CN105601113B - Antibacterial enamel material and its preparation method and application - Google Patents
Antibacterial enamel material and its preparation method and application Download PDFInfo
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- CN105601113B CN105601113B CN201511025580.0A CN201511025580A CN105601113B CN 105601113 B CN105601113 B CN 105601113B CN 201511025580 A CN201511025580 A CN 201511025580A CN 105601113 B CN105601113 B CN 105601113B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
- F24C7/00—Stoves or ranges heated by electric energy
- F24C7/02—Stoves or ranges heated by electric energy using microwaves
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
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Abstract
The present invention provides antibacterial enamel materials and its preparation method and application, which includes: base stock；Adhesive agent, adjuvant；And antibacterial agent.The antibacterial enamel material, while with the performances such as good high temperature resistant, acid and alkali-resistance, scratch-resistant, corrosion-resistant, there is ideal anti-microbial property, lower sintering temperature, gas will not be generated when in conjunction with metal base, the compactness of enamel is good, and pin hole rate is low, and with the adherence of metal base is good, binding force is strong, enamel material is not easily to fall off, in addition, the enamel material has lesser absorbing property, microwave output rating is high.
Description
Technical field
The present invention relates to field of material technology, specifically, being related to antibacterial enamel material and its preparation method and application.
Background technique
Enamel material is with its high-grade appearance, brilliant rub resistance, acid and alkali-resistance, corrosion-resistant, high temperature resistance and good
Performance easy to clean is constantly subjected to widely pay close attention to and study.The internal work environment temperature of the kitchen appliances product such as micro-wave oven and oven
Degree is high, Long Term Contact greasy dirt, acid alkaline seasoning and detergent, easily with sharp, sharp object contacts, and micro-wave oven with
And micro-wave oven attachment is chronically exposed under microwave environment, these require micro-wave oven, oven inner container and its accessory class product
Outer surface will have the performances such as high temperature resistant, acid and alkali-resistance, scratch-resistant, corrosion-resistant；In addition, since kitchen appliance class product high-frequency connects
Touch the substances such as food, condiment, it is easy to lead to the growth of bacterium, it is therefore desirable to which kitchen appliance class product there will be the performance of antibacterial
Consumer demand can be better met.Microwave outer surface of liner will also have humble wave to damage in addition to meeting above-mentioned performance
The performance of consumption, and above-mentioned performance be microwave current, oven and its common stainless steel material of accessory class product, cold-rolled steel sheet or
Heat zinc coating plate outer surface, which is dusted, waits materials institute inaccessiable.Carrying out enamel spraying material processing in metal surface can meet
The problems such as easily being abraded with solution microwave current, oven and its resistance to temperature difference of accessory class product, perishable, surface.
But there is also certain problems for current enamel technology, in terms of microwave, oven and its accessory class product
The problem of be mainly manifested in: 1) metal surface carry out enamel spraying material processing after, surface is also easy to produce pin hole, leads to enamel appearance
Difference, smoothness are low；2) frit for porcelain enamel ingredient has absorbing property, and the microwave oven inner container for causing enamel material to be surface-treated absorbs big
The microwave energy of amount, so that micro-wave oven delivery efficiency declines；3) poor adhesive force between enamel material and metal base, enamel layer
It is easy to fall off；4) enamel class product does not have anti-microbial property.Problem above constrain enamel material micro-wave oven and oven and its
Application on accessory class product.
Thus, current enamel technology still has much room for improvement.
Summary of the invention
The present invention is the following discovery based on inventor and completes:
Oven and oven accessory class products application enamel technology are more at present, and the liner of oven, the baking tray etc. of oven are attached
Part surface treatment mostly uses enamel material.But since current enamel technology needs 800 DEG C or more of high temperature that can will just ward off
Glaze is sintered in metallic substrate surface, and simple substance carbon micro in metal material (C) is caused to aoxidize with glaze component
Reduction reaction generates hydrogen (H2), the H of generation2Diffusion velocity is substantially accelerated at a higher temperature, quickly expands from glaze inside
It is dissipated to air layer, and then causes enamel surfaces appearance that Pinhole-shaped is presented, influences the material and product that carry out enamel surfaces processing
Appearance and service performance.Moreover, leading to microwave energy containing a large amount of high absorbing property component in existing frit for porcelain enamel composition
Amount loss influences the practical microwave energy utilization rate of micro-wave oven so that microwave delivery efficiency declines.Meanwhile existing kitchen appliance product
It is relatively poor with the adherence between frit for porcelain enamel and metal base, when product is impacted, it be easy to cause the de- of enamel layer
It falls.In addition, kitchen appliance class enamel product product usually all carries out, it is easy to cause under high temperature environment in cook food
The juice and residue of food are adhered to enamel layer surface, and a period of time does not clear up the growth for easilying lead to bacterium, influences to make
The health of user.The problem above of the prior art constrains enamel material in micro-wave oven and microwave attachment, oven and oven attachment
Application on product so that the high temperature resistant of enamel material, acid and alkali-resistance, scratch-resistant, it is corrosion-resistant the advantages that can not be in microwave, oven etc.
