CN106348787A - Rare earth added antibacterial ceramic glaze and preparation method thereof - Google Patents

Rare earth added antibacterial ceramic glaze and preparation method thereof Download PDF

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Publication number
CN106348787A
CN106348787A CN201610990367.1A CN201610990367A CN106348787A CN 106348787 A CN106348787 A CN 106348787A CN 201610990367 A CN201610990367 A CN 201610990367A CN 106348787 A CN106348787 A CN 106348787A
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parts
oxide
rare earth
glaze
ceramic glaze
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CN201610990367.1A
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Inventor
张焕明
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Foshan Lan Tu Science And Technology Ltd
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Foshan Lan Tu Science And Technology Ltd
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Priority to CN201610990367.1A priority Critical patent/CN106348787A/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • C04B41/86Glazes; Cold glazes
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00Glasses, glazes or enamels with special properties
    • C03C2204/02Antibacterial glass, glaze or enamel

Abstract

The invention provides rare earth added antibacterial ceramic glaze and a preparation method thereof and relates to the field of ceramic preparation. The ceramic glaze mainly comprises the following raw materials in parts by weight: 25-45 parts of silicon dioxide, 5-13 parts of aluminum oxide, 3-5 parts of deep sea mineral mud, 3-6 parts of magnesium oxide, 2-6 parts of copper oxide, 1-5 parts of zinc oxide, 4-8 parts of zirconium silicate, 1-3 parts of titanium dioxide, 3-9 parts of opal shale, 0.2-0.5 part of polyethylene glycol, 2-7 parts of sodium metaphosphate, 2-12 parts of rare-earth metal oxide and 67-95 parts of organic solvents; and the raw materials also comprise 2-6 parts of silver nitrate. The rare earth added antibacterial ceramic glaze provided by the invention is lasting in antibacterial time and high in efficiency, and other performances of ceramic products are not influenced.

