participate in the formation of borate boron oxygen triangle vitreous body, contribute to improving the slow release effect of the antibacterial purple sand ceramic, and play a role in stabilizing and slow release.
Preferably, in the step C, the step of removing crystallization water includes that the purple sand ceramic blank is placed into a sintering furnace for removing crystallization water and sintering, the sintering furnace is heated from room temperature to 110 ℃ at a heating rate of 110 ℃/h, is kept at 110 ℃ for 30min, is heated to 500 ℃ at a heating rate of 50 ℃/h, and is kept at the temperature for 30 min.
The sintering furnace is firstly heated from room temperature to 110 ℃ at the heating rate of 110 ℃/h as the dehydration stage of the purple sand ceramic blank, and after the temperature is kept at 110 ℃ for 30min, the temperature is heated to 500 ℃ at the heating rate of 50 ℃/h and is kept for 30min to remove the purple sand ceramic blank (Al)2O3·2SiO2·2H2And O) crystallizing water, wherein dry cracks are easily generated in the inner part and the surface of the purple sand ceramic blank in the temperature rising process, and the cracking of the purple sand ceramic blank is avoided by slowly rising the temperature.
Preferably, in the step C, the pre-sintering treatment is to pre-sinter the purple sand ceramic blank after the crystallization water removal treatment in a sintering furnace, the sintering furnace is heated from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h, then heated at a heating rate of 100 ℃/h, and is kept at 700-800 ℃ for 30-60 min, and the porosity of the purple sand ceramic blank obtained after the crystallization water removal treatment and the pre-sintering treatment is 10-20%.
The purple sand ceramic blank forms tiny gaps through pre-sintering treatment, then the purple sand ceramic blank is placed into the antibacterial ion solution for soaking, silver ions and zinc ions with broad-spectrum sterilization and antibacterial functions in the antibacterial ion solution are adsorbed through the tiny gaps formed after the pre-sintering treatment of the purple sand ceramic blank, the temperature is increased from 500 ℃ to 600 ℃ at the heating rate of 50 ℃/h, then the temperature is increased at the heating rate of 100 ℃/h, the temperature is maintained at 700-800 ℃ for 30-60 min, the heating rate during pre-sintering is controlled, the purple sand ceramic blank can be controlled to form tiny gaps, if the heat preservation temperature is too low or the heat preservation time is too short, the porosity of the purple sand ceramic blank is too high, the heat preservation temperature is too high or the heat preservation time is too long, the porosity of the purple sand ceramic blank is too low, in order to enable the antibacterial ionic solution to better enter the purple sand ceramic blank and be absorbed by the purple sand ceramic blank, the heat preservation time and the heat preservation temperature are controlled to ensure that the porosity of the purple sand ceramic blank is 10-20%, if the porosity is too low, the antibacterial ionic solution is difficult to enter the purple sand ceramic blank, and if the porosity is too high, the depth of the antibacterial ionic solution entering the purple sand ceramic blank is too deep, the antibacterial ions entering the deep space are difficult to release, and the slow release effect is influenced.
Preferably, in the step D, the soaking time of the purple sand ceramic blank in the antibacterial ion solution is 30-60 s.
Due to Ag+And Zn2+The bactericidal ions mainly have the dissolution bactericidal function on the outer layer of the purple sand ceramic, the soaking time of the purple sand ceramic blank in the antibacterial ion solution is controlled, and the Ag on the outer layer of the purple sand ceramic blank is realized by soaking+And Zn2+Saturated absorption of bactericidal ions, Ag if the soaking time is too long+And Zn2+The depth of the bactericidal ions entering the purple sand ceramic blank is too deep, and the Ag entering the depth of the purple sand ceramic blank+And Zn2+The bactericidal ions basically have no chance to be leached out, if the soaking time is too short, the pair Ag of the purple sand ceramic blank+And Zn2+The adsorption of the bactericidal ions is too little, and the antibacterial and bactericidal effects of the purple sand ceramics are weakened.