Showed in kitchen appliance product.
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, inventor passes through
Cross it is a large amount of explore and experimental verification, propose that a kind of compactness is good, pin hole rate is low, lossy microwave is small, adhesive force is strong or antibacterial
The enamel material haveing excellent performance.
In view of this, in one aspect of the invention, the present invention provides a kind of antibacterial enamel materials.It is according to the present invention
Embodiment, which includes: base stock；Adhesive agent；Adjuvant；And antibacterial agent.Inventors have found that according to this hair
The antibacterial enamel material of bright embodiment, while with the performances such as good high temperature resistant, acid and alkali-resistance, scratch-resistant, corrosion-resistant,
With excellent anti-microbial property, requirement of the user to anti-microbial property and health can satisfy, moreover, the antibacterial enamel material has
Lower sintering temperature will not generate gas when in conjunction with metal base, the compactness of enamel is good, and pin hole rate is low, and with gold
The adherence of category substrate is good, binding force is strong, and enamel material is not easily to fall off, in addition, the enamel material has lesser absorbing property,
Microwave output rating is high.
According to an embodiment of the invention, base stock includes at least one of: the oxide of alkali metal；Third major element
Oxide；The oxide of 4th major element；The oxide of 4th subgroup element.
According to an embodiment of the invention, the oxide of alkali metal is at least one in lithia, sodium oxide molybdena, potassium oxide
Kind；The oxide of third major element is selected from least one of diboron trioxide, aluminum oxide；4th major element
Oxide is silica；The oxide of 4th subgroup element is selected from least one of titanium dioxide, zirconium dioxide.
According to an embodiment of the invention, adhesive agent include at least one of: the oxide of the 5th major element, the 6th is secondary
The oxide of race's element.
According to an embodiment of the invention, the oxide of the 6th subgroup element is molybdenum oxide；The oxide of 5th major element
For selected from least one of antimony oxide, bismuth oxide.
According to an embodiment of the invention, adjuvant includes at least one of: the oxide of alkaline-earth metal；5th subgroup member
The oxide of element；The oxide of 8th race's metallic element；The oxide of lanthanide series；And first B metal element oxidation
Object.
According to an embodiment of the invention, the oxide of alkaline-earth metal be in magnesia, strontium oxide strontia, barium monoxide at least
It is a kind of；The oxide of 5th subgroup element is vanadic anhydride；The oxide of 8th race's metallic element be selected from di-iron trioxide,
At least one of cobalt oxide；The oxide of lanthanide series is selected from least one of cerium sesquioxide, yttria；The
The oxide of one B metal element is copper oxide.
According to an embodiment of the invention, antibacterial agent is selected from least one of nano silver, silver nitrate, zinc oxide.
According to an embodiment of the invention, the gross mass based on antibacterial enamel material, according to mass percentage, antibacterial enamel
Material includes: base stock 73%~89%；Adhesive agent 3%~6%；Adjuvant 8%~21% and antibacterial agent 0.01%~
0.03%.
According to an embodiment of the invention, the gross mass based on antibacterial enamel material, according to mass percentage, antibacterial enamel
Material includes: the oxide 15%~35% of alkali metal；The oxide 4%~12% of alkaline-earth metal；The oxygen of third major element
Compound 8%~16%；The oxide 12%~32% of 4th major element；The oxide 15%~30% of 4th subgroup element；
The oxide 2%~4% of 5th major element；The oxide 2%~4% of 5th subgroup element；The oxidation of 6th subgroup element
Object 1%~2%；The oxide 1%~5% of 8th race's metallic element；The oxide 0.01%~0.02% of lanthanide series；First
The oxide 1%~2% of B metal element；And antibacterial agent 0.01%~0.03%.
According to an embodiment of the invention, not less than 50 microns of the granularity of antibacterial enamel material (being not less than 300 mesh).
In another aspect of this invention, the present invention provides a kind of methods for preparing mentioned-above antibacterial enamel material.
According to an embodiment of the invention, obtaining glaze mixture this method comprises: glaze is mixed, wherein glaze includes base stock,
Adhesive agent, adjuvant and antibacterial agent；Glaze mixture is subjected to melt process, obtains glaze melt；Successively by glaze melt
Water Quenching and drying and processing are carried out, frit is obtained；Frit is subjected to ball-milling treatment, obtains antibacterial enamel material.Invention human hair
It is existing, using this method according to an embodiment of the present invention, can fast and effeciently prepare anti-microbial property is good, sintering temperature is low,
Absorbing property is poor, with the strong antibacterial enamel material of metal base binding ability, and it is simple, convenient, it is easy to accomplish.
In another aspect of the invention, the present invention provides a kind of heating equipments.According to an embodiment of the invention, the society adds
Hot equipment includes: ontology；And it is formed in the coating at least part surface of ontology, the coating is by mentioned-above antibacterial
Enamel material is formed.The heating equipment has all feature and advantage of mentioned-above antibacterial enamel material, not another herein
One repeats.
