CN101058510A - Method of preparing highly effective nano antibiotic functional ceramic and application thereof - Google Patents
Method of preparing highly effective nano antibiotic functional ceramic and application thereof Download PDFInfo
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Abstract
The invention discloses a making method and application of high-effective nanometer antibiotic ceramic, which is characterized by the following: preparing titanium acid sol as the predecessor of TiO2 optical catalyst; making biscuit firing body and glost firing body of ceramic or coarse-grain earthen ware; adopting sol-gel method to load the doped titanium acid sol on the surface of ceramic or coarse-grain earthen ware; sintering; obtaining the product with diameter between 10mm and 20mm and loading quantity at 0. 21mg/cm2.
Description
Technical field
The present invention relates to the highly effective nano antibiotic functional ceramic preparation method and the application of (pottery or stoneware comprise pottery or stoneware ball).
Technical background
Nanotechnology is being emerging research field aspect antibiotic, the sterilization of pottery, and its core is that antiseptic-germicide is made nanometer materials, makes nanoparticle have very high surfactivity, for antiseptic-germicide contacts the good condition of creating with bacterium, improves sterilizing rate.Antibiotic functional ceramic is a class ceramic product that rises the end of the eighties in last century, and the bacterial reproduction that its glaze can suppress to adhere to kills each bacterioid, avoids the cross infection of bacterium effectively.Most widely used antimicrobial technology has two kinds at present: a kind of technology is to adopt TiO
2For the photocatalyst of representing produces very strong hydroxyl radical free radical of oxidation capacity and activated state oxygen under illumination condition, this technology can be used for sterilization and makes organic pollutant resolve into nontoxic carbonic acid gas, water and simple inorganics.This technology can not only sterilization, and the bacterium remains are thoroughly decomposed, and can not cause new pollution.The present invention " efficient nano TiO
2Photocatalysis antibacterial pottery or stoneware " belong to this technology category just, take at TiO
2Mix a spot of silver, iron, rare earth element chemical ingredients in addition, to improve photocatalysis efficiency.While TiO
2Granular size after the film forming is a nano level, and the film forming thickness of shape also is nano level, is a kind of highly effective nano antibiotic functional ceramic therefore.Another kind of sterilising technology is the insoluble metal compound with anti-microbial effect, wherein the most representative with inorganic silver salt, they react by the sulfydryl with cell protein, make it to lose the fissiparity ability, this type of antiseptic-germicide effect is lasting, wide spectrum, heat-resisting, safety, is difficult for developing immunity to drugs.Entered since the nineties, developed country studies active aspect anti-biotic material, and anti-bacteria ceramic and goods put goods on the market one after another, and wherein nano antibiotic functional ceramic is becoming the focus of research and development.The starting late of China in this field with external obvious in the research gap aspect product development and the anti-biotic material, but also has some relevant patent achievements reports, as:
CN1320580 discloses a kind of making method of antibacterial ceramic products, this method by base, biscuiting or not biscuiting, execute common glaze, execute antibacterial glaze, operation such as sintering forms.Wherein glazing operation is 2 glazings, promptly executed behind the common glaze and executed by antiseptic-germicide and the antibacterial glaze that is mixed and made into the common glaze of former goods, antibacterial glaze is mixed and made into by antiseptic-germicide and common glaze, and the principle of preparation is that the concentration of the antibacterial metal oxide compound in the antibacterial glaze is 1~8wt%.This invention has simplifies working process, reduces cost, and energy efficient, easy and simple to handle, antibiotic rate advantages of higher can be widely used in the making of various ceramics.
It is that carrier is incorporated in the glaze with calcium phosphate that CN1301678 discloses good anti-bacterial effect, safe and reliable silver, zine ion, and introduce Calcium Fluoride (Fluorspan) in the glaze, solubility promoter such as potassium felspar sand, burn till in oxidizing atmosphere with below 1500 ℃ and to make anti-bacteria ceramic; Its antibacterial and mouldproof effect is obvious.This invention need not change the production technique of original pottery, need not drop into by increase equipment, adds solubility promoter temperature of glaze firing is reduced, and makes antibacterial ceramic products once-firing at a lower temperature, has saved the energy, has reduced cost.