Preferably, in the step E, the second sintering of the purple sand ceramic blank is to put the purple sand ceramic blank into a sintering furnace, the sintering furnace is firstly heated from room temperature to 900 ℃ at a heating rate of 250 ℃/h, is kept warm at 900 ℃ for 30min, is heated at a heating rate of 200 ℃/h, is kept warm at 1100-1150 ℃ for 30min, and is cooled to room temperature after the second sintering, so that the porosity of the slow-release antibacterial purple sand ceramic is 1.5-2.5%.
The red porcelain ceramic blank is sintered for the second time, the temperature of the sintering furnace is increased from room temperature to 900 ℃ at the heating rate of 250 ℃/h, and the temperature is rapidly increased to avoid Ag in the red porcelain ceramic blank+And Zn2+Sterilizing ion volatilization loss, and keeping the temperature at 900 ℃ for 30min to ensure that aluminosilicate of kaolin and boric acid in the purple sand ceramic blank enterFully react to form Ag+And Zn2+The sterilization ions enter the borate boric oxygen triangular vitreous body, the temperature is reduced to room temperature after secondary sintering, the obtained slow-release antibacterial purple sand ceramic is high in density and high in density, the sintering temperature of the secondary sintering is controlled at the moment, the temperature is kept for 30min when the temperature is raised to 1100-1150 ℃, the porosity of the slow-release antibacterial purple sand ceramic is controlled, and only can the water solution be guaranteed to enter the slow-release antibacterial purple sand ceramic through the pores, the sterilization ions are effectively released by the borate boric oxygen triangular vitreous body at the moment, the higher the sintering temperature of the secondary sintering is, the lower the porosity is, if the porosity is too low, the slow-release effect is poor, the lower the sintering temperature of the secondary sintering is, the higher the porosity is, and the too high porosity can reduce the strength of the slow-release antibacterial purple sand ceramic.
Preferably, in the step A, the aged purple sand mud is added into a boric acid water solution, the pugging temperature is 90-100 ℃, the pugging time is 1-3 hours, and the aging time for sealing and aging is 24-48 hours.
The pugging temperature of adding the aged purple sand mud into a boric acid water solution for pugging is controlled to be 90-100 ℃, if the temperature is too high, the boric acid water solution is volatilized too early, enough boric acid cannot be provided to react with aluminosilicate to generate borate boric oxygen triangular vitreous bodies, the slow release effect is poor, pugging and aging are carried out, the pugging of the purple sand mud is more uniform, and the plasticity and the density of the pugging are improved.
The slow-release antibacterial purple sand ceramic is prepared by using the preparation process of the slow-release antibacterial purple sand ceramic.
The slow-release antibacterial purple sand ceramic prepared by the preparation process of the slow-release antibacterial purple sand ceramic has slow-release broad-spectrum sterilization and antibacterial functions, can be applied to daily utensils and catering utensils, and has good antibacterial and bactericidal effects and stable and lasting antibacterial and bactericidal properties.
The technical solution of the present invention is further explained by the following embodiments.
And (3) performance testing:
1. and (3) determination of antibacterial rate: the antibacterial rate is determined according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance.
2. And (3) antibacterial durability measurement: the antibacterial durability is determined according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance.
3. And (3) testing the slow release performance: soaking purple sand ceramic sample wafers with the same thickness and area in deionized water at constant temperature of 25 ℃ for 10 days, taking the soaking solution to detect the concentration of silver ions, then repeating the next test on the sample, wherein the detection interval is 10 days each time, sampling for four times and recording the measurement result.
Example 1
The slow-release antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 4% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 700 ℃ for 30min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 30s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the slow-release antibacterial purple sand ceramic.
Example 2
The slow-release antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 25g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 25% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, firstly heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, then heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, carrying out crystallization water removal treatment, then carrying out presintering treatment, firstly heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, then heating at a heating rate of 100 ℃/h, preserving heat at 750 ℃ for 40min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 40s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1125 ℃ for 30min, and naturally cooling to room temperature to obtain the slow-release antibacterial purple sand ceramic.