Antibacterial enamel material according to an embodiment of the present invention and preparation method thereof, it is intended to solve current outer surface and carry out enamel
The micro-wave oven of processing, oven, microwave attachment and oven accessory product surface pinholes rate are high, lossy microwave is big, microwave output effect
Rate is low, does not have the problems such as anti-microbial property.Using alkali metal oxide, the sintering temperature of enamel material can be effectively reduced, mention
The adhesion property of high enamel material and metal base, and then reduce pin hole rate；Using the oxide of lanthanide series, can effectively change
The surface physics effect and chemical action of kind enamel material and metal base, improve the compactness and and Metal Substrate of enamel material
The adhesive force on material surface；The addition of the oxide of 4th subgroup element can effectively improve the glossiness and chemistry of enamel material
Stability, and the covering power of enamel material can be increased, and can have anti-microbial property to a certain extent；Antibacterial agent adds
Enter, can make enamel material that there is good antibacterial ability, in addition, the metal oxide that the present invention uses, relatively existing kitchen appliance
Especially micro-wave oven enamel material has smaller absorbing property, better adherence ability, after can substantially reducing enamel sintering
The pin hole of appearance and the generation of burst porcelain phenomenon.Antibacterial enamel material of the invention be applied to micro-wave oven, oven, microwave attachment and
The surface treatment of oven accessory product, it will solve current technology pin hole rate height, lossy microwave is asked greatly, without anti-microbial property etc.
Topic improves the performances such as the high temperature resistant of the said goods, acid and alkali-resistance, scratch-resistant, corrosion-resistant, while can increase enamel product in kitchen
Utility ratio in electric appliance especially micro-wave oven and oven class product, promotes the quality of such product.
The present invention at least has the advantages that
1) antibacterial enamel material provided by the invention, considerably reduces its sintering temperature, so that base during the sintering process
This is generated without gas, and enamel material compactness is good, pin hole rate is low, appearance；
2) in antibacterial enamel material prescription according to an embodiment of the present invention, without containing the material with strong absorption microwave property
Material, greatly reduces absorption and loss of the enamel material itself for microwave energy, by antibacterial enamel material application of the invention
In microwave oven inner container outer surface, the microwave delivery efficiency of micro-wave oven is improved, so that enamel material is applied in micro-wave oven and its attached
Microwave property in part class product gets a promotion, and enamel material can be enabled more to be widely applied to micro-wave oven and its accessory class production
In product；
3) adhesive agent of antibacterial enamel materials'use according to an embodiment of the present invention with more preferable adhesion property, make enamel
Material can preferably adhere to substrate；
4) antibacterial agent suitable for enamel material of the present invention is added in antibacterial enamel material according to an embodiment of the present invention,
Making material of the present invention not only has the basic performance of enamel material, but also has good anti-microbial property.
Detailed description of the invention
Fig. 1 shows the flow chart of the method according to an embodiment of the present invention for preparing antibacterial enamel material.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the present invention provides a kind of antibacterial enamel materials.According to an embodiment of the invention, should
Antibacterial enamel material includes: base stock；Adhesive agent；Adjuvant；And antibacterial agent.Inventors have found that according to embodiments of the present invention
The antibacterial enamel material, while with the performances such as good high temperature resistant, acid and alkali-resistance, scratch-resistant, corrosion-resistant, anti-microbial property
Preferably, the higher and higher health requirements of user be can satisfy, and the enamel material has lower sintering temperature, with Metal Substrate
Material will not generate gas when combining, and the compactness of enamel is good, and pin hole rate is low, and with the adherence of metal base is good, binding force
By force, enamel material is not easily to fall off, in addition, the antibacterial enamel material has lesser absorbing property, microwave output rating is high.
According to an embodiment of the invention, base stock includes at least one of: the oxide of alkali metal；Third major element
Oxide；The oxide of 4th major element；The oxide of 4th subgroup element.Enamel material according to an embodiment of the present invention
Material, the oxide of alkali metal element impart alkali metal element since the outermost layer of alkali metal atom only has an electronics
Oxide extensive chemical activity, its sintering temperature can be effectively reduced for enamel material, improve the compactness of enamel material；The
The addition of the oxide of three major elements, it is possible to reduce the absorption microwave property of enamel material improves the delivery efficiency of microwave, and
The mechanical performance of enamel material can be improved；The addition of the oxide of 4th major element, can effectively improve enamel material
The mechanical performance of chemical durability and material；The addition of the oxide of 4th subgroup element, can effectively improve enamel material
Glossiness and chemical stability, and the covering power of enamel material can be increased, and can have antibacterial to a certain extent
Performance.
