CN103964690B - A kind of composition as enamel material and application thereof - Google Patents
A kind of composition as enamel material and application thereof Download PDFInfo
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- CN103964690B CN103964690B CN201310039629.2A CN201310039629A CN103964690B CN 103964690 B CN103964690 B CN 103964690B CN 201310039629 A CN201310039629 A CN 201310039629A CN 103964690 B CN103964690 B CN 103964690B
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Abstract
The present invention relates to a kind of composition as enamel material, the composition includes silica, aluminum oxide, boron oxide, calcium oxide, cobalt oxide, titanium oxide, zirconium oxide, basic anhydride.The composition is not leaded, fluorine, it is safe, so that the enamel material surface that said composition is made is smooth, densification, it is difficult scaling, resistance to acids and bases is strong, and the shrinkage factor of the enamel material and the metal contracts rate of metal are almost completely the same, it are particularly and the shrinkage factor of stainless steel is almost completely the same, can prevents from cracking the enamel coating of metal surface because of convergent-divergent drastically.The invention further relates to the purposes of said composition, for by the composition enamel to the surface of metal base.
Description
Technical field
The invention belongs to enamel material field, and in particular to a kind of composition as enamel material and application thereof.
Background technology
Metal rusting can be prevented by carrying out the enamel application of slip in metal surface, make metal be unlikely to be formed on surface when heated
Oxide layer and the erosion that various liquid can be resisted.Enamelware not only safety non-toxic, it is easy to which washing is clean, can widely use
Make on the ware and washing implement and household electrical appliance that are used in daily life, and under given conditions, enamel is applied
The premium properties such as the hardness height, high temperature resistant, the wear-resisting and insulating effect that are shown on metal body are warded off, there is enamelware
More extensive purposes.
Tubular metal heating element heater be widely used in current all electric heating elements, simple in construction, dependable performance, using the longevity
Order a kind of long Encapsulated electric thermal element.Early in the '30s, there are Huo Teboyinte companies of Britain just by tubular metal heating unit
Part is applied on household electrical appliance.At present, electrothermal tube is widely used to Injection Industry, chemical industry, auxiliary heating at home, outside
Deng on the electrical equipment such as industry and Household electric oven, vertical air conditioner.
The characteristics of present tubular metal heating element heater has multifarious in many kinds, structure, but common all uses
Tubular metal material as heating element heater shell because and heating physical contact between media, shell easily occur scaling,
Situations such as corrosion, cause heating element heater timeliness, indivedual producers use some common enamel materials in heater element surface, but material
Expect that surface is easily uneven, solidification process easily produces foaming, and be also easy to produce and split in the presence of expanding with heat and contract with cold for a long time
Line, effect is not satisfactory.
CN1878734A discloses a kind of enamel composition being used in heating element heater enamel layer, includes 0-10 mass %'s
V2O5, 0-10 mass % PbO, 5-13 mass % B2O3, 33-53 mass % SiO2, 5-15 mass % Al2O3With 20-30 matter
Measure % CaO；In addition, the invention also includes the heating element heater comprising this sub-assembly.The enamel composition make it that electric heating element can be with
Durability and enhanced security with improvement.
Above-mentioned patent and provide in the prior art be used for enamel material composition, or there is metallic heating element
The good thermal efficiency, or make metallic heating element that there is preferable decay resistance, but its still have or scaling or
Person in the presence of long-time is expanded with heat and contract with cold the problems such as crackle is also easy to produce, in order to obtain a kind of combination property more preferably enamel material
Composition, spy proposes the present invention.
The content of the invention
It is an object of the invention to provide a kind of composition as enamel material, said composition is not leaded, fluorine, security
Height, so that the enamel material surface that said composition is made is smooth, densification, is difficult scaling, resistance to acids and bases is strong, and the enamel material
Shrinkage factor and the metal contracts rate of metal are almost completely the same, be particularly and the shrinkage factor of stainless steel is almost completely the same, can
To prevent from cracking the enamel coating of metal surface because of convergent-divergent drastically.
In order to realize the purpose of the present invention, spy uses following technical scheme：
A kind of composition as enamel material, the composition includes silica, aluminum oxide, boron oxide, calcium oxide, oxygen
Change cobalt, titanium oxide, zirconium oxide, basic anhydride.