Example 3
The slow-release antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into 8% boric acid water solution for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 8g of silver nitrate and 20g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 8% of the silver nitrate and 20% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 800 ℃ for 30min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 50s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1150 ℃ for 30min, and naturally cooling to room temperature to obtain the slow-release antibacterial purple sand ceramic.
Comparative example 1
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into 1% boric acid water solution for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 700 ℃ for 40min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 40s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the antibacterial purple sand ceramic.
Comparative example 2
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 10g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 10% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 700 ℃ for 30min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 30s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the antibacterial purple sand ceramic.
Comparative example 3
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 650 ℃ for 30min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 30s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the antibacterial purple sand ceramic.
Comparative example 4
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 700 ℃ for 20min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 30s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the antibacterial purple sand ceramic.
Comparative example 5
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 850 ℃ for 30min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 30s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the antibacterial purple sand ceramic.
Comparative example 6
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 700 ℃ for 70min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 30s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the antibacterial purple sand ceramic.
Comparative example 7
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 700 ℃ for 30min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 15s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at 1100 ℃ for 30min, and naturally cooling to room temperature to obtain the antibacterial purple sand ceramic.
Comparative example 8
An antibacterial purple sand ceramic is prepared by the following steps:
(1) adding aged Yixing Dingshan Huang Longshan purple sand mud into a boric acid aqueous solution with the mass concentration of 5% for pugging for 1h, wherein the pugging temperature is 90 ℃, sealing and aging for 24h, and then airing to prepare a purple sand ceramic blank;
(2) weighing 5g of silver nitrate and 15g of zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into 100mL of deionized water to prepare an antibacterial ion solution with the mass concentration of 5% of the silver nitrate and 15% of the zinc nitrate for later use;
(3) putting the purple sand ceramic blank prepared in the step (1) into a sintering furnace, heating from room temperature to 110 ℃ at a heating rate of 110 ℃/h, preserving heat at 110 ℃ for 30min, heating to 500 ℃ at a heating rate of 50 ℃/h, preserving heat for 30min, performing crystallization water removal treatment, then performing pre-sintering treatment, heating from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h in the sintering furnace, heating at a heating rate of 100 ℃/h, preserving heat at 700 ℃ for 30min, and then naturally cooling to room temperature;
(4) putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step (2) for soaking for 30s, taking out and drying;
(5) and (2) putting the purple sand ceramic blank into a sintering furnace for secondary sintering, heating the sintering furnace from room temperature to 900 ℃ at the heating rate of 250 ℃/h, preserving the heat at 900 ℃ for 30min, heating at the heating rate of 200 ℃/h, preserving the heat at the sintering temperature of 1200 ℃ for 30min, and naturally cooling to room temperature to obtain the slow-release antibacterial purple sand ceramic.
The performance of the purple sand ceramics prepared in examples 1 to 3 and comparative examples 1 to 8 was tested, and the results are shown in tables 1 and 2.
TABLE 1 examples and comparative examples Performance tests (antibacterial Rate and antibacterial durability)
TABLE 2 examples and comparative examples Performance test (sustained Release Performance)
As can be seen from the test results in tables 1 and 2, the antibacterial purple sand ceramics prepared in examples 1-3 have good antibacterial performance, which reaches the index JC/T897-2014 antibacterial ceramic product antibacterial performance, the antibacterial rate is not less than 90%, the antibacterial durability is not less than 85%, and the examples 1-3 can slowly release Ag through the slow release performance test+The bactericidal ions have stable slow-release effect, boric acid reacts with aluminosilicate to generate borate boroxine glass body during sintering by adding boric acid aqueous solution for pugging, the purple sand ceramic blank forms tiny gaps through pre-sintering treatment, and the purple sand ceramic wool is soaked in the antibacterial ion solutionThe blank has broad-spectrum sterilization and antibacterial functions on Ag in the antibacterial ion solution+And Zn2+Adsorption of Ag+And Zn2+Can be better blended into borate boron oxygen triangle glass body, simultaneously utilizes the fact that borate glass has certain slightly solubility to water, can be slowly dissolved in water, and still can test Ag from the test solution when undergoing four times of slow release performance test sampling+The content of the bactericidal ions achieves the slow-release bactericidal effect of slowly releasing the bactericidal ions, and the bactericidal and antibacterial effects are good, lasting and stable.