According to an embodiment of the invention, the specific type of base stock is not particularly limited, in some embodiments of the present invention
In, the oxide of alkali metal can be for selected from least one of lithia, sodium oxide molybdena, potassium oxide；The oxidation of third major element
Object can be for selected from least one of diboron trioxide, aluminum oxide；The oxide of 4th major element can be dioxy
SiClx；The oxide of 4th subgroup element can be for selected from least one of titanium dioxide, zirconium dioxide.On selecting as a result,
Stating base stock can make enamel material have lower sintering temperature, gas will not be generated when in conjunction with metal base, with gold
Gas will not be generated by belonging to when substrate combines, and the compactness of enamel is good, and pin hole rate is low, and gas will not be generated when in conjunction with metal base
Body, pin hole rate is low, and the compactness of enamel is good, and strong with the binding force of matrix, not easily to fall off, in addition, between above-mentioned each component, with
It can preferably act synergistically between other components, further increase the service performance of enamel material.
According to an embodiment of the invention, adhesive agent may include the oxide and the 6th subgroup element of the 5th major element
At least one of oxide.The physical property of enamel material can be improved in the addition of 5th major element oxide, can also mention
The adherence ability of high enamel material and metal base；The addition of 6th subgroup element oxide is cooperateed with the 5th main group oxide
Effect, can be further improved the adhesion property between enamel material and metal base.
According to an embodiment of the invention, the specific type of adhesive agent is not particularly limited, in some embodiments of the present invention
In, the oxide of the 6th subgroup element can be molybdenum oxide；The oxide of 5th major element can for selected from antimony oxide,
At least one of bismuth oxide.Adhesion property as a result, between enamel material and metal base is preferable.
According to an embodiment of the invention, adjuvant includes at least one of: the oxide of alkaline-earth metal；5th subgroup member
The oxide of element；The oxide of 8th race's metallic element；The oxide of lanthanide series；And first B metal element oxidation
Object.Inventors have found that the addition of the oxide of alkali earth metal, can effectively improve the chemical resistance and machinery of enamel material
Performance；The addition of the oxide of 5th subgroup element, can be improved the compactness of enamel material layer, and have preferable fluxing work
With；The addition of the oxide of 8th race's metallic element primarily serves toning and increases the effect of adhesion property；The oxygen of lanthanide series
The addition of compound can be effectively improved the surface physics effect and chemical action of enamel material and metal base, improve enamel material
The compactness of material and adhesive force with metallic substrate surface；The addition of first B metal element oxide, can effectively rise
To toning and the effect for increasing anti-microbial property.
According to an embodiment of the invention, the specific type of adjuvant is not particularly limited, in some embodiments of the present invention
In, the oxide of alkaline-earth metal can be for selected from least one of magnesia, strontium oxide strontia, barium monoxide；5th subgroup element
Oxide can be vanadic anhydride；The oxide of 8th race's metallic element can be in di-iron trioxide, cobalt oxide
It is at least one；The oxide of lanthanide series can be for selected from least one of cerium sesquioxide, yttria；First subgroup
The oxide of metallic element is copper oxide.Thereby, it is possible to further decrease sintering temperature, appearance, the physics of enamel material are improved
Chemical property, compactness and binding force of metallic matrix etc., and more favorably cooperateed with each group molecule of enamel material, comprehensive work
With so that enamel material can be widely applied to the products such as micro-wave oven, oven and its attachment with ideal service performance
In.
According to an embodiment of the invention, the specific type of antibacterial agent is not particularly limited, as long as antibacterial can be played effectively
Effect.In some embodiments of the invention, antibacterial agent can in nano silver, silver nitrate, zinc oxide at least
It is a kind of.As a result, antibacterial agent has good high temperature resistance while enamel material has ideal anti-microbial property, fit
It shares in the electric appliances such as micro-wave oven, oven.
According to an embodiment of the invention, the specific proportion of each component is not particularly limited in the antibacterial enamel material, ability
Field technique personnel can be adjusted flexibly according to the actual situation.In some embodiments of the invention, it is based on antibacterial enamel material
The gross mass of material, according to mass percentage, the antibacterial enamel material includes: described matrix agent 73%~89%；It is described close
Agent 3%~6%；The adjuvant 8%~21%；And the antibacterial agent 0.01%~0.03%.Each component can be with as a result,
It is matched with most suitable ratio, so that the enamel material has ideal anti-microbial property, high compactness, low pin hole rate, symbol
Close desired appearance, high adherence and low absorbing property etc..
According to an embodiment of the invention, the gross mass based on antibacterial enamel material, according to mass percentage, the antibacterial
Enamel material includes: the oxide 15%~35% of alkali metal；The oxide 4%~12% of alkaline-earth metal；Third major element
Oxide 8%~16%；The oxide 12%~32% of 4th major element；The oxide 15% of 4th subgroup element~
30%；The oxide 2%~4% of 5th major element；The oxide 2%~4% of 5th subgroup element；6th subgroup element
Oxide 1%~2%；The oxide 1%~5% of 8th race's metallic element；The oxide 0.01%~0.02% of lanthanide series；
The oxide 1%~2% of first B metal element；And antibacterial agent 0.01%~0.03%.Said components and proportion as a result,
Antibacterial enamel material there is the service performance of the enamel material better than other components and proportion, each component collaboration, comprehensive function,
So that the antibacterial enamel material has ideal anti-microbial property, sintering temperature and low, high compactness, low pin hole rate, meets the requirements
The performances such as appearance, high microwave output rating, can be good at the requirement for meeting microwave rate, oven etc..
