CN103964690A - Composition adopted as enamel material, and use thereof - Google Patents
Composition adopted as enamel material, and use thereof Download PDFInfo
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- CN103964690A CN103964690A CN201310039629.2A CN201310039629A CN103964690A CN 103964690 A CN103964690 A CN 103964690A CN 201310039629 A CN201310039629 A CN 201310039629A CN 103964690 A CN103964690 A CN 103964690A
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Abstract
The present invention relates to a composition adopted as an enamel material. The composition comprises silicon oxide, aluminum oxide, boron oxide, calcium oxide, cobalt oxide, titanium oxide, zirconium oxide and an alkali oxide, does not contain lead and fluorine, and has high safety. The enamel material prepared from the composition has characteristics of smooth and compact surface, furring production resistance, strong acid-resistance and strong alkali-resistance, and has a shrinkage exactly the same as the metal shrinkage of metals, particularly exactly the same as the shrinkage of stainless steel, such that the condition that the enamel coating on the metal surface produces cracks due to sharp shrinkage can be prevented. The present invention further relates to a use of the composition, wherein the composition can be enameled on the surface of the metal substrate.
Description
Technical field
The invention belongs to enamel material field, be specifically related to a kind of composition and use thereof as enamel material.
Background technology
Carry out the enamel application of slip in metallic surface and can prevent metal rusting, make metal in the time being heated, be unlikely to the erosion that forms zone of oxidation and can resist various liquid on surface.Enamelware is safety non-toxic not only, be easy to washing clean, can be widely used as on the ware and washing implement and household electrical appliance using in daily life, and under given conditions, the premium propertiess such as high, high temperature resistant, the wear-resisting and insulating effect of hardness that the enamel application of slip shows on metal body, make enamelware have purposes more widely.
Tubular metal heating unit be in current all electrical heating elements, be widely used, a kind of Encapsulated electric thermoelectric converter of simple in structure, dependable performance, long service life.As far back as the '30s, there is Huo Teboyinte company of Britain just tubular metal heating unit to be applied on household electrical appliance.At present, electrothermal tube has been widely used on the electrical equipment such as industry and Household electric oven, vertical air conditioner such as Injection Industry, chemical industry, auxiliary heating at home, outward.
Present tubular metal heating unit has a variety of, multifarious in structure, but common feature is all to use the shell of tubular metal material as heating unit, because directly contact with heating medium, so easily there is the situation such as scaling, corrosion in shell, cause heating unit timeliness, indivedual producers are used some common enamel materials on heating unit surface, but material surface is easily uneven, solidification process easily produces foaming, and under the effect of long-time heat expansion shrinkage, easily crack, effect is not satisfactory.
CN1878734A discloses a kind of enamel composition for heating unit enamel layer, the V that comprises 0-10 quality %
2o
5, the PbO of 0-10 quality %, the B of 5-13 quality %
2o
3, 33-53 quality % SiO
2, 5-15 quality % Al
2o
3caO with 20-30 quality %; In addition, this invention also comprises the heating unit that comprises this subassembly.This enamel composition makes electrical heating element can have the weather resistance of improvement and the security of enhancing.
In above-mentioned patent and prior art, provide for enamel material composition, or make metallic heating element there is good thermo-efficiency, or make metallic heating element there is good corrosion resistance nature, but it is existence or scaling or the problem such as under the effect of long-time heat expansion shrinkage, easily crack still, in order to obtain the better enamel material composition of a kind of over-all properties, special proposition the present invention.
Summary of the invention
The object of the present invention is to provide a kind of composition as enamel material, said composition is not leaded, fluorine, safe, enamel material smooth surface, the densification made from said composition, be difficult for scaling, resistance to acids and bases is strong, and the shrinking percentage of this enamel material and metal metal contracts rate almost in full accord, particularly almost in full accord with stainless shrinking percentage, can prevent from because of convergent-divergent sharply, the enamel coating of metallic surface being cracked.
In order to realize object of the present invention, spy by the following technical solutions:
As a composition for enamel material, described composition comprises silicon oxide, aluminum oxide, boron oxide, calcium oxide, cobalt oxide, titanium oxide, zirconium white, basic oxide.
