CN104761290A - Preparation method of rare-earth-added water-soluble antibacterial ceramic glaze - Google Patents
Preparation method of rare-earth-added water-soluble antibacterial ceramic glaze Download PDFInfo
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- CN104761290A CN104761290A CN201510126395.4A CN201510126395A CN104761290A CN 104761290 A CN104761290 A CN 104761290A CN 201510126395 A CN201510126395 A CN 201510126395A CN 104761290 A CN104761290 A CN 104761290A
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Abstract
The invention discloses a preparation method of a rare-earth-added water-soluble antibacterial ceramic glaze. The preparation method is characterized by comprising the following technical steps: in a reactor, adding, by mass, 25-35% of ammonium hexafluorozirconate, 2-5% of sodium hexametaphosphate, 40-50% of zinc silicofluoride, 8-18% of ammonium fluoroborate, 2-6% of silver nitrate, and 5-15% of lanthanum nitrate, wherein the sum of each component is 100%; and performing grinding for uniform mixing to obtain the rare-earth-added water-soluble antibacterial ceramic glaze. A use method of the rare-earth-added water-soluble antibacterial ceramic glaze comprises: dissolving the rare-earth-added water-soluble antibacterial ceramic glaze in water to prepare a saturated solution; uniformly spraying the solution of the rare-earth-added water-soluble antibacterial ceramic glaze onto a ceramic biscuit by a sprayer; and baking the ceramic biscuit at a high temperature of 950-1000 DEG C to obtain a finished product. The ceramic glaze has excellent bactericidal activity and good glossiness.
Description
Technical field
The invention belongs to domestic ceramics technical field, particularly a kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth interpolation rare earth.
Background technology
Bacterium, mould (fungi) have very large harm as the life of pathogenic bacteria to people, have had a strong impact on the health of people.The mankind bring into use antibacterial thing very early, from B.C. Egyptian use tar, frankincense, Chinese cassia tree, to Wei Le urea synthesis in 1828, entered for 20th century, after people have grasped the chemical structure of agricultural chemicals fish, rattan ketone and pyrethrin etc., a large amount of organic antibacterial agents has been born.The 1950's, exploitation and the antimicrobial technology of antiseptic-germicide grow up gradually.Enter the eighties, people start to focus on quality of life, and pursue the living environment of comfort and health, antibiotic odourproof fiber is made into.From then on, anti-bacteria ceramic, antibiotic paint, antibacterial film, antibacterial food, antibacterial cosmetic etc. arise at the historic moment.After the nineties, Japan, the U.S. etc. have carried out extensive and deep research to anti-bacteria ceramic, inorganic antiseptic and goods thereof become with its safety, reliable, stable and lasting anti-microbial property the object that everybody mainly studies, and are commercially proposed the products such as Antimicrobial sanitation sanitary equipment, antibacterial glazed tiles and antibacterial tableware.Along with the progress of society and the raising of people's living standard, the Growth and reproduction of control and elimination unwanted bacteria becomes the important topic of scientific research field day by day, and constantly receives the concern of more and more people, becomes the important component part of environment-friendly materials.The research of China to anti-bacteria ceramic is also in the starting stage, and antibacterial glaze is exactly to eliminate and reducing the harm of these pathogenic bacterias and the new glaze kind developed.
Organic antibacterial agent can not be used in ceramic glaze, the metals such as inorganic antiseptic silver, copper, zinc have antibacterial ability, antiseptic-germicide is made on the surface they being fixed on the material such as zeolite, silicate, is then joined the material namely obtaining in corresponding goods and have antibacterial ability.The metals such as mercury, cadmium, lead also have antibacterial ability, but harmful; Copper, nickel, cobalt plasma are with color, and will affect the attractive in appearance of product, zinc has certain germ resistance, but its antibacterial strength is only 1/1000 of silver ions.Therefore, silver ion antimicrobial agent occupies dominant position in inorganic antiseptic, and because the price comparison of silver is high, the consumption conference of silver increases the cost of product, when adding rare earth element in enamel, and the larger Ag of the ionic radius due to rare earth element
+inlay wherein comparatively indissoluble go out, thus improve anti-microbial property.