It should be noted that content can be according to following since the oxide of billows series elements and the content of antibacterial agent are lower
Mode calculates: the quality of the raw material in addition to the oxide of billows series elements and antibacterial agent is based on removing according to 100 percent meter
The oxide of billows series elements and the gross mass of the raw material except antibacterial agent, the mass fraction of antibacterial agent can for 0.01%~
0.03%, the mass fraction of the oxide of lanthanide series can be 0.01%~0.02%.
According to an embodiment of the invention, not less than 50 microns of the granularity of antibacterial enamel material (being not less than 300 mesh).By
This, is conducive to subsequent applications.
In another aspect of this invention, the present invention provides a kind of methods for preparing mentioned-above antibacterial enamel material.
According to an embodiment of the invention, method includes the following steps:
S100: glaze is mixed, and obtains glaze mixture, wherein and glaze includes base stock, adhesive agent, adjuvant, and
Antibacterial agent.As a result, by the mutual synergistic effect of above-mentioned each component, the enamel material prepared has ideal antibiotic property
Can, the ingredient of lower sintering temperature, enamel material will not occur physical-chemical reaction with metal base and generate gas, so that
The pin hole rate of enamel material is low, appearance, while can significantly provide the binding force of the enamel material and metallic matrix, separately
Outside, without containing the material that absorbing property is strong in the antibacterial enamel material, when being applied to micro-wave oven, microwave damage can be effectively reduced
It loses, improves microwave output rating.
According to an embodiment of the invention, the specific type of each component in above-mentioned glaze, proportion and can play specific
Consistent described in effect and mentioned-above enamel material, this is no longer going to repeat them.
S200: glaze mixture is subjected to melt process, obtains glaze melt.Thereby, it is possible to effectively will be each in glaze
Component is uniformly mixed, and is conducive to the service performance for improving enamel material.
According to an embodiment of the invention, the concrete mode of melt process is not particularly limited, as long as glaze can be obtained effectively
Expect melt.In some embodiments of the invention, it can be carried out at the melting in 900-1100 degrees Celsius of kiln
Reason.It is easy to operate as a result, it is convenient and efficient.
S300: by glaze melt successively to carry out Water Quenching and drying and processing, frit is obtained.
According to an embodiment of the invention, in this step, glaze melt can be placed in progress cold quenching processing in cold water, so
Afterwards, frit cold quenching handled, which is put into drying box, carries out drying and processing, obtains frit.
S400: frit is subjected to ball-milling treatment, obtains enamel material.
According to an embodiment of the invention, in this step, the granularity for the enamel material that ball milling obtains is not less than 300 mesh.By
This, is conducive to subsequent applications.
Inventors have found that can quickly and effectively prepare antibiotic property using this method according to an embodiment of the present invention
Energy is good, sintering temperature is low, absorbing property is poor and the strong antibacterial enamel material of metal base binding ability, and easy to operate, side
Just, easy to accomplish.
In another aspect of the invention, the present invention provides a kind of heating equipments.According to an embodiment of the invention, the heating
Equipment includes: ontology；And it is formed in the coating at least part surface of ontology, which is warded off by mentioned-above antibacterial
Ceramic material is formed.The heating equipment has all feature and advantage of mentioned-above enamel material, and this is no longer going to repeat them.
According to an embodiment of the invention, the specific type of the heating equipment is not particularly limited, for example including but be not limited to
Micro-wave oven, oven, baking tray and its attachment etc..Specifically, can use above-mentioned enamel material micro- in above-mentioned heating equipment
The outer surface of wave furnace, oven etc. and its surface of attachment (such as baking tray of oven) etc. form enamel coating, and the heating is set as a result,
For while can have the performances such as good high temperature resistant, acid and alkali-resistance, scratch-resistant, corrosion-resistant, enamel material has preferable anti-
Bacterium performance, and the compactness of enamel is good, and pin hole rate is low, and with the adherence of metal base is good, binding force is strong, enamel material is not
Easy to fall off, in addition, the enamel material has lesser absorbing property, microwave output rating is high.
The embodiment of the present invention is described below in detail.