CN1331059 disclose anti-bacteria ceramic by body preparation, impose operations such as common glaze or antibacterial glaze (or only executing antibacterial glaze), sintering, check respectively and make, it is characterized in that: 1. the component of base substrate and content are: SiO
268~71%, Al
2O
316~20%, Fe
2O
30.3~0.7%, CaO 0.4~0.5%, MgO 0.6%, K
2O+Na
2O 3~4%; 2. the component concentration of common glaze is: SiO
271~73%, Al
2O
313~15%, Fe
2O
30.2~0.4%, CaO 0.4~0.5%, MgO 3~4%, K
2O+Na
2O 7~9%; 3. antibacterial glaze is the mixture of high-temp inorganic antibacterial agent and common glaze, and its blending ratio is: high-temp inorganic antibacterial agent is 0.2~5: 1 with the ratio of common glaze, and the gained material has advantages such as antibacterial effect is good, durable in use.
CN1519051 the invention discloses a kind of spray coating liquor that is used to make the photocatalysis antibacterial pottery, belongs to the anti-bacteria ceramic production technical field.By nano-TiO
2Colloidal sol and account for nano-TiO
2The loaded TiO of colloidal sol weight 2~3%
2Fine catalyst.Nano-TiO
2Colloidal sol is made by the tetrabutyl titanate hydrolysis reaction, adds an amount of organic acid control nano-TiO in the reaction process
2The granularity of colloidal sol particulate.Loaded TiO
2Fine catalyst is to support any metal of Pt, Fe, Rh, V or the Detitanium-ore-type TiO of metal oxide
2Powder.The anti-bacteria ceramic catalyst film that utilizes spray coating liquor of the present invention to make combines closely with pottery, and anti-microbial property is good, but the TiO that directly uses
2Powder is difficult to reach nano level.
CN1362386 discloses a kind of nano-TiO
2The preparation method of anti-bacteria ceramic utilizes nano-anatase phase TiO
2Photochemidal activity, with nano-TiO
2Be scattered in the medium equably.Coat ceramic surface then equably, carry out high-temperature calcination, make TiO
2Nanoparticle is distributed on the glaze equably, and does not influence overglaze smooth finish.Utilize TiO
2Under illumination with surface water and airborne O
2Effect discharge atomic oxygen and hydroxyl radical free radical and sterilization, but there is above-mentioned deficiency equally in this method.
The pottery of catalyst system therefor of the present invention or stoneware carrier are the main productss of Jiangsu Gaochun Ceramics Co., Ltd..Pottery or stoneware are a kind of potteries between between pottery and porcelain, have advantages such as the stripping quantity of harmful elements such as physical strength height, Heat stability is good, inexpensive, lead and cadmium is low, are a kind of ideal solid support materials, do not find so far about with adulterated TiO
2Be carried on pottery or stoneware patent.The TiO that the present invention makes
2Film (the TiO of sensitization especially
2Film) ability of acquisition highly effective nano antibiotic function and degradable organic pollutant especially can be used as the ideal material for water treatment.The pottery of this highly effective nano antibiotic function can have the comprehensive action to water molecules simultaneously, is used to improve the ability of the dissolved oxygen of water; Dissolving power to soap increases, surface tension reduces, also has certain interfacial activity effect, has the pollutent ability of decomposition; Can be used for processing such as tap water, cleaning, domestic water, swimming pool water, can also be used for the processing of waste water etc.
Summary of the invention
The present invention seeks to: propose a kind of highly effective nano antibiotic functional ceramic and preparation method and application, the nano functional pottery has powerful antibiotic and germicidal action, organic pollutant to trace in tap water or the domestic water etc. has the ability of thorough decomposition, and in use human body is not produced harm.The present invention is especially to adopting nano-TiO
2The technology of photocatalysis technology sterilization is improved, and T improves the photochemical catalysis effect; Owing to mixed silver and rare earth, making special-purpose sterilization ball or other vessel in the dark also has germicidal action simultaneously.Especially pottery and stoneware ball are used for the efficient, durable of water and the application method of purifying treatment easily to propose a kind of will sterilize pottery or stoneware.