Composition as enamel material provided by the invention is not leaded, fluorine, safe, the enamel coating making in metallic surface through enameling process with said composition, its smooth surface, hardness is high, surface is difficult for retaining impurity, be difficult for scaling, and compact structure, zero defect, can effectively keep out pitting attack, in addition, the shrinking percentage of this enamel coating and metal is almost in full accord, particularly almost in full accord with stainless shrinking percentage, can avoid because of convergent-divergent sharply, the enamel coating that overlays on metallic surface being cracked.Further, the metallic heating element of the coating of making by enameling process with said composition, the work-ing life that can greatly improve heating unit.
By quality percentage composition, in described composition, the content of silicon oxide is 28 ~ 48%, the content of aluminum oxide is 3 ~ 13%, the content of boron oxide is 30 ~ 44%, the content of calcium oxide is 2 ~ 5%, the content of cobalt oxide is 2 ~ 6%, the content of titanium oxide is 2 ~ 8%, zirconic content is 1 ~ 5%, the content of basic oxide is 1 ~ 5%.
Provided by the invention as in the composition of enamel material, taking silicon oxide and boron oxide as main ingredient, the two is good acidproof component, when the content of silicon oxide is 28 ~ 48%, the content of boron oxide is while being 30 ~ 44%, the enamel making not only has good acid resistance, and its alkaline resistance properties can not decline to a great extent, can also improve resistance to impact shock and the heatproof acute degeneration of enamel.In addition, boron oxide can also significantly reduce surface tension, improves adherence, improves the surface luster of enamel.
Titanium oxide, zirconium white, calcium oxide, cobalt oxide are not only acidproof but also alkaline-resisting components; when the content of calcium oxide is 2 ~ 5%, the content of cobalt oxide is 2 ~ 6%, the content of titanium oxide is 2 ~ 8%, zirconic content is while being 1 ~ 5%; enamel has extraordinary resistance to acids and bases; particularly zirconium white and titanium oxide; can make the protective membrane of enamel surfaces formation acid and alkali-resistance, greatly improve the erosion resistance of enamel.In the time that the content of aluminum oxide is 3 ~ 13%, can form fine and close nucerite structure, make enamel there is good chemical stability and higher physical strength.The effect of basic oxide is to regulate the coefficient of expansion and solubility promoter, but basic oxide are neither acidproof not alkaline-resisting again, the content of neutral and alkali oxide compound of the present invention is lower, in not affecting the resistance to acids and bases of enamel, takes into account the effect of its adjusting coefficient of expansion and solubility promoter.
Contriver is surprised to find that, the enamel coating of making in metallic surface after mixing with the composition of above-mentioned composition and content, the percent thermal shrinkage of its percent thermal shrinkage and metal is almost in full accord, particularly almost in full accord with stainless shrinking percentage, surface by said composition enamel at metallic substance, can avoid because of convergent-divergent sharp, the coating that overlays on metallic surface being cracked in heat-processed, extend the metallic substance of band coating work-ing life in hot-cool environment, the particularly surface at metallic heating element by said composition enamel, the work-ing life of this metallic heating element will greatly be improved.
Preferably, by quality percentage composition, in described composition, the content of silicon oxide is 32 ~ 44%, the content of aluminum oxide is 5 ~ 10%, the content of boron oxide is 34 ~ 40%, the content of calcium oxide is 2 ~ 5%, the content of cobalt oxide is 2 ~ 6%, the content of titanium oxide is 2 ~ 8%, zirconic content is 1 ~ 5%, the content of basic oxide is 1 ~ 5%.
Described basic oxide comprise one or more in sodium oxide, potassium oxide, Lithium Oxide 98min, calcium oxide, magnesium oxide.
Preferably, described basic oxide are the mixture of sodium oxide, potassium oxide, Lithium Oxide 98min.
The effect of basic oxide is to regulate the coefficient of expansion and solubility promoter, but basic oxide are neither acidproof not alkaline-resisting again, introduces sodium oxide, potassium oxide and Lithium Oxide 98min in composition simultaneously, and the resistance to acids and bases of the enamel of preparation is best.
Preferably, described composition also comprises transition metal; The content of described transition metal is 1 ~ 2%.The present invention progressive one adds transition metal in each component of composition, with antibacterial, antibacterial, the sterilization of enhancing composition, antiviral texts
Preferred, described transition metal comprises one or more in silver, copper, nickel, niobium.Silver, copper, nickel, niobium with composition in the nucerite with specific structure that forms through enameling process according to a certain percentage of other component, can greatly strengthen that this enamel is antibacterial, antibacterial, sterilization, antiviral effect.
A purposes for foregoing composition, for the surface to metal base by described composition enamel.
Described metal base comprises the metal shell of metallic heating element, metal ware, metal washing implement, household electrical appliance.