Description

A kind of interpolation rare earth antibacterial ceramic glaze and preparation method thereof
Technical field
The invention belongs to ceramic technology field, concretely relate to a kind of interpolation rare earth antibacterial ceramic glaze and its preparation side Method.
Background technology
Our wares used in everyday, typically all wear smooth, smooth clothes all over the body, and particularly domestic ceramics is right " clothes " are more exquisite, and have is as white as polished jade, and have is colorful, very attractive in appearance.This clothes of pottery, are named as " glaze ".Pottery Enamel has the physics being analogous to glassy state and chemical characteristic, waterproof, smooth and glossy, is difficult to stain, and can improve system The mechanical strength of product, heat stability and chemical stability.Glaze paint also can adopt the artistic effect to strengthen product for the various decorations.
Ceramic applications are quite varied, and wherein demand in life for the ceramic is bigger, such as sanitary ware, tableware etc..With Growth in the living standard, health is the problem that people become more concerned with, therefore, the modern widely used glazing of pottery using Technique improves the external quality of ceramic.With the raising of social progress and people's living standard, control and eliminate harmful Antibacterial be multiplied into an important problem.Directly during ceramic is standby, add antibacterial in prior art, can affect Other performances of pottery, and antibacterial effect is not lasting.
Content of the invention
For solving above-mentioned technical problem, the present invention provides a kind of interpolation rare earth antibacterial ceramic glaze and preparation method thereof.To carry Lasting, efficient for a kind of antibacterial time, and do not interfere with the antibacterial ceramic glaze of other performances of ceramic.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of interpolation rare earth antibacterial ceramic glaze, by parts by weight meter, mainly includes following raw material: silicon dioxide 25-45 part, three oxygen Change two aluminum 5-13 parts, deep-sea mineral mud 3-5 part, magnesium oxide 3-6 part, copper oxide 2-6 part, zinc oxide 1-5 part, Zirconium orthosilicate. 4-8 part, Titanium dioxide 1-3 part, opal shale 3-9 part, Polyethylene Glycol 0.2-0.5 part, Polymeric sodium metaphosphate. 2-7 part, rare-earth oxide 2-12 part, organic solvent 67-95 part.
Preferably, in the preferred embodiment, described raw material also includes silver nitrate 2-6 part;Antiseptic elements silver with Zinc oxide combines, strong antibacterial, and the time is lasting.
Preferably, in the preferred embodiment, described rare-earth oxide is Dithulium trioxide, yittrium oxide, oxidation Any two kinds of compositions in scandium, lanthana or Erbia;Add rare-earth oxide, oxidation silver antibacterial agent can be fixed, It is made slowly to discharge, holding effect is more long.
Preferably, in the preferred embodiment, described organic solvent is in dimethylbenzene, acetone or dehydrated alcohol A kind of.
In addition, present invention also offers a kind of preparation method adding rare earth antibacterial ceramic glaze, comprising the following steps:
(1) 25-45 part silicon dioxide, 5-13 part aluminium sesquioxide, 3-5 part deep-sea mineral mud, 3-6 part oxygen are weighed by weight Change magnesium, 2-6 part copper oxide, 1-5 part zinc oxide, 4-8 part Zirconium orthosilicate., 1-3 part titanium dioxide, 3-9 part opal shale, 0.2- 0.5 part of Polyethylene Glycol, 2-7 part Polymeric sodium metaphosphate., 2-12 part rare-earth oxide and 2-6 part silver nitrate add in agitator, with 60-100r/min stirs, by each component mix homogeneously;
(2) again the raw material after mixing is sent in high temperature furnace, under nitrogen protection, in 1000-1100 DEG C of high-temperature calcination twice, obtain Microcrystalline powder;
(3) described microcrystalline powder is added in ball mill, and add described organic solvent wet ball-milling, in 20-40r/min ball milling 21-25 hour, being milled to fineness is 300-500 mesh, and sieve to obtain pulpous state glaze liquid;
(4) described pulpous state glaze liquid is uniformly sprayed on ceramic body;
(5) ceramic body after described glaze spraying is sintered in argon, sintering temperature is 1100-1280 DEG C, sintering time For 30-160min, it is cooled to 20-35 DEG C after stopping heating, obtains finished product.
Preferably, in the preferred embodiment, described sintering temperature is warming up to the speed of 100 DEG C/min 1100-1280℃.
Preferably, in the preferred embodiment, described microcrystalline powder particle diameter is 30-100nm;Mixed-powder passes through After high temperature is calcined repeatedly, obtain the crystal grain refining, can faster, more permanently discharge antiseptic elements.
Beneficial effects of the present invention: the invention provides a kind of antibacterial time is persistently, efficiently, and do not interfere with ceramic The antibacterial ceramic glaze of other performances.Antiseptic elements silver is combined with zinc oxide, strong antibacterial, and the time is lasting.Add rare earth metal Oxide, forms network structure, can fix oxidation silver antibacterial agent so as to slow discharge, holding effect is more long.Mixed-powder passes through After high temperature is calcined repeatedly, obtain the crystal grain refining, can faster, more permanently discharge antiseptic elements, the albumen in addition adding Stone shale, deep-sea mineral mud, also can improve the antibiotic and sterilizing performance of ceramic glaze.