Technical scheme of the present invention is: the preparation method of highly effective nano antibiotic functional ceramic prepares adulterated TiO
2Photocatalyst presoma-doped titanic acid colloidal sol, the biscuiting body and the glaze firing body of preparation pottery or stoneware, adopt sol-gel method that doped titanic acid colloidal sol is loaded on pottery or stoneware surface, promptly mix, obtain nano-TiO through roasting with rare earth element ions such as silver, cerium or lanthanums
2Photocatalysis ceramics or stoneware.Preparation technology of the present invention may further comprise the steps:
1, preparation doped Ti O
2The preparation method of photocatalyst presoma-doped titanic acid colloidal sol, it is characterized in that metatitanic acid colloidal sol be by butyl (tetra) titanate, acid, alcohol, water, ethylene glycol amine according to its molar mass than 1: 6~10: 8~20: 2~6: 1~5, described acid is hydrochloric acid, oxalic acid, Glacial acetic acid or methacrylic acid etc.; Described alcohol is ethanol, n-propyl alcohol, Virahol or propyl carbinol etc.Add rare earth element ions such as silver, cerium or lanthanum again, i.e. silver: cerium or lanthanum element ratio are 1: 0.3~2, its quality and be 0.1~2% of colloidal sol, and described silver, cerium or lanthanum are soluble salt (nitrate or acetate or vitriol); They are fully mixed, obtain even, transparent metatitanic acid colloidal sol.Especially adopt nitrate.
Can also add iron ion, silver is 1: 0.3~2 with the ferro element ratio, and its iron is solubility nitrate or acetate.They are fully mixed, obtain even, transparent doped titanic acid colloidal sol.
2, preparation pottery or stoneware ball biscuiting body
The prescription of pottery or stoneware ball is: planetesimal kaolin 20-30%, Jiujiang kaolin 25-30%, small stream mouth soil 12-18%, bright small stream soil 12-18% etc.; Prescription chemical constitution: SiO
267.7 ± 2%, Al
2O
327.2 ± 2%, K
2O 2.5 ± 0.5%, Fe
2O
31.4 ± 0.2%.Surplus is sodium, calcium, magnesium oxide, and chemical constitution is Na
2O 0.4%, and CaO 0.4%, and Mg 0.4%.The preparation method of pottery or stoneware ball biscuiting body adds the water for ball milling after-filtration with raw material to press dry, by thick white silk, old, concise after, make and be shaped as diameter 10mm~20mm spheroid, wash, dry the back again through repairing and obtain the biscuiting body at 900 ℃ of following roasting 10~15hr, product is stand-by after checking.
3, preparation pottery or stoneware glaze firing body
The prescription of transparent is: feldspar 45 ± 3%, quartz 18 ± 2%, calcite 15 ± 2%, Suzhou soil 8 ± 1% etc., prescription chemical constitution: SiO
261.4 ± 2%, Al
2O
312.1 ± 1%, CaO 11.8 ± 1%, ZnO 6.8 ± 1%, K
2O 4.9 ± 0.5%, and MgO 1.5 ± 0.2%, Na
2O 1.3 ± 0.2%, Fe
2O
30.2 ± 0.05% etc.Carry out ball milling, deironing, sub-sieve separation, adjusting slurry specific gravity 1.45g/ml after in marzacotto, adding 40~60% water then, make slurries glazing on vacuum spraying normal direction pottery or the stoneware biscuiting body, at 1200 ℃ of following roasting 10~15hr, obtain the glaze firing body of pottery or stoneware then.Can prepare pottery or stoneware ball, pottery that bakes or stoneware ball glaze firing body diameter are 10mm~20mm, and any surface finish has certain mechanical strength, and water-intake rate is 25~35%.