The composition as enamel material that the present invention is provided is not leaded, fluorine, safe, with said composition through application of slip work
Skill is in enamel coating made from metal surface, and its surface is smooth, and hardness is high, and surface is difficult to retain impurity, is difficult scaling, and knot
Structure is fine and close, and zero defect can effectively keep out spot corrosion, in addition, the shrinkage factor of the enamel coating and metal is almost completely the same, it is special
It is not almost completely the same with the shrinkage factor of stainless steel, can avoids making to overlay on metal surface because of convergent-divergent drastically
Enamel coating is cracked.Further, the metallic heating element for the coating being made up with said composition of enameling process,
The service life of heating element heater can be drastically increased.
Based on weight/mass percentage composition, in the composition content of silica be the content of 28 ~ 48%, aluminum oxide be 3 ~
13%th, the content of boron oxide is that the content that the content of 30 ~ 44%, calcium oxide is 2 ~ 5%, cobalt oxide is that 2 ~ 6%, content of titanium oxide is
2 ~ 8%, the content of zirconium oxide is that the content of 1 ~ 5%, basic anhydride is 1 ~ 5%.
In the composition as enamel material that the present invention is provided, using silica and boron oxide as key component, the two is equal
For good resistance to acid constituents, when the content that the content of silica is 28 ~ 48%, boron oxide is 30 ~ 44%, obtained enamel is not only
With preferable acid resistance, and its alkaline resistance properties will not decline to a great extent, moreover it is possible to improve impact strength and the heatproof sudden turn of events of enamel
Property.In addition, boron oxide can also significantly reduce surface tension, improve adherence, improve the lustrous surface of enamel.
Titanium oxide, zirconium oxide, calcium oxide, cobalt oxide are not only acidproof but also alkaline-resisting components, when calcium oxide content for 2 ~ 5%,
When the content of cobalt oxide is that the content of 2 ~ 6%, titanium oxide is that the content of 2 ~ 8%, zirconium oxide is 1 ~ 5%, enamel has extraordinary resistance to
Acid-base property, particularly zirconium oxide and titanium oxide, can make the diaphragm of enamel surfaces formation acid and alkali-resistance, drastically increase enamel
Corrosion resistance.When the content of aluminum oxide is 3 ~ 13%, the nucerite structure of densification can be formed so that enamel has preferable
Chemical stability and higher mechanical strength.The effect of basic anhydride is to adjust the coefficient of expansion and cosolvent, but alkaline oxygenated
Thing is neither acidproof and not alkaline-resisting, and the content of neutral and alkali oxide of the present invention is relatively low, while the resistance to acids and bases of enamel is not influenceed,
Take into account its effect for adjusting the coefficient of expansion and cosolvent.
Inventor with the enamel being made after above-mentioned composition and the mixing of the composition of content in metal surface it was unexpectedly observed that applied
The percent thermal shrinkage of layer, its percent thermal shrinkage and metal is almost completely the same, is particularly and the shrinkage factor of stainless steel is almost completely the same,
By said composition enamel on the surface of metal material, it can avoid making to overlay on because of sharp convergent-divergent in heating process
The coating of metal surface is cracked, and is extended service life of the band coating metal material in hot-cool environment, particularly should
Composition enamel will be greatly enhanced the service life of the metallic heating element on the surface of metallic heating element.
It is preferred that, based on weight/mass percentage composition, the content of silica is 32 ~ 44%, content of aluminum oxide in the composition
It is that the content of 34 ~ 40%, calcium oxide is that the content of 2 ~ 5%, cobalt oxide is containing for 2 ~ 6%, titanium oxide for the content of 5 ~ 10%, boron oxide
The content measured as 2 ~ 8%, zirconium oxide is that the content of 1 ~ 5%, basic anhydride is 1 ~ 5%.
The basic anhydride include the one or more in sodium oxide molybdena, potassium oxide, lithia, calcium oxide, magnesia.
It is preferred that, the basic anhydride are sodium oxide molybdena, potassium oxide, the mixture of lithia.
The effect of basic anhydride is the regulation coefficient of expansion and cosolvent, but basic anhydride are neither acidproof and not alkaline-resisting,
Introduce sodium oxide molybdena, potassium oxide and lithia in the composition simultaneously, the resistance to acids and bases of the enamel of preparation is best.