Embodiment 1
As follows, antibacterial enamel material is prepared:
1) by the Li of alkali metal oxide 3%2O, 20% Na2O, 8% K2O, the MgO of alkaline earth oxide 5%,
3% SrO, the Al of third main group metal oxides 8%2O3, 5% B2O3, the SiO of the 4th host element oxide 20%2, the 4th
The TiO of subgroup element oxide 15%2, 2% ZrO2, the Sb of the oxide 1% of the 5th major element2O3, 2% Bi2O3, the
The V of the oxide 3% of five subgroup elements2O5, the MoO of the 6th subgroup element oxide 1%3, the 8th family metal oxide 2%
Fe2O3, 1% cobalt oxide CoO, the CuO of the first B metal oxide 1%, the Ce of lanthanide oxide 0.02%2O3, antibacterial agent
0.01% nano silver, 0.01% ZnO.It is placed in 1100 DEG C of kiln and melts, the substance after melting is placed in cold water and is carried out
Frit after Water Quenching is put into baking oven and dries by Water Quenching, and frit is made；
2) 1) frit obtained in is subjected to ball-milling treatment and obtains the powdered frit of 300 mesh or more, can be obtained with antibiotic property
The enamel material of energy.
Embodiment 2
As follows, antibacterial enamel material is prepared:
1) by the Li of alkali metal oxide 2%2O, 15% Na2O, 5% K2O, the MgO of alkaline earth oxide 3%,
3% BaO, 2% SrO, the Al of third main group metal oxides 10%2O3, 2% B2O3, the 4th host element oxide 30%
SiO2, the TiO of the 4th subgroup element oxide 12%2, 5% ZrO2, the Sb of the oxide 1% of the 5th major element2O3、
1% Bi2O3, the V of the oxide 2% of the 5th subgroup element2O5, the MoO of the 6th subgroup element oxide 2%3, the 8th race's metal
The cobalt oxide CoO of oxide 3%, the CuO of the first B metal oxide 2%, the Ce of lanthanide oxide 0.01%2O3, 0.01%
Yb2O3, antibacterial agent 0.01%AgNO3, 0.01% ZnO.Be placed in 1100 DEG C of kiln and melt, by the substance after melting into
Enter and carry out Water Quenching in cold water, the frit after Water Quenching is put into baking oven and is dried, frit is made；
2) 1) frit obtained in is subjected to ball-milling treatment and obtains the powdered frit of 300 mesh or more, can be obtained with antibiotic property
The enamel material of energy.
Embodiment 3
As follows, antibacterial enamel material is prepared:
1) by the Na of alkali metal oxide 5%2O, 10% K2O, the MgO of alkaline earth oxide 5%, 4% BaO,
3% SrO, the Al of third main group metal oxides 10%2O3, 6% B2O3, the SiO of the 4th host element oxide 32%2, the
The TiO of four subgroup element oxides 7%2, 8% ZrO2, the Sb of the oxide 1% of the 5th major element2O3, 2% Bi2O3,
The V of the oxide 2% of 5th subgroup element2O5, the MoO of the 6th subgroup element oxide 1%3, the 8th family metal oxide 2%
Cobalt oxide CoO, 1% Fe2O3, the CuO of the first B metal oxide 1%, the Yb of lanthanide oxide 0.02%2O3, antibacterial
Nano silver, the 0.01%AgNO of agent 0.01%3, 0.01% ZnO.It is placed in 1100 DEG C of kiln and melts, by the object after melting
Matter, which enters, carries out Water Quenching in cold water, the frit after Water Quenching is put into baking oven and is dried, and frit is made；
2) 1) frit obtained in is subjected to ball-milling treatment and obtains the powdered frit of 300 mesh or more, can be obtained with antibiotic property
The enamel material of energy.
Embodiment 4
As follows, antibacterial enamel material is prepared:
1) by the Li of alkali metal oxide 10%2O, 12% Na2O, 13% K2O, alkaline earth oxide 3%
MgO, 1% BaO, the Al of third main group metal oxides 5%2O3, 3% B2O3, the SiO of the 4th host element oxide 28%2,
The TiO of 4th subgroup element oxide 12%2, 6% ZrO2, the Bi of the oxide 2% of the 5th major element2O3, the 5th subgroup
The V of the oxide 2% of element2O5, the MoO of the 6th subgroup element oxide 1%3, the cobalt oxide of the 8th family metal oxide 1%
CoO, the CuO of the first B metal oxide 1%, the Yb of lanthanide oxide 0.02%2O3, the nano silver of antibacterial agent 0.01%,
0.01% ZnO.It is placed in 1100 DEG C of kiln and melts, the substance after melting is entered and carries out Water Quenching in cold water, by water
Frit of quenching that treated, which is put into baking oven, dries, and frit is made；
2) 1) frit obtained in is subjected to ball-milling treatment and obtains the powdered frit of 300 mesh or more, can be obtained with antibiotic property
The enamel material of energy.