Composition of the present invention can be with reference to the enameling process enamel of prior art at metallic surface, but preferred, adopts following technique:
(1) each component of composition is mixed according to recipe quantity, be heated to molten state, cooling, abrasive dust;
(2) by dry method or wet-process enamelling;
(3) be heated to 800 ~ 900 DEG C, be incubated 10 ~ 20 minutes;
(4) be cooled to room temperature.
The present invention is before the metallic surface application of slip, first by the each component heating and melting in composition cooling abrasive dust, the one, being conducive to each component can mix more fully, the 2nd, before enameling process, make each component according to certain rule arranged distribution, form crystallite structure, and then carry out enameling process, the coating hardness obtaining is high, compact structure, properties is all improved.
Dry method in described step (2) or wet-process enamelling all can be with reference to the dust coat technique of prior art or wet-process enamelling techniques, and those skilled in the art are without paying performing creative labour.
Wet-process enamelling technique mainly contains the methods such as spraying, dip-coating and the rolling application of slip.By metal is rotated in three-dimensional space, make its all surface all coat glaze slip, unnecessary residue and liquid all must be disposed, and are only covered with glaze slip thin layer, uniform and continuous with security deposit's metal surface.
Dust coat technique is taking electrostatic spraying as main.Electrostatic spraying is compared with wet method system, and it has reduced cost, has saved energy, and material use efficiency can reach 97%.In addition, it has also reduced the pollution to environment.In the present invention, preferably adopt electrostatic spraying.
After the application of slip, carry out enamel firing, in the time that temperature is elevated to 700 DEG C of left and right, each component starts to melt and form enamel coating, temperature continues to raise, in the present invention, enamel firing temperature remains between 830-860 DEG C, and the time is 10-20 minute, with this understanding, metallic surface has formed the coating of one deck hard, compact structure.
Compared with prior art, beneficial effect of the present invention is:
(1) not leaded, the fluorine of the composition as enamel material provided by the invention, safety and environmental protection, in addition, the smooth surface of the enamel material making with said composition, hardness is high, and surface is difficult for retaining impurity, is difficult for scaling, and compact structure, zero defect, can effectively keep out pitting attack.
(2) shrinking percentage of enamel coating and metal is almost in full accord, particularly almost in full accord with stainless shrinking percentage, surface by said composition enamel at metallic substance, can avoid making because of convergent-divergent in heat-processed the enamel coating that overlays on metallic surface to crack, extend the metallic substance of band coating work-ing life in hot-cool environment.
(3) composition provided by the invention also has very strong antibacterial, antibacterial, sterilization, the effect such as antiviral.
Embodiment
Below by specific embodiment, summary of the invention of the present invention is described further, but does not therefore limit content of the present invention.
Embodiment 1
Each component is mixed by following quality percentage composition: the content of silicon oxide is 28%, the content of aluminum oxide is 13%, the content of boron oxide is 44%, the content of calcium oxide is 2%, the content of cobalt oxide is 2%, the content of titanium oxide is 5%, zirconic content is 1%, the content of sodium oxide is 5%; Reheat to molten state, cooling, abrasive dust.
By wet spray, thin layer, uniform and continuous coating in stainless steel heating unit surface coverage, be heated to 900 DEG C, be incubated 20 minutes; Be cooled to room temperature, obtain final product.The thickness of this enamel coating is 100 μ m.
Embodiment 2
Each component is mixed by following quality percentage composition: the content of silicon oxide is 48%, the content of aluminum oxide is 3%, the content of boron oxide is 30%, the content of calcium oxide is 2%, the content of cobalt oxide is 3%, the content of titanium oxide is 8%, zirconic content is 5%, the content of calcium oxide is 1%; Reheat to molten state, cooling, abrasive dust.
By electrostatic spraying, in stainless steel heating unit surface application of slip coating, be heated to 800 DEG C, be incubated 10 minutes; Be cooled to room temperature, obtain final product.The thickness of this enamel coating is 10 μ m.
Embodiment 3
Each component is mixed by following quality percentage composition: the content of silicon oxide is 32%, the content of aluminum oxide is 10%, the content of boron oxide is 40%, the content of calcium oxide is 5%, the content of cobalt oxide is 6%, the content of titanium oxide is 2%, zirconic content is 2%, the content of potassium oxide is 3%; Reheat to molten state, cooling, abrasive dust.