4, adopt sol-gel method that doped titanic acid colloidal sol is loaded on pottery or stoneware (tableware of pottery or stoneware or ball) surface.To prepare pottery or stoneware ball biscuiting body impregnated in 1~10min in the doped titanic acid sol solutions, lifting linear velocity is 1~10cm/min, dries, and this process repeats 1~10 thickness with the control load film.
5, load TiO
2Burning till of thin-film ceramics or stoneware tableware or ball.Adopt programmed temperature method in electric furnace, to fire, promptly the speed with 3~8 ℃/min begins to heat up from room temperature, respectively keep 30~40min at 80~160 ℃, 170~240 ℃, 280~360 ℃, 400~500 ℃, outlet temperature rises to 500~600 ℃, keep cooling to room temperature with the furnace behind the 60min, obtaining diameter is the efficient nano TiO of 10mm~20mm
2Photocatalysis sterilization pottery or stoneware tableware or ball finished product.
The application of highly effective nano antibiotic functional ceramic, described pottery or stoneware be the pottery and or the stoneware ball, be used for water treatment applications., also can be pottery or stoneware tableware, in particular for high-grade sclerotin ceramic.
Characteristics of the present invention are: the pottery or stoneware utensil or the ball that utilize the present invention to make, TiO on the carrier
2Film transverse section SEM photo demonstrates its good structure.The present invention is the efficient nano TiO to preparing also
2The physico-chemical property of photocatalysis sterilization pottery or stoneware tableware or ball detects, and the ability of organic pollutant in the sterilising effect of finished product, the purifying slightly polluted water is also tested, and the present invention adopts photoactivated nano-TiO
2The photocatalysis technology sterilization, TiO
2Under the effect of light, can produce very strong hydroxyl radical free radical of oxidation capacity and active oxygen, can kill various bacteriums, also can make various organic matter degradations become harmless simple inorganics.Obviously than plain TiO
2Photocatalysis sterilization efficient height, the sterilization ability improves more than 20%.The present invention is at TiO
2In mixed the generation that iron, rare earth ion are intended to promote hydroxyl radical free radical and active oxygen, improve the photochemical catalysis effect; Simultaneously, make the sterilization ball that germicidal action in the dark also be arranged, the processing of water and tap water is had better effect owing to mixed silver and rare earth.The present invention is also with adulterated TiO
2The system film is carried on pottery or stoneware surface, makes it fully to contact with process object, improves treatment effect.It is the carrier of catalyzer that the present invention selects the pottery of physical strength height, Heat stability is good or stoneware for use, and main component is silicon oxide, aluminum oxide, titanium oxide etc., its chemical form and TiO
2Photocatalyst is similar, easily forms chemical bond between them and in conjunction with firmly, loaded film is difficult drop-off also.Therefore it will be very efficient, durable and easily this sterilization pottery or stoneware or ceramic and stoneware ball being used to drink water purification.
The charge capacity of the photocatalysis membrana of finished product of the present invention on pottery or stoneware ball is 0.21mg/cm
2, TiO
2Particle diameter is 15~20nm, and the thickness of loaded film is 300~400nm.The efficient nano TiO of present method preparation
2Photocatalysis antibacterial pottery or stoneware ball are 98~100% to the sterilization rate of bacterium in the water and colibacillus 24h, to COD (chemical oxygen demand (COD)) removal effect in the multiple micro-polluted water also clearly.