Specific embodiment
With reference to specific embodiment, technical scheme of the present invention is further described.
Embodiment 1:
A kind of preparation method adding rare earth antibacterial ceramic glaze, comprises the following steps:
(1) 25 parts of silicon dioxide, 5 parts of aluminium sesquioxide, 3 parts of deep-sea mineral mud, 3 parts of magnesium oxide, 2 parts of oxygen are weighed by weight Change copper, 1 part of zinc oxide, 4 parts of Zirconium orthosilicate .s, 1 part of titanium dioxide, 3 parts of opal shale, 0.2 part of Polyethylene Glycol, 2 parts of Polymeric sodium metaphosphate ies, 1 part of Dithulium trioxide, 1 part of Scia and 2 parts of silver nitrate add in agitator, with 60r/min stirring, by each component mix homogeneously;
(2) again the raw material after mixing is sent in high temperature furnace, under nitrogen protection, in 1000 DEG C of high-temperature calcinations twice, obtain particle diameter Microcrystalline powder for 30nm;
(3) microcrystalline powder is added in ball mill, and add 67 parts of dehydrated alcohol wet ball-millings, little in 20r/min ball milling 21 When, being milled to fineness is 300 mesh, and sieve to obtain pulpous state glaze liquid;
(4) pulpous state glaze liquid is uniformly sprayed on ceramic body;
(5) by the ceramic body after glaze spraying in argon, it is warming up to 1100 DEG C with the speed of 100 DEG C/min and is sintered, sintering Time is 30min, is cooled to 20 DEG C, obtains finished product after stopping heating.
Embodiment 2:
A kind of preparation method adding rare earth antibacterial ceramic glaze, comprises the following steps:
(1) 25-45 part silicon dioxide, 5-13 part aluminium sesquioxide, 3-5 part deep-sea mineral mud, 3-6 part oxygen are weighed by weight Change magnesium, 2-6 part copper oxide, 1-5 part zinc oxide, 4-8 part Zirconium orthosilicate., 1-3 part titanium dioxide, 3-9 part opal shale, 0.2- 0.5 part of Polyethylene Glycol, 2-7 part Polymeric sodium metaphosphate., 6 parts of yittrium oxide, 6 parts of Scias and 6 parts of silver nitrate add in agitators, with 100r/min stirs, by each component mix homogeneously;
(2) again the raw material after mixing is sent in high temperature furnace, under nitrogen protection, in 1100 DEG C of high-temperature calcinations twice, obtain particle diameter Microcrystalline powder for 100nm;
(3) microcrystalline powder is added in ball mill, and add 95 parts of dehydrated alcohol wet ball-millings, little in 40r/min ball milling 25 When, being milled to fineness is 500 mesh, and sieve to obtain pulpous state glaze liquid;
(4) pulpous state glaze liquid is uniformly sprayed on ceramic body;
(5) by the ceramic body after glaze spraying in argon, it is warming up to 1280 DEG C with the speed of 100 DEG C/min and is sintered, sintering Time is 160min, is cooled to 35 DEG C, obtains finished product after stopping heating.
Embodiment 3:
A kind of preparation method adding rare earth antibacterial ceramic glaze, comprises the following steps:
(1) weigh by weight 35 parts of silicon dioxide, 6 parts of aluminium sesquioxide, 4 parts of deep-sea mineral mud, 4.5 parts of magnesium oxide, 4 parts Copper oxide, 3 parts of zinc oxide, 6 parts of Zirconium orthosilicate .s, 2 parts of titanium dioxide, 6 parts of opal shale, 0.35 part of Polyethylene Glycol, 4.5 parts of inclined phosphorus Sour sodium, 3 parts of yittrium oxide, 4 parts of lanthanas and 4 parts of silver nitrate add in agitator, with 80r/min stirring, will be equal for the mixing of each component Even;
(2) again the raw material after mixing is sent in high temperature furnace, under nitrogen protection, in 1050 DEG C of high-temperature calcinations twice, obtain particle diameter Microcrystalline powder for 65nm;
(3) microcrystalline powder is added in ball mill, and add 81 parts of dehydrated alcohol wet ball-millings, little in 30r/min ball milling 23 When, being milled to fineness is 400 mesh, and sieve to obtain pulpous state glaze liquid;
(4) pulpous state glaze liquid is uniformly sprayed on ceramic body;
(5) by the ceramic body after glaze spraying in argon, it is warming up to 1190 DEG C with the speed of 100 DEG C/min and is sintered, sintering Time is 95min, is cooled to 27 DEG C, obtains finished product after stopping heating.
Sterilization treatment is carried out to the antibacterial ceramic products surface of ceramic glaze of the present invention preparation, is coated with certain density thin Bacterium, after 24h, tests its antibiotic rate.
Table 1 embodiment 1-3 the performance test results
Embodiment Staphylococcus aureuses Escherichia coli
Embodiment 1 99.4 98.32
Embodiment 2 99.2 98.05
Embodiment 3 99.5 98.72
Using embodiment 1-3 antibacterial ceramic glaze preparation antibacterial ceramic products to the sterilizing rate of staphylococcus aureuses 99% More than, to colibacillary sterilizing rate more than 98%, bactericidal effect is excellent.