It is preferred that, the composition also includes transition metal；The content of the transition metal is 1 ~ 2%.The present invention is in combination
Progressive one adds transition metal in each component of thing, to strengthen the antibacterial of composition, antibacterial, sterilization, antiviral and other effects
It is furthermore preferred that the transition metal includes the one or more in silver, copper, nickel, niobium.Silver, copper, nickel, niobium with group
The nucerite with specific structure of other components according to a certain percentage by enameling process formation in compound, can pole
The earth enhances the enamel antibacterial, antibacterial, sterilization, antiviral effect.
A kind of purposes of foregoing composition, for by described composition enamel to the surface of metal base.
The metal base includes metallic heating element, metal ware, metal washing implement, the metal of household electrical appliance
Shell.
The composition of the present invention can refer to the enameling process enamel of prior art in metallic surface, but it is preferable that using
Following technique：
（1）The each component of composition is mixed according to recipe quantity, molten state is heated to, cooled down, milling；
（2）Pass through the dry or wet application of slip；
（3）800 ~ 900 DEG C are heated to, 10 ~ 20 minutes are incubated；
（4）It is cooled to room temperature.
Each component heating in composition is first melted before the metallic surface application of slip and cools down milling, one by the present invention
Being advantageous for each component can more fully be well mixed, and two be to have made each component before enameling process according to certain aligned transfer
Distribution, forms crystallite structure, enameling process is then carried out again, and obtained coating hardness is high, and compact structure, properties are equal
It is improved.
The step（2）In the dry or wet application of slip can refer to the dust coat technique or wet-process enamelling of prior art
Technique, those skilled in the art need not pay performing creative labour.
Wet-process enamelling technique mainly has spraying, dip-coating and rolls the methods such as the application of slip.By making metal turn in three dimensions
It is dynamic, its all surface is all coated glaze slip, unnecessary residue and liquid must all be disposed, to ensure that metal surface is only covered with
A thin layer of, uniform and continuous glaze slip.
Dust coat technique is then based on electrostatic spraying.Electrostatic spraying is compared with wet method system, and it reduces cost, saves
Energy, stock utilization can reach 97%.In addition, it also reduces the pollution to environment.In the present invention, it is preferred to use electrostatic
Spraying process.
Enamel firing is carried out after the application of slip, when temperature is increased to 700 DEG C or so, each component starts to melt and formed enamel coating, temperature
Continue to raise, enamel firing temperature is maintained between 830-860 DEG C in the present invention, the time is 10-20 minutes, on this condition, metal
Surface form the coating of one layer of hard, compact structure.
Compared with prior art, beneficial effects of the present invention are：
（1）The composition as enamel material that the present invention is provided is not leaded, fluorine, safety and environmental protection, in addition, with said composition
The surface of obtained enamel material is smooth, and hardness is high, and surface is difficult to retain impurity, is difficult scaling, and compact structure, intact
Fall into, can effectively keep out spot corrosion.
（2）The shrinkage factor of enamel coating and metal is almost completely the same, is particularly and the shrinkage factor of stainless steel is almost complete
Unanimously, by said composition enamel on the surface of metal material, it can avoid making to overlay on because of convergent-divergent in heating process
The enamel coating of metal surface is cracked, and extends service life of the band coating metal material in hot-cool environment.
（3）The composition that the present invention is provided also has the effect such as very strong antibacterial, antibacterial, sterilization, antiviral.
Embodiment
The content of the invention of the present invention is described further below by specific embodiment, but does not therefore limit this hair
Bright content.
Embodiment 1
Each component is mixed by following weight/mass percentage composition：The content of silica is that the content of 28%, aluminum oxide is 13%, oxygen
The content for changing boron is that the content of 44%, calcium oxide is that the content of 2%, cobalt oxide is that the content of 2%, titanium oxide is containing for 5%, zirconium oxide
Amount is that the content of 1%, sodium oxide molybdena is 5%；Molten state is again heated to, is cooled down, milling.
By wet spray, a thin layer of, uniform and continuous coating is covered with stainless steel heater element surface,
900 DEG C are heated to, 20 minutes are incubated；Room temperature is cooled to, is produced.The thickness of the enamel coating is 100 μm.