Description of drawings
Fig. 1 is efficient nano TiO of the present invention
2Photocatalysis sterilization pottery or stoneware ball
Fig. 2 is TiO on pottery of the present invention or the stoneware carrier
2Film transverse section SEM photo
Embodiment
Efficient nano TiO
2The embodiment of the preparation technology of photocatalysis sterilization pottery or stoneware ball, physicochemical property detection, sterilization and purifying water effect test is as follows:
Step 1, doped Ti O
2The preparation of presoma-metatitanic acid colloidal sol
Get an amount of butyl (tetra) titanate, acid, alcohol, water and ethylene glycol amine earlier, its molar mass ratio is: butyl (tetra) titanate: acid: alcohol: water: ethylene glycol amine equals 1: 6~and 10: 8~20: 2~6: 1~5, described acid is hydrochloric acid, oxalic acid, Glacial acetic acid or methacrylic acid etc., and described alcohol is ethanol, n-propyl alcohol, Virahol or propyl carbinol etc.Add rare earth element ions such as silver, iron, cerium or lanthanum (each element ratio equates, its quality and less than 0.1~2% of colloidal sol) again and make, its silver, iron, cerium or lanthanum are solubility nitrate.They are fully mixed, obtain even, transparent doped titanic acid colloidal sol.
Step 2, preparation pottery or stoneware ball biscuiting body
The prescription of pottery or stoneware ball is: planetesimal kaolin 20-30%, Jiujiang kaolin 25-30%, small stream mouth soil 12-18%, bright small stream soil 12-18% etc.; Prescription chemical constitution: SiO
267.7 ± 2%, Al
2O
327.2 ± 2%, K
2O 2.5 ± 0.5%, Fe
2O
31.4 ± 0.2%.Surplus is sodium, calcium, magnesium oxide, and chemical constitution is Na
2O 0.4%, and CaO 0.4%, and Mg 0.4%.The preparation method of pottery or stoneware ball biscuiting body adds the water for ball milling after-filtration with raw material to press dry, by thick white silk, old, concise after, make and be shaped as diameter 10mm~20mm spheroid, wash, dry the back again through repairing and obtain the biscuiting body at 900 ℃ of following roasting 10~15hr, product is stand-by after checking.
Step 3, preparation pottery or stoneware ball glaze firing body
The prescription of transparent is: feldspar 45 ± 3%, quartz 18 ± 2%, calcite 15 ± 2%, Suzhou soil 8 ± 1% etc., prescription chemical constitution: SiO
261.4 ± 2%, Al
2O
312.1 ± 1%, CaO 11.8 ± 1%, ZnO 6.8 ± 1%, K
2O 4.9 ± 0.5%, and MgO 1.5 ± 0.2%, Na
2O 1.3 ± 0.2%, Fe
2O
30.2 ± 0.05% etc.Carry out ball milling, deironing, sub-sieve separation, adjusting slurry specific gravity 1.45g/ml after in marzacotto, adding 40~60% water then, make slurries glazing on vacuum spraying normal direction pottery or the stoneware ball biscuiting body, at 1200 ℃ of following roasting 10~15hr, obtain the glaze firing body of pottery or stoneware ball then.Pottery that bakes or stoneware spherical diameter are 10mm~20mm, and any surface finish has certain mechanical strength, and water-intake rate is 25~35%.
Step 4, sol-gel method load on pottery or stoneware ball surface with metatitanic acid colloidal sol
To prepare pottery or stoneware ball biscuiting body impregnated in 1~10min in the doped titanic acid sol solutions, lifting linear velocity is 1~10cm/min, dries, and this process repeats 1~10 thickness with the control load film.
Step 5, load TiO
2Burning till of thin-film ceramics or stoneware ball
Adopt programmed temperature method in electric furnace, to fire, promptly the speed with 3~8 ℃/min begins to heat up from room temperature, respectively keep 30~40min at 80~160 ℃, 170~240 ℃, 280~360 ℃, 400~500 ℃, outlet temperature rises to 500~600 ℃, keep cooling to room temperature with the furnace behind the 60min, obtaining diameter is the efficient nano TiO of 10mm~20mm
2Photocatalysis sterilization pottery or stoneware ball finished product (seeing accompanying drawing 1).
Step 6, efficient nano TiO
2Photocatalysis ceramics or stoneware ball physicochemical property detect
The detection method and the result of main physicochemical property are as follows:
1. according to standard GB/T3298-91 " domestic ceramics device thermal stability determination method ", record efficient nano TiO
2Photocatalysis ceramics or stoneware ball do not ftracture standing to change between 250 ℃~20 ℃ for 3 times, show that thermostability meets national standard.