Ceramic glaze research also many, but to having ceramic glaze research less of specific function.A kind of antimicrobial ceramic glaze preparation method is disclosed in Chinese patent CN1933733B, it is characterized in that the zinc borate giving a large amount of ceramic product antimicrobial property, with extra free zinc oxide, the zinc borate of wherein said antibiont ceramic glazing composition and the ppm ratio of free zinc oxide are from 10:90 to 90:10.Disclose a kind of ceramic glaze and the using method thereof with Nano self-cleaning sterilizing function in Chinese patent CN103387421 A, be characterized in introducing Ag while refinement cover-coat enamel particle
2o and ZnO, as composite nano germicide, makes cover-coat enamel have nano level phase separation structure and sterilizing ability, once fires form acquisition ceramic ware for daily use 1200 ~ 1250 DEG C of temperature ranges.Disclose a kind of self-cleaning antibacterial ceramic glaze and preparation method thereof and ceramic product in Chinese patent CN101580342 B, it is characterized in that containing Ti element and Ag element.Malleable iron one-tenth etc., have studied preparation and the performance thereof of anti-bacteria ceramic ornamental brick, its antimicrobial component is Ag
3pO
4, (malleable iron one-tenth etc., the preparation of anti-bacteria ceramic ornamental brick and performance study thereof, Chinese pottery industry, 2002,9(1), 1 ~ 5).
Traditional ceramic glaze is make slurry mostly, then evenly impose on biscuit and sinter, this method is complex process when preparing the slurry of glaze, be coated onto biscuit requires very even, technique is more complicated also, and the globule size of enamel particle directly affects the quality of enamel.It is to dissolve with water that the application prepares a kind of ceramic glaze, uniformly spray on biscuit with atomizer and sinter, bright and clean beautiful one deck enamel can be formed at ceramic surface, and form the particle very fine uniform of enamel, using method is simple, chemical stability good, changes the technological process of the slurry of original ceramic glaze.
Summary of the invention
Order of the present invention is to provide the water-soluble antibacterial ceramic glaze of a kind of interpolation rare earth, has excellent germ resistance, improves hardness and the glossiness of glaze simultaneously, adds preparation method and the technique of the water-soluble antibacterial ceramic glaze of rare earth;
Object of the present invention is achieved through the following technical solutions.
A kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, be characterised in that the method has following processing step: in the reactor, the hexafluoro adding 25% ~ 35% by mass percentage closes zirconic acid ammonium, 2% ~ 5% Sodium hexametaphosphate 99,40% ~ 50% Zinc Fluosilicate, 8% ~ 18% ammonium borofluoride, 2% ~ 6% Silver Nitrate, 5% ~ 15% lanthanum nitrate, each component sum is absolutely, and ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.
Add in the preparation method of the water-soluble antibacterial ceramic glaze of rare earth a kind of, described Zinc Fluosilicate is the Zinc Fluosilicate containing 6 crystal water.
Add in the preparation method of the water-soluble antibacterial ceramic glaze of rare earth a kind of, described lanthanum nitrate is the lanthanum nitrate containing 6 crystal water.
Add in the preparation method of the water-soluble antibacterial ceramic glaze of rare earth a kind of, described lanthanum nitrate: the mol ratio of Silver Nitrate optimum is 1:0.9 ~ 1.1.
A kind of using method of adding the water-soluble antibacterial ceramic glaze of rare earth that the present invention obtains: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, with atomizer, the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze is sprayed on the biscuit of pottery, through the high-temperature firings of 950 ~ 1000 DEG C to finished product.
Compared with the prior art, tool has the following advantages and beneficial effect in the present invention:
(1) the present invention obtains and adds the water-soluble antibacterial ceramic glaze of rare earth, and be characterized in that water miscible spraying is convenient, avoiding traditional ceramic glaze is the loaded down with trivial details technological process making slurry mostly.
(2) the present invention obtains and adds the water-soluble antibacterial ceramic glaze of rare earth, and containing antiseptic elements silver, zinc and rare earth element, antibacterial ability is strong, and the time is lasting, harmless.
(3) the present invention obtains and adds the water-soluble antibacterial ceramic glaze of rare earth, form because the water-soluble antibacterial ceramic glaze of interpolation rare earth closes the chemical compositions such as zirconic acid ammonium, ammonium borofluoride and Zinc Fluosilicate by the hexafluoro of fluoride ion, moltenly with the silicate in the biscuit of pottery can be integrated, glossiness be good so enamel has, chemical stabilization.
(4) the present invention obtains and adds the water-soluble antibacterial ceramic glaze of rare earth, and preparation technology is simple, and condition is easy to control, and production cost is low, is easy to suitability for industrialized production.