By electrostatic spraying, in stainless steel heating unit surface application of slip coating, be heated to 840 DEG C, be incubated 15 minutes; Be cooled to room temperature, obtain final product.The thickness of this enamel coating is 50 μ m.
Embodiment 4
Each component is mixed by following quality percentage composition: the content of silicon oxide is 44%, the content of aluminum oxide is 5%, the content of boron oxide is 34%, the content of calcium oxide is 3%, the content of cobalt oxide is 3%, the content of titanium oxide is 6%, zirconic content is 2%, the content of Lithium Oxide 98min is 3%; Reheat to molten state, cooling, abrasive dust.
By electrostatic spraying, in stainless steel heating unit surface application of slip coating, be heated to 850 DEG C, be incubated 10 minutes; Be cooled to room temperature, obtain final product.The thickness of this enamel coating is 350 μ m.
Embodiment 5
Each component is mixed by following quality percentage composition: the content of silicon oxide is 28%, the content of aluminum oxide is 13%, the content of boron oxide is 44%, the content of calcium oxide is 5%, the content of cobalt oxide is 4%, the content of titanium oxide is 2%, zirconic content is 1%, the content of sodium oxide is 1%, the content of nickel is 2%; Reheat to molten state, cooling, abrasive dust.
By electrostatic spraying, in stainless steel cup sub-surface application of slip coating, be heated to 860 DEG C, be incubated 10 minutes; Be cooled to room temperature, obtain final product.The thickness of this enamel coating is 500 μ m.
Embodiment 6
Each component is mixed by following quality percentage composition: the content of silicon oxide is 48%, the content of aluminum oxide is 3%, the content of boron oxide is 30%, the content of calcium oxide is 2%, the content of cobalt oxide is 2%, the content of titanium oxide is 8%, zirconic content is 5%, the content of potassium oxide is 1%, the content of copper is 1%; Reheat to molten state, cooling, abrasive dust.
By electrostatic spraying, in stainless steel heating unit surface application of slip coating, be heated to 845 DEG C, be incubated 12 minutes; Be cooled to room temperature, obtain final product.The thickness of this enamel coating is 40 μ m.
Embodiment 7
Each component is mixed by following quality percentage composition: the content of silicon oxide is 32%, the content of aluminum oxide is 10%, the content of boron oxide is 40%, the content of calcium oxide is 2%, the content of cobalt oxide is 6%, the content of titanium oxide is 2%, zirconic content is 1%, the content of sodium oxide is 5%, the content of silver is 1%, the content of niobium is 1%; Reheat to molten state, cooling, abrasive dust.
By electrostatic spraying, in stainless steel heating unit surface application of slip coating, be heated to 845 DEG C, be incubated 12 minutes; Be cooled to room temperature, obtain final product.The thickness of this enamel coating is 40 μ m.
Experimental example 1
This experimental example has been tested the enamel coating of making on metallic heating element surface with composition provided by the invention at the properties after high temperature.
1, high temperature test
By the heating unit energising heating of coating, make its surface temperature be increased to gradually 1500 DEG C, take out, then naturally cool to room temperature, repeat 50 times, observe the variation of its outward appearance, the results are shown in Table 1.
Table 1
2, endurance life test
The heating unit of coating is put into water-bath energising heating, carry out, after 3000 circulation cold shock testings, observing the variation of its outward appearance, the results are shown in Table 2.
Table 2
3, bacteria-eliminating efficacy
The heating unit of coating to be measured is respectively put into 1L water-bath, and energising is heated to boiling, and the total hardness of tap water is (with CaCO
3meter) be 480mg/L, 128 of total plate count, detected result is in table 3.
Table 3
Above-mentioned test-results shows, the smooth surface of the heating unit of coating provided by the invention, hardness is high, compact structure, can effectively keep out pitting attack, zero defect, surface is difficult for retaining impurity, be difficult for scaling, the shrinking percentage of coating and the shrinking percentage of metallic heating element almost always, can prevent from cracking because of convergent-divergent in heat-processed long service life, and the heating unit of coating provided by the invention also has extraordinary antibacterial, antibacterial, sterilization, antivirus action.
The heating unit of the coating that the present invention also provides other embodiment has also carried out above-mentioned test, has obtained similar result, and because length is limited, this is no longer going to repeat them.
Claims (10)
1. as a composition for enamel material, it is characterized in that, described composition comprises silicon oxide, aluminum oxide, boron oxide, calcium oxide, cobalt oxide, titanium oxide, zirconium white, basic oxide.