2. according to standard GB/T3534-2002 " domestic ceramics device aluminium, cadmium stripping measuring method ", record Pb in two kinds of anti-bacteria ceramics
2+Stripping quantity less than 0.1ppm, Cd
2+Stripping quantity less than 0.01ppm, all be lower than national standard.
3. adopt weighing method to record TiO
24 the charge capacity amounts of film on pottery or stoneware ball are 0.23mg/cm
2
4. use scanning electron microscope method (SEM) to measure TiO
2The configuration of surface of film and thickness the results are shown in accompanying drawing 2.The photo below is pottery or stoneware ball glaze, is the TiO of load on the glaze
2Film shows that face is even, smooth, TiO
2Particle diameter is about about 20nm, and the thickness of film is about 300~400nm, and thickness is even.
Step 6, efficient nano TiO
2Photocatalysis ceramics or stoneware ball sterile test
Sterile test has adopted dual mode, and a kind of is to place a certain amount of sewage in the food and drink tool, and timing sampling is measured bacterium, is referred to as " immersion " sterile test; Another kind is to allow food and drink tool inwall keep the sewage rete, regularly measures bacterium with moistening aseptic cotton scouring wall, is referred to as " film contact " sterile test.Bacteria-measuring carries out according to the flat band method among the standard GB 5750-85 in the sample solution, and coil determination carries out according to the multitube fermentation method among the standard GB 5750-85 in the sample solution.24hr soaks sterile test and shows, when total plate count in the water sample is that 2900/ml, intestinal bacteria are when being 790 floras/100ml milliliter, its to the sterilization rate of bacterium greater than 98.0%, to colibacillary sterilization rate is 99%, and film contact sterile test is 100% to bacterium and colibacillary sterilization rate.
Step 7, efficient nano TiO
2Photocatalysis ceramics or the test of stoneware ball place to go organic pollutant
With the 300W medium pressure mercury lamp is light source, adds water and a certain amount of TiO of 1 liter of little pollution
2Photocatalysis ceramics or stoneware ball are measured COD behind the 1h
CrValue (chemical oxygen demand (COD)) changes, and the result is: phenol synthetic water COD
CrClearance is 80.5%, the COD of dyeing waste water
CrrValue is 64.4%, the COD of pharmacy waste water
CClearance is 70%, the Qinhuaihe River, Nanjing water COD
CrClearance is 50%.
Claims (10)
1, the preparation method of highly effective nano antibiotic functional ceramic is characterized in that: prepare adulterated TiO
2Photocatalyst presoma-doped titanic acid colloidal sol, the biscuiting body and the glaze firing body of preparation pottery or stoneware, adopt sol-gel method that doped titanic acid colloidal sol is loaded on pottery or stoneware surface, promptly mix, obtain nano-TiO through roasting with rare earth element ions such as silver, cerium or lanthanums
2Photocatalysis ceramics or stoneware.
2,, it is characterized in that adopting doped Ti O according to the preparation method of the described highly effective nano antibiotic functional ceramic of claim 1
2The preparation method of photocatalyst presoma-assorted metatitanic acid colloidal sol, metatitanic acid colloidal sol be by butyl (tetra) titanate, acid, alcohol, water, ethylene glycol amine according to its molar mass than 1: 6~10: 8~20: 2~6: 1~5, described acid is hydrochloric acid, oxalic acid, Glacial acetic acid or methacrylic acid etc.; Described alcohol is ethanol, n-propyl alcohol, Virahol or propyl carbinol etc.; Add rare earth element ions such as silver, cerium or lanthanum again, promptly silver, cerium or lanthanum element ratio are 1: 0.3~2, its quality and be 0.1~2% of colloidal sol, and described silver, cerium or lanthanum are soluble salt; They are fully mixed, obtain even, transparent metatitanic acid colloidal sol.