Embodiment
Embodiment 1
A kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, in the reactor, add 30g hexafluoro respectively and close zirconic acid ammonium, 3g Sodium hexametaphosphate 99,45g Zinc Fluosilicate, 13g ammonium borofluoride, 2g Silver Nitrate, 7g lanthanum nitrate, ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.Its using method: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, is sprayed on the biscuit of pottery with atomizer by the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze, through the high-temperature firings of 950 DEG C to finished product.
Embodiment 2
A kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, in the reactor, add 35g hexafluoro respectively and close zirconic acid ammonium, 5g Sodium hexametaphosphate 99,40g Zinc Fluosilicate, 9g ammonium borofluoride, 3g Silver Nitrate, 8g lanthanum nitrate, ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.Its using method: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, is sprayed on the biscuit of pottery with atomizer by the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze, through the high-temperature firings of 960 DEG C to finished product.
Embodiment 3
A kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, in the reactor, add 25g hexafluoro respectively and close zirconic acid ammonium, 2g Sodium hexametaphosphate 99,42g Zinc Fluosilicate, 10g ammonium borofluoride, 6g Silver Nitrate, 15g lanthanum nitrate, ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.Its using method: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, is sprayed on the biscuit of pottery with atomizer by the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze, through the high-temperature firings of 970 DEG C to finished product.
Embodiment 4
A kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, in the reactor, add 26g hexafluoro respectively and close zirconic acid ammonium, 2g Sodium hexametaphosphate 99,50g Zinc Fluosilicate, 8g ammonium borofluoride, 4g Silver Nitrate, 10g lanthanum nitrate, ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.Its using method: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, is sprayed on the biscuit of pottery with atomizer by the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze, through the high-temperature firings of 980 DEG C to finished product.
Embodiment 5
A kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, in the reactor, add 25g hexafluoro respectively and close zirconic acid ammonium, 3g Sodium hexametaphosphate 99,40g Zinc Fluosilicate, 15g ammonium borofluoride, 5g Silver Nitrate, 12g lanthanum nitrate, ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.Its using method: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, is sprayed on the biscuit of pottery with atomizer by the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze, through the high-temperature firings of 990 DEG C to finished product.
Embodiment 6
A kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, in the reactor, add 32g hexafluoro respectively and close zirconic acid ammonium, 4g Sodium hexametaphosphate 99,48g Zinc Fluosilicate, 18g ammonium borofluoride, 2g Silver Nitrate, 5g lanthanum nitrate, ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.Its using method: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, is sprayed on the biscuit of pottery with atomizer by the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze, through the high-temperature firings of 1000 DEG C to finished product.
Embodiment 7
The water-soluble antibacterial ceramic glaze of interpolation rare earth prepared by embodiment 1 to embodiment 6 is applied to finished product prepared by biscuit of ceramics and carries out technical indicator test, result is as follows:
(1) sintering temperature: 950 ~ 1000 DEG C;
(2) glossiness: between 90 ~ 105;
(3) chemical stability:
Acid resistance is tested: finished product is at 25 ± 2 DEG C, and mass percentage concentration is soak 48 hours in the acetum of 4%, and thing corrodes vestige;
Alkali resistance is tested: finished product is at 50 ± 2 DEG C, and mass percentage concentration is soak 48 hours in the sodium carbonate solution of 1%, and thing corrodes vestige;
(4) thermostability experiment: finished product is placed in circuit, is raised to 200 DEG C from room temperature, be incubated 20 minutes, drops into rapidly in 25 DEG C of water, and take out after 10 minutes and dry, color lump is without temperature shock crackle;
(5) coefficient of linear expansion: 5.0 ~ 6.5 × 10
-6/ DEG C;
(6) antibacterial effect
According to GB15979-2002 Disposable Sanitary Accessory hygienic standard, carry out sterilization experiment for intestinal bacteria and staphylococcus aureus.After aseptic deionized water cleaning sample, dry 48 hours, get certain density bacterium drop and contaminate above it, place and after 24 hours, residual bacterium is counted for 60 DEG C.Result shows: the enamel of the application is 99% to colibacillary kill ratio, and be 98% to staphylococcus aureus kill ratio, sterilization effect is ideal.