2. composition according to claim 1, it is characterized in that, by quality percentage composition, in described composition, the content of silicon oxide is 28 ~ 48%, the content of aluminum oxide is 3 ~ 13%, the content of boron oxide is 30 ~ 44%, the content of calcium oxide is 2 ~ 5%, the content of cobalt oxide is 2 ~ 6%, the content of titanium oxide is 2 ~ 8%, zirconic content is 1 ~ 5%, the content of basic oxide is 1 ~ 5%.
3. composition according to claim 2, it is characterized in that, by quality percentage composition, in described composition, the content of silicon oxide is 32 ~ 44%, the content of aluminum oxide is 5 ~ 10%, the content of boron oxide is 34 ~ 40%, the content of calcium oxide is 2 ~ 5%, the content of cobalt oxide is 2 ~ 6%, the content of titanium oxide is 2 ~ 8%, zirconic content is 1 ~ 5%, the content of basic oxide is 1 ~ 5%.
4. composition according to claim 1, is characterized in that, described basic oxide comprise one or more in sodium oxide, potassium oxide, Lithium Oxide 98min, calcium oxide, magnesium oxide.
5. composition according to claim 4, is characterized in that, described basic oxide are the mixing of sodium oxide, potassium oxide, Lithium Oxide 98min.
6. according to the composition described in claim 1-5 any one, it is characterized in that, described composition also comprises transition metal.
7. composition according to claim 6, is characterized in that, described transition metal comprises one or more in silver, copper, nickel, niobium.
8. composition according to claim 6, is characterized in that, the content of described transition metal is 1 ~ 2%.
9. a purposes for the composition described in claim 1-8 any one, is characterized in that, for the surface to metal base by described composition enamel.
10. purposes according to claim 9, is characterized in that, described metal base comprises the metal shell of metallic heating element, metal ware, metal washing implement, household electrical appliance.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927414A (en) * | 2015-05-22 | 2015-09-23 | 苏州市嘉明机械制造有限公司 | Insulating coating used for protecting mirror plate |
| CN105349932A (en) * | 2015-12-10 | 2016-02-24 | 苏州市嘉明机械制造有限公司 | Manufacturing method for insulated mirror boards based on plasma spraying process |
| CN105420655A (en) * | 2015-12-10 | 2016-03-23 | 苏州市嘉明机械制造有限公司 | Insulating thrust runner production process based on impregnation process |
| CN106219977A (en) * | 2016-07-26 | 2016-12-14 | 广西驰胜农业科技有限公司 | A kind of enamel reaction still material being exclusively used in polyaluminium chloride production |
| CN109052953A (en) * | 2018-10-18 | 2018-12-21 | 安徽省德邦瓷业有限公司 | It is a kind of for enhancing the glaze feed additives of domestic ceramics corrosion resistance |
| CN109620521A (en) * | 2019-01-21 | 2019-04-16 | 黄艳华 | A kind of ligament thermotherapy device for rehabilitation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927414A (en) * | 2015-05-22 | 2015-09-23 | 苏州市嘉明机械制造有限公司 | Insulating coating used for protecting mirror plate |
| CN104927414B (en) * | 2015-05-22 | 2017-10-24 | 苏州市嘉明机械制造有限公司 | A kind of insulating coating for being used to protect runner plate |
| CN105349932A (en) * | 2015-12-10 | 2016-02-24 | 苏州市嘉明机械制造有限公司 | Manufacturing method for insulated mirror boards based on plasma spraying process |
| CN105420655A (en) * | 2015-12-10 | 2016-03-23 | 苏州市嘉明机械制造有限公司 | Insulating thrust runner production process based on impregnation process |
| CN106219977A (en) * | 2016-07-26 | 2016-12-14 | 广西驰胜农业科技有限公司 | A kind of enamel reaction still material being exclusively used in polyaluminium chloride production |
| CN106219977B (en) * | 2016-07-26 | 2018-12-28 | 广西驰胜农业科技有限公司 | A kind of enamel reaction still material being exclusively used in polyaluminium chloride production |
| CN109052953A (en) * | 2018-10-18 | 2018-12-21 | 安徽省德邦瓷业有限公司 | It is a kind of for enhancing the glaze feed additives of domestic ceramics corrosion resistance |
| CN109620521A (en) * | 2019-01-21 | 2019-04-16 | 黄艳华 | A kind of ligament thermotherapy device for rehabilitation |
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|---|---|
| CN103964690B (en) | 2017-11-07 |
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