Embodiment 5
As follows, antibacterial enamel material is prepared:
1) by the Li of alkali metal oxide 9%2O, 5% Na2O, 12% K2O, the MgO of alkaline earth oxide 6%,
6% BaO, the Al of third main group metal oxides 2%2O3, 6% B2O3, the SiO of the 4th host element oxide 12%2, the 4th
The TiO of subgroup element oxide 23%2, 7% ZrO2, the Bi of the oxide 2% of the 5th major element2O3, 2% Sb2O3, the
The V of the oxide 4% of five subgroup elements2O5, the MoO of the 6th subgroup element oxide 2%3, the 8th family metal oxide 1%
Fe2O3, the CuO of the first B metal oxide 1%, the Ce of lanthanide oxide 0.01%2O3, 0.01% Yb2O3, antibacterial agent
0.01% nano silver, 0.01% AgNO3.It is placed in 1100 DEG C of kiln and melts, the substance after melting is entered in cold water
Water Quenching is carried out, the frit after Water Quenching is put into baking oven and is dried, frit is made；
2) 1) frit obtained in is subjected to ball-milling treatment and obtains the powdered frit of 300 mesh or more, can be obtained with antibiotic property
The enamel material of energy.
Embodiment 6
1) production method of template
According to identical spraying process, the existing enamel material (SiO of 35~50 mass % is sprayed with static gun respectively2,
The TiO of 10~40 mass %2, the B of 16~25 mass %2O3, the alkali metal oxide of 1~5 mass %, 8~15 mass %'s
Fe2O3, the MnO of 1~2 mass %2) and the present invention in enamel material obtained by 1~embodiment of embodiment 5 it is in 0.6mm thick
The metallic substrate surface of 10cm*10cm, and it is sintered, the sintering temperature of existing enamel material is 850 DEG C, of the invention
The sintering temperature of enamel material is 530 DEG C, respectively obtains template to be tested.Respectively enchashment have enamel material make template and
The template of Examples 1 to 5 enamel material production is each 3 pieces (10cm*10cm*0.6mm), counts every kind of template (same ceramics respectively
3 pieces of material) on pin hole quantity, be averaged (result be accurate to a position), the results are shown in Table 1.
2) by existing enamel material and the enamel material of Examples 1 to 5 using identical technique be sprayed on same size,
In the microwave oven inner container of shape, and liner is attached separately in the micro-wave oven of same model.Water l oad is done with 1000g ± 5g, is surveyed
After determining initial temperature T1, pour into the Pyrex container of same material, same size, same shape.Container is put into microwave
The centre of the minimum point of furnace internal-lining.Under the input of micro-wave oven voltage rating, starts micro-wave oven and start timing, use maximum fire
So that temperature is risen to T2, and measures heating time t.Microwave output power P is calculated using following formula, the results are shown in Table 1.
Wherein, P is output power (W), and t is the time (second) of heating, and T2 is final temperature DEG C, and T1 is initial temperature DEG C,
T0 is environment temperature DEG C, and Mw is the quality (g) of water, and Mc is the quality (g) of container.
3) existing enamel material and embodiment 1-5 are tested referring to " disinfection technology standard " Ministry of Public Health version -2.1.5.3 in 2002
In the anti-microbial property of enamel material for preparing, when testing result is contacted using Escherichia coli and staphylococcus aureus " 0 "
Between clump count ratio after clump count on sample and culture in 24 hours on sample, test result is shown in Table 2.
The comparison of the existing enamel material of table 1 and enamel material of the present invention in pin hole quantity and microwave delivery efficiency
By table 1, it is apparent that the pinhole number for the template that enamel material of the invention makes will be warded off significantly lower than existing
Ceramic material production template pinhole number, microwave delivery efficiency also compared with the prior art improve 7% or so, existing enamel material it is micro-
Wave delivery efficiency is unsatisfactory for A grades of efficiencies (A grades of efficiencies are >=54%), and enamel material of the invention is sprayed on microwave oven inner container
In, microwave delivery efficiency can be made to meet the requirement of A grades of efficiencies.
The comparison of the existing enamel material of table 2 and enamel material of the present invention in sterilizing rate
| Escherichia coli sterilizing rate | Staphylococcus aureus sterilizing rate | |
| The prior art | 33.16% | 12.96% |
| Embodiment 1 | > 99.97% | 95.83% |
| Embodiment 2 | > 99.97% | 95.32% |
| Embodiment 3 | > 99.97% | 95.86% |
| Embodiment 4 | > 99.97% | 95.05% |
| Embodiment 5 | > 99.97% | 95.65% |
By table 2, it is apparent that sterilizing rate (Escherichia coli, golden yellow Portugal of antibacterial enamel material produced by the present invention
Grape coccus) it to be apparently higher than existing kitchen appliance enamel technology, it can satisfy consumer for the need of kitchen appliance class product bactericidal property
It asks.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (5)
1. a kind of antibacterial enamel material characterized by comprising
Base stock；
Adhesive agent；
Adjuvant；And
Antibacterial agent,
Wherein, the gross mass based on the antibacterial enamel material, according to mass percentage,
Described matrix agent includes:
The oxide 15%~35% of alkali metal, the oxide of the alkali metal be in lithia, sodium oxide molybdena, potassium oxide extremely
Few one kind；
The oxide 8%~16% of third major element, the oxide of the third major element are selected from diboron trioxide, three
At least one of Al 2 O；
The oxide 12%~32% of 4th major element, the oxide of the 4th major element are silica；
The oxide 15%~30% of 4th subgroup element, the oxide of the 4th subgroup element are selected from titanium dioxide, two
At least one of zirconium oxide,
The adhesive agent include:
The oxide 2%~4% of 5th major element, the oxide of the 5th major element are selected from antimony oxide, three
Aoxidize at least one of two bismuths；
The oxide 1%~2% of 6th subgroup element, the oxide of the 6th subgroup element are molybdenum oxide,
The adjuvant includes:
The oxide 4%~12% of alkaline-earth metal, the oxide of the alkaline-earth metal are selected from magnesia, strontium oxide strontia, barium monoxide
At least one of；
The oxide 2%~4% of 5th subgroup element, the oxide of the 5th subgroup element are vanadic anhydride；
The oxide 1%~5% of 8th race's metallic element, the oxide of the 8th race's metallic element are selected from cobalt oxide, three
Aoxidize at least one of two iron；
The oxide 0.01%~0.02% of lanthanide series, the oxide of the lanthanide series are selected from yttria, three oxygen
Change at least one of two ceriums；
The oxide 1%~2% of first B metal element, the oxide of the first B metal element are copper oxide,
The mass percentage of the antibacterial agent is 0.01%~0.03%.