Claims (5)
1. one kind is added the preparation method of the water-soluble antibacterial ceramic glaze of rare earth, be characterised in that the method has following processing step: in the reactor, the hexafluoro adding 25% ~ 35% by mass percentage closes zirconic acid ammonium, 2% ~ 5% Sodium hexametaphosphate 99,40% ~ 50% Zinc Fluosilicate, 8% ~ 18% ammonium borofluoride, 2% ~ 6% Silver Nitrate, 5% ~ 15% lanthanum nitrate, each component sum is absolutely, and ground and mixed is even, must add the water-soluble antibacterial ceramic glaze of rare earth, the water-soluble antibacterial ceramic glaze plastics of the interpolation rare earth obtained are packed, and want sealed damp-proof.
2. a kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth according to claim 1, is characterized in that, described Zinc Fluosilicate is the Zinc Fluosilicate containing 6 crystal water.
3. a kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth according to claim 1, is characterized in that, described lanthanum nitrate is the lanthanum nitrate containing 6 crystal water.
4. a kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth according to claim 1, is characterized in that, described lanthanum nitrate: the mol ratio of Silver Nitrate optimum is 1:0.9 ~ 1.1.
5. the water-soluble antibacterial ceramic glaze of interpolation rare earth according to claim 1 prepared by a kind of preparation method adding the water-soluble antibacterial ceramic glaze of rare earth, it is characterized in that, described interpolation rare earth water-soluble antibacterial ceramic glaze using method: the water-soluble antibacterial ceramic glaze of this interpolation rare earth is dissolved in the water, saturated solution, with atomizer, the dissolution homogeneity adding rare earth water-soluble antibacterial ceramic glaze is sprayed on the biscuit of pottery, through the high-temperature firings of 950 ~ 1000 DEG C to finished product.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272377A (en) * | 2015-11-03 | 2016-01-27 | 昆明理工大学 | Preparation method of antibacterial ceramic |
| CN106348787A (en) * | 2016-11-10 | 2017-01-25 | 佛山蓝途科技有限公司 | Rare earth added antibacterial ceramic glaze and preparation method thereof |
| CN106746668A (en) * | 2016-12-14 | 2017-05-31 | 顾马飞 | A kind of antibacterial ceramic glaze liquid and preparation method thereof |
| CN109851396A (en) * | 2019-04-24 | 2019-06-07 | 同曦集团有限公司 | A kind of antibiotic ceramic tile and preparation method thereof |
| CN109970341A (en) * | 2019-04-23 | 2019-07-05 | 廖祥胜 | Antifouling and antibiosis ceramic glaze and preparation method thereof |
| CN110759642A (en) * | 2018-07-03 | 2020-02-07 | 佛山欧神诺陶瓷有限公司 | Rare earth antibacterial ceramic glaze |
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| KR20010078990A (en) * | 2001-05-30 | 2001-08-22 | 이광덕 | The manutacture of poredpottory antibiotic |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272377A (en) * | 2015-11-03 | 2016-01-27 | 昆明理工大学 | Preparation method of antibacterial ceramic |
| CN106348787A (en) * | 2016-11-10 | 2017-01-25 | 佛山蓝途科技有限公司 | Rare earth added antibacterial ceramic glaze and preparation method thereof |
| CN106746668A (en) * | 2016-12-14 | 2017-05-31 | 顾马飞 | A kind of antibacterial ceramic glaze liquid and preparation method thereof |
| CN106746668B (en) * | 2016-12-14 | 2019-05-14 | 江西精隆陶瓷有限公司 | A kind of antibacterial ceramic glaze liquid and preparation method thereof |
| CN110759642A (en) * | 2018-07-03 | 2020-02-07 | 佛山欧神诺陶瓷有限公司 | Rare earth antibacterial ceramic glaze |
| CN109970341A (en) * | 2019-04-23 | 2019-07-05 | 廖祥胜 | Antifouling and antibiosis ceramic glaze and preparation method thereof |
| CN109970341B (en) * | 2019-04-23 | 2022-03-08 | 潮州市华利达陶瓷制作有限公司 | Antifouling antibacterial ceramic glaze and preparation method thereof |
| CN109851396A (en) * | 2019-04-24 | 2019-06-07 | 同曦集团有限公司 | A kind of antibiotic ceramic tile and preparation method thereof |
| CN109851396B (en) * | 2019-04-24 | 2022-07-12 | 同曦集团有限公司 | Antibacterial ceramic tile and preparation method thereof |
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