3, according to the preparation method of the described highly effective nano antibiotic functional ceramic of claim 1, the preparation method who it is characterized in that pottery or stoneware biscuiting body is: the prescription of biscuiting base substrate is: planetesimal kaolin 20~30%, Jiujiang kaolin 25~30%, small stream mouth soil 12~18%, bright small stream soil 12~18% etc.; Prescription chemical constitution: SiO
267.7 ± 2%, Al
2O
327.2 ± 2%, K
2O 2.5 ± O.5%, Fe
2O
31.4 ± 0.2%, surplus is sodium, calcium, magnesium oxide, i.e. Na
2O 0.4%, and CaO 0.4%, and MgO 0.4%.
4, according to the preparation method of the described highly effective nano antibiotic functional ceramic of claim 2, the preparation method who it is characterized in that pottery or stoneware carrier biscuiting base substrate is, the biscuiting body for preparing pottery or stoneware earlier, manufacture craft is: formula material → add water for ball milling → press filtration to extract → thick white silk → old → 2 time vacuum is concise → make diameter and be 10mm~20mm pottery or stoneware ball or other goods → dry → repair to wash → dry → in 900 ℃ of following roasting 10~15hr → checks → stand-by, obtain pottery or stoneware biscuiting body.
5, according to the preparation method of the described highly effective nano antibiotic functional ceramic of claim 4, the preparation method who it is characterized in that pottery or stoneware biscuiting body is, the configuration marzacotto, its composition is: feldspar 45 ± 3%, quartz 18 ± 2%, calcite 15 ± 2%, Suzhou soil 8 ± 1% etc., prescription chemical constitution: SiO
261.4 ± 2%, Al
2O
312.1 ± 1%, CaO 11.8 ± 1%, ZnO 6.8 ± 1%, K
2O 4.9 ± 0.5%, and MgO 1.5 ± 0.2%, Na
2O 1.3 ± 0.2%, Fe
2O
30.2 ± 0.05% etc.
6, according to the preparation method of the described highly effective nano antibiotic functional ceramic of claim 5, it is characterized in that the marzacotto collocation method is, marzacotto added carry out ball milling, deironing, sub-sieve behind 40~60% water and separate, regulate slurry specific gravity 1.45g/ml, make slurries glazing on vacuum spraying normal direction pottery or the stoneware biscuiting body, 1200 ℃ of following glaze firing, obtain the glaze firing body of pottery or stoneware ball then.
7, according to the preparation method of claim 2 or 6 described highly effective nano antibiotic functional ceramics, it is characterized in that: the preparation technology of pottery or stoneware glaze firing body adopts sol-gel method that doped titanic acid colloidal sol is loaded on pottery or stoneware ball surface, the glaze firing body of pottery or stoneware ball floods 1~10min in the doped titanic acid sol solutions, lifting the linear velocity of leaving liquid level is 1~10cm/min, dry, this process repeats 1~10 time.
8, according to the preparation method of the described highly effective nano antibiotic functional ceramic of claim 7, the TiO that it is characterized in that the glaze firing load
2Pottery or stoneware, adopt programmed temperature method in electric furnace, to fire, promptly the speed with 3~8 ℃/min begins to heat up from room temperature, respectively keep 30~40min at 80~160 ℃, 170~240 ℃, 280~360 ℃, 400~500 ℃, outlet temperature rises to 500~600 ℃, keep cooling to room temperature with the furnace behind the 60min, obtaining diameter is the efficient nano TiO of 10mm~20mm
2Photocatalysis sterilization pottery or stoneware finished product.
9, according to the preparation method of the described highly effective nano antibiotic functional ceramic of claim 2, it is characterized in that adding iron ion, silver element: the ferro element ratio is 1: 0.3~2, and its silver, iron, cerium or lanthanum are solubility nitrate.
10, the application of highly effective nano antibiotic functional ceramic, it is characterized in that institute's pottery or stoneware for the pottery and or the stoneware ball, be used for water treatment.
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