2. antibacterial enamel material according to claim 1, which is characterized in that the antibacterial agent is selected from nano silver, nitric acid
At least one of silver, zinc oxide.
3. antibacterial enamel material according to claim 1, which is characterized in that the granularity of the antibacterial enamel material is not less than
50 microns.
4. a kind of method for preparing antibacterial enamel material according to any one of claims 1 to 3 characterized by comprising
Glaze is mixed, glaze mixture is obtained, wherein the glaze includes lithia, sodium oxide molybdena, at least one in potassium oxide
Kind；At least one of magnesia, strontium oxide strontia, barium monoxide；At least one of diboron trioxide, aluminum oxide；Titanium dioxide
At least one of silicon, titanium dioxide, zirconium dioxide；At least one of antimony oxide, bismuth oxide；Five oxidations two
At least one of vanadium, molybdenum oxide, cobalt oxide, di-iron trioxide；At least one of yttria, cerium sesquioxide；Oxygen
Change copper；And antibacterial agent；
The glaze mixture is subjected to melt process, obtains glaze melt；
The glaze melt is successively subjected to Water Quenching and drying and processing, obtains frit；
The frit is subjected to ball-milling treatment, obtains antibacterial enamel material.
5. a kind of heating equipment characterized by comprising
Ontology；And
Coating, the coating are formed at least part surface of the ontology, and the coating in claims 1 to 3 by appointing
Antibacterial enamel material described in one is formed.
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| CN108203243B (en) * | 2016-12-17 | 2022-02-08 | 江西科盛环保股份有限公司 | Preparation method of ultra-high strength steel plate Q550 and Q690 double-sided enamel fish-scaling-proof enamel |
| CN110423501B (en) * | 2019-06-19 | 2021-07-09 | 永康市嘉禧厨具有限公司 | Antibacterial non-stick pan coating, preparation method and non-stick pan |
| CN110255905B (en) * | 2019-07-02 | 2022-06-03 | 浙江开尔新材料股份有限公司 | Antibacterial enamel glaze slurry, preparation method and preparation method of antibacterial enamel plate |
| CN110255907A (en) * | 2019-08-06 | 2019-09-20 | 淄博中升机械有限公司 | A kind of wide bandgap semiconductor nanometer enamel and enamel firing method for reaction kettle |
| CN111393026A (en) * | 2020-02-25 | 2020-07-10 | 广东沃尔姆斯电器有限公司 | Preparation method of enamel product with antibacterial property and enamel product with antibacterial property |
| CN114351142A (en) * | 2021-11-26 | 2022-04-15 | 格力电器（武汉）有限公司 | Preparation method of antibacterial enamel liner, antibacterial enamel liner and water heater comprising antibacterial enamel liner |
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| CN1843995A (en) * | 2006-05-12 | 2006-10-11 | 丁文战 | Antibacterial enamel and preparation method thereof |
| CN103466948A (en) * | 2013-08-15 | 2013-12-25 | 河北省沙河玻璃技术研究院 | Leadless environmentally-friendly glass glaze, preparation method thereof, and glazed surface preparation method |
| CN104891805A (en) * | 2015-05-25 | 2015-09-09 | 广东美的厨房电器制造有限公司 | Enamel material, and preparation method and application thereof |
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| CN1843995A (en) * | 2006-05-12 | 2006-10-11 | 丁文战 | Antibacterial enamel and preparation method thereof |
| CN103466948A (en) * | 2013-08-15 | 2013-12-25 | 河北省沙河玻璃技术研究院 | Leadless environmentally-friendly glass glaze, preparation method thereof, and glazed surface preparation method |
| CN104891805A (en) * | 2015-05-25 | 2015-09-09 | 广东美的厨房电器制造有限公司 | Enamel material, and preparation method and application thereof |
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