Claims (7)

1. a kind of interpolation rare earth antibacterial ceramic glaze is it is characterised in that by parts by weight meter, mainly include following raw material: titanium dioxide Silicon 25-45 part, aluminium sesquioxide 5-13 part, deep-sea mineral mud 3-5 part, magnesium oxide 3-6 part, copper oxide 2-6 part, zinc oxide 1-5 Part, Zirconium orthosilicate. 4-8 part, titanium dioxide 1-3 part, opal shale 3-9 part, Polyethylene Glycol 0.2-0.5 part, Polymeric sodium metaphosphate. 2-7 part, Rare-earth oxide 2-12 part, organic solvent 67-95 part.
2. according to claim 1 interpolation rare earth antibacterial ceramic glaze it is characterised in that: described raw material also includes silver nitrate 2- 6 parts.
3. according to claim 1 interpolation rare earth antibacterial ceramic glaze it is characterised in that: described rare-earth oxide be oxygen Change any two kinds of compositions in thulium, yittrium oxide, Scia, lanthana or Erbia.
4. according to claim 1 interpolation rare earth antibacterial ceramic glaze it is characterised in that: described organic solvent be dimethylbenzene, One of acetone or dehydrated alcohol.
5. a kind of preparation method of the interpolation rare earth antibacterial ceramic glaze as described in any one as claim 1-4 is it is characterised in that wrap Include following steps:
(1) 25-45 part silicon dioxide, 5-13 part aluminium sesquioxide, 3-5 part deep-sea mineral mud, 3-6 part oxygen are weighed by weight Change magnesium, 2-6 part copper oxide, 1-5 part zinc oxide, 4-8 part Zirconium orthosilicate., 1-3 part titanium dioxide, 3-9 part opal shale, 0.2- 0.5 part of Polyethylene Glycol, 2-7 part Polymeric sodium metaphosphate., 2-12 part rare-earth oxide and 2-6 part silver nitrate add in agitator, with 60-100r/min stirs, by each component mix homogeneously;
(2) again the raw material after mixing is sent in high temperature furnace, under nitrogen protection, in 1000-1100 DEG C of high-temperature calcination twice, obtain Microcrystalline powder;
(3) described microcrystalline powder is added in ball mill, and add described organic solvent wet ball-milling, in 20-40r/min ball milling 21-25 hour, being milled to fineness is 300-500 mesh, and sieve to obtain pulpous state glaze liquid;
(4) described pulpous state glaze liquid is uniformly sprayed on ceramic body;
(5) ceramic body after described glaze spraying is sintered in argon, sintering temperature is 1100-1280 DEG C, sintering time For 30-160min, it is cooled to 20-35 DEG C after stopping heating, obtains finished product.
6. according to claim 5 add rare earth antibacterial ceramic glaze preparation method it is characterised in that: described sintering temperature It is warming up to 1100-1280 DEG C with the speed of 100 DEG C/min.
7. according to claim 5 add rare earth antibacterial ceramic glaze preparation method it is characterised in that: described microcrystalline powder Particle diameter is 30-100nm.
CN201610990367.1A 2016-11-10 2016-11-10 Rare earth added antibacterial ceramic glaze and preparation method thereof Pending CN106348787A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107721402A (en) * 2017-11-21 2018-02-23 苏州科茂电子材料科技有限公司 A kind of preparation method of antimicrobial form piezoelectric
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
CN111548015A (en) * 2020-04-24 2020-08-18 佛山科学技术学院 Ceramic glaze with antibacterial and mildew-proof effects and preparation method and application thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107721402A (en) * 2017-11-21 2018-02-23 苏州科茂电子材料科技有限公司 A kind of preparation method of antimicrobial form piezoelectric
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
CN111548015A (en) * 2020-04-24 2020-08-18 佛山科学技术学院 Ceramic glaze with antibacterial and mildew-proof effects and preparation method and application thereof

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