Embodiment 2
Each component is mixed by following weight/mass percentage composition：The content of silica is that the content of 48%, aluminum oxide is 3%, oxygen
The content for changing boron is that the content of 30%, calcium oxide is that the content of 2%, cobalt oxide is that the content of 3%, titanium oxide is containing for 8%, zirconium oxide
Amount is that the content of 5%, calcium oxide is 1%；Molten state is again heated to, is cooled down, milling.
By electrostatic spraying, in stainless steel heater element surface application of slip coating, 800 DEG C are heated to, 10 minutes are incubated；Cooling
To room temperature, produce.The thickness of the enamel coating is 10 μm.
Embodiment 3
Each component is mixed by following weight/mass percentage composition：The content of silica is that the content of 32%, aluminum oxide is 10%, oxygen
The content for changing boron is that the content of 40%, calcium oxide is that the content of 5%, cobalt oxide is that the content of 6%, titanium oxide is containing for 2%, zirconium oxide
Amount is that the content of 2%, potassium oxide is 3%；Molten state is again heated to, is cooled down, milling.
By electrostatic spraying, in stainless steel heater element surface application of slip coating, 840 DEG C are heated to, 15 minutes are incubated；Cooling
To room temperature, produce.The thickness of the enamel coating is 50 μm.
Embodiment 4
Each component is mixed by following weight/mass percentage composition：The content of silica is that the content of 44%, aluminum oxide is 5%, oxygen
The content for changing boron is that the content of 34%, calcium oxide is that the content of 3%, cobalt oxide is that the content of 3%, titanium oxide is containing for 6%, zirconium oxide
Amount is that the content of 2%, lithia is 3%；Molten state is again heated to, is cooled down, milling.
By electrostatic spraying, in stainless steel heater element surface application of slip coating, 850 DEG C are heated to, 10 minutes are incubated；Cooling
To room temperature, produce.The thickness of the enamel coating is 350 μm.
Embodiment 5
Each component is mixed by following weight/mass percentage composition：The content of silica is that the content of 28%, aluminum oxide is 13%, oxygen
The content for changing boron is that the content of 44%, calcium oxide is that the content of 5%, cobalt oxide is that the content of 4%, titanium oxide is containing for 2%, zirconium oxide
Amount is that the content of 1%, sodium oxide molybdena is that the content of 1%, nickel is 2%；Molten state is again heated to, is cooled down, milling.
By electrostatic spraying, in stainless steel cup's surface application of slip coating, 860 DEG C are heated to, 10 minutes are incubated；It is cooled to room
Temperature, is produced.The thickness of the enamel coating is 500 μm.
Embodiment 6
Each component is mixed by following weight/mass percentage composition：The content of silica is that the content of 48%, aluminum oxide is 3%, oxygen
The content for changing boron is that the content of 30%, calcium oxide is that the content of 2%, cobalt oxide is that the content of 2%, titanium oxide is containing for 8%, zirconium oxide
Amount is that the content of 5%, potassium oxide is that the content of 1%, copper is 1%；Molten state is again heated to, is cooled down, milling.
By electrostatic spraying, in stainless steel heater element surface application of slip coating, 845 DEG C are heated to, 12 minutes are incubated；Cooling
To room temperature, produce.The thickness of the enamel coating is 40 μm.
Embodiment 7
Each component is mixed by following weight/mass percentage composition：The content of silica is that the content of 32%, aluminum oxide is 10%, oxygen
The content for changing boron is that the content of 40%, calcium oxide is that the content of 2%, cobalt oxide is that the content of 6%, titanium oxide is containing for 2%, zirconium oxide
Amount be 1%, sodium oxide molybdena content be 5%, the content that the content of silver is 1%, niobium be 1%；Molten state is again heated to, is cooled down, milling.
By electrostatic spraying, in stainless steel heater element surface application of slip coating, 845 DEG C are heated to, 12 minutes are incubated；Cooling
To room temperature, produce.The thickness of the enamel coating is 40 μm.
Experimental example 1
This experimental example is tested the composition provided with the present invention and existed in the enamel coating that metallic heating element surface is made
Properties after high temperature.