The antibacterial rate and the antibacterial durability of the antibacterial purple sand ceramic prepared in the comparative example 1 are obviously reduced, the silver ion concentration is very high when the first detection is carried out in the test of slow release performance test, the silver ion concentration is very low when the second detection is carried out, the silver ion concentration cannot be detected when the third detection and the fourth detection are carried out, and because the mass concentration of the boric acid aqueous solution in the comparative example 1 is too low, borate boron oxygen tetrahedron which has no slow release effect on antibacterial ions is basically formed when the boric acid aqueous solution participates in the vitrification reaction of a purple sand ceramic blank, the prepared antibacterial purple sand ceramic has poor slow release effect, and at the moment, the antibacterial ions only stay on the surface of the antibacterial purple sand ceramic and are easy to dissociate out after being soaked in the antibacterial ion solution, so the antibacterial performance and the antibacterial durability are poor;
the antibacterial rate and the antibacterial durability of the antibacterial purple sand ceramic prepared in the comparative example 2 cannot reach indexes of JC/T897-2014 antibacterial ceramic product antibacterial performance, the slow release performance is reduced, and the Zn concentration of the antibacterial ion solution is too low because the mass concentration of the zinc nitrate of the antibacterial ion solution is too low when the antibacterial ion solution is prepared in the comparative example 22+Antibacterial purple sand ceramic pair Zn with reduced antibacterial ions2+The adsorption amount of antibacterial ions is decreased, the antibacterial ratio is decreased, and Zn is formed at this time2+Too little to participate in the formation of borate boroxine triangular vitreous body, so that the antibacterial durability and the slow release effect are poor;
the antibacterial rate and the antibacterial durability of the antibacterial purple sand ceramics prepared in the comparative examples 3 and 4 are poor, the slow release performance test result is poor, the presintering temperature of the comparative example 3 is too low, the presintering time of the comparative example 4 is too short, so that the porosity of a purple sand ceramic blank is too high, the depth of the antibacterial ion solution entering the purple sand ceramic blank is too deep, the antibacterial ions entering the deep depth are difficult to release, and when the antibacterial ions on the superficial surface of the antibacterial purple sand ceramic are completely released, the ions in the deep inner part cannot be released, so that the antibacterial effect and the slow release effect are influenced;
the antibacterial rate and the antibacterial durability of the antibacterial purple sand ceramics prepared in the comparative examples 5 and 6 are poor, the slow release performance test result is poor, the pre-sintering temperature of the comparative example 5 is too high, the pre-sintering time of the comparative example 6 is too long, so that the porosity of the purple sand ceramic blank is too low, an antibacterial ion solution is difficult to enter the purple sand ceramic blank and only stays on the surface of the antibacterial purple sand ceramic, and is easy to dissociate, and the antibacterial effect and the slow release effect of the antibacterial purple sand ceramic are greatly influenced;
the antibacterial rate and the antibacterial durability of the antibacterial purple sand ceramic prepared in the comparative example 7 are obviously reduced, and the purple sand ceramic blank prepared in the comparative example 7 is too short in soaking time in the antibacterial ion solution, so that the purple sand ceramic blank is Ag-resistant+And Zn2+The adsorption of the bactericidal ions is too little, the antibacterial and bactericidal effects of the purple sand ceramic are weakened, a small amount of antibacterial ions are quickly dissociated on the surface layer of the antibacterial purple sand ceramic in the slow release performance test, and the concentration of silver ions cannot be detected by sampling for the second time in the slow release performance test;
the antibacterial rate and the antibacterial durability of the antibacterial purple sand ceramic prepared in the comparative example 8 are poor, the slow release performance test result is poor, and the sintering temperature of the comparative example 8 in the secondary sintering process is too high, so that the porosity of the prepared antibacterial purple sand ceramic is too low, antibacterial ions in the antibacterial purple sand ceramic are difficult to release, and the antibacterial effect and the slow release effect are poor.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. A preparation process of a slow-release antibacterial purple sand ceramic is characterized by comprising the following steps:
A. adding the aged purple sand mud into a boric acid aqueous solution for pugging, sealing, aging and airing to obtain a purple sand ceramic blank;
B. weighing silver nitrate and zinc nitrate, and dissolving the silver nitrate and the zinc nitrate into deionized water to prepare an antibacterial ionic solution for later use;
C. b, carrying out crystallization water removal treatment and pre-sintering treatment on the purple sand ceramic blank prepared in the step A, and then cooling to room temperature;
D. b, putting the purple sand ceramic blank into the antibacterial ion solution prepared in the step B for soaking, and then taking out and drying;
E. and (3) carrying out secondary sintering on the purple sand ceramic blank, and then cooling to room temperature to obtain the slow-release antibacterial purple sand ceramic.
2. The preparation process of the slow-release antibacterial purple sand ceramic according to claim 1, wherein in the step A, the mass concentration of the boric acid aqueous solution is 4-10%, and the addition amount of the boric acid aqueous solution is 1mL of the boric acid aqueous solution per 10g of the purple sand mud.
3. The preparation process of the slow-release antibacterial purple sand ceramic according to claim 1, wherein in the step B, the mass concentration of silver nitrate in the antibacterial ionic solution is 5-10%, and the mass concentration of zinc nitrate in the antibacterial ionic solution is 15-25%.
4. The process for preparing a slow-release antibacterial purple sand ceramic according to claim 1, wherein in the step C, the step of crystallizing water removing treatment is to put the blank of the purple sand ceramic into a sintering furnace for crystallizing water removing and sintering, wherein the sintering furnace is firstly heated from room temperature to 110 ℃ at a heating rate of 110 ℃/h, and after the temperature is kept at 110 ℃ for 30min, the temperature is heated to 500 ℃ at a heating rate of 50 ℃/h and then kept for 30 min.
5. The preparation process of the slow-release antibacterial purple sand ceramic according to claim 1, wherein in the step C, the pre-sintering treatment is to pre-sinter the purple sand ceramic blank after the crystallization water removal treatment in a sintering furnace, the sintering furnace is firstly heated from 500 ℃ to 600 ℃ at a heating rate of 50 ℃/h, then heated at a heating rate of 100 ℃/h, and is kept at the temperature of 700-800 ℃ for 30-60 min, and the porosity of the purple sand ceramic blank obtained after the crystallization water removal treatment and the pre-sintering treatment is 10-20%.
6. The preparation process of the slow-release antibacterial purple sand ceramic as claimed in claim 1, wherein in the step D, the soaking time of the purple sand ceramic blank in the antibacterial ionic solution is 30-60 s.
7. The preparation process of the slow-release antibacterial purple sand ceramic according to claim 1, wherein in the step E, the purple sand ceramic blank is subjected to secondary sintering to be placed into a sintering furnace, the sintering furnace is heated from room temperature to 900 ℃ at a heating rate of 250 ℃/h, is subjected to heat preservation at 900 ℃ for 30min, is heated at a heating rate of 200 ℃/h, is heated to the sintering temperature of 1100-1150 ℃ and is subjected to heat preservation for 30min, and is subjected to secondary sintering and then is cooled to room temperature, so that the porosity of the obtained slow-release antibacterial purple sand ceramic is 1.5-2.5%.
8. The preparation process of the slow-release antibacterial purple sand ceramic according to claim 1, wherein in the step A, the aged purple sand mud is added into a boric acid aqueous solution for pugging, the pugging temperature is 90-100 ℃, the pugging time is 1-3 hours, and the aging time for sealing and aging is 24-48 hours.
9. The slow-release antibacterial purple sand ceramic is characterized by being prepared by using the preparation process of the slow-release antibacterial purple sand ceramic according to any one of claims 1 to 8.
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