1st, hot test
By the heating element heater electrified regulation of coating, its surface temperature is gradually risen to 1500 DEG C, take out, then it is natural
Room temperature is cooled to, is repeated 50 times, is observed the change of its outward appearance, the results are shown in Table 1.
Table 1
2nd, endurance life test
The heating element heater of coating is put into electrified regulation in water-bath, carried out after 3000 circulation cold shock testings,
The change of its outward appearance is observed, 2 are the results are shown in Table.
Table 2
3rd, bacteria-eliminating efficacy
The heating element heater of coating to be measured is respectively put into 1L water-baths, electrified regulation to seething with excitement, running water it is total hard
Degree（With CaCO3Meter）For 480mg/L, total number of bacteria 128, testing result is shown in Table 3.
Table 3
Above-mentioned result of the test shows that the surface of the heating element heater for the coating that the present invention is provided is smooth, and hardness is high, structure
Densification, can effectively keep out spot corrosion, and zero defect, surface is difficult to retain impurity, be difficult scaling, the shrinkage factor and metal of coating
The shrinkage factor of heating element heater almost always, can prevent from heating process cracking because of convergent-divergent, service life is long,
Also, the heating element heater for the coating that the present invention is provided also has extraordinary antibacterial, antibacterial, sterilization, antivirus action.
The heating element heater for the coating that the present invention is also provided other embodiments has also carried out above-mentioned experiment, obtains phase
As result, because length is limited, this is no longer going to repeat them.
Claims (8)
1. a kind of composition as enamel material, it is characterised in that based on weight/mass percentage composition, the composition includes content
Boron oxide that the aluminum oxide for being 5~10% for 32~44% silica, content, content are 34~40%, content are 2~5%
Zirconium oxide that titanium oxide that cobalt oxide that calcium oxide, content are 2~6%, content are 2~8%, content are 1~5%, content are 1
~5% basic anhydride.
2. composition according to claim 1, it is characterised in that the basic anhydride include sodium oxide molybdena, potassium oxide, oxygen
Change the one or more in lithium, calcium oxide, magnesia.
3. composition according to claim 2, it is characterised in that the basic anhydride are sodium oxide molybdena, potassium oxide, oxidation
The mixing of lithium.
4. the composition according to claim any one of 1-3, it is characterised in that the composition also includes transition metal.
5. composition according to claim 4, it is characterised in that the transition metal includes one in silver, copper, nickel, niobium
Plant or a variety of.
6. composition according to claim 4, it is characterised in that the content of the transition metal is 1~2%.
7. the purposes of the composition described in a kind of any one of claim 1-6, it is characterised in that for described composition to be warded off
Porcelain is to the surface of metal base.
8. purposes according to claim 7, it is characterised in that the metal base includes metallic heating element, metal and drunk
Feeder tool, metal washing implement, the metal shell of household electrical appliance.
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| CN201310039629.2A CN103964690B (en) | 2013-01-31 | 2013-01-31 | A kind of composition as enamel material and application thereof |
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| CN201310039629.2A CN103964690B (en) | 2013-01-31 | 2013-01-31 | A kind of composition as enamel material and application thereof |
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| CN103964690B true CN103964690B (en) | 2017-11-07 |
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| 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 |
| 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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| JPH01122937A (en) * | 1987-11-04 | 1989-05-16 | Nakashima:Kk | Frit for glass flame spraying |
| CN1810693A (en) * | 2005-01-24 | 2006-08-02 | 肖特股份公司 | Lead-free and cadmium-free glass for glazing, enameling and decoration of glasses or glass-ceramics |
| CN1827544A (en) * | 2005-03-01 | 2006-09-06 | 王德强 | Leadless cadmium-free high-stability low-melting-point glass for glass colored glaze |
| CN101263004A (en) * | 2005-09-14 | 2008-09-10 | 费罗公司 | Extended firing range enamels to produce frost effects |
| CN101905951A (en) * | 2009-06-04 | 2010-12-08 | 梁梦林 | One-time-coating enamel and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01122937A (en) * | 1987-11-04 | 1989-05-16 | Nakashima:Kk | Frit for glass flame spraying |
| CN1810693A (en) * | 2005-01-24 | 2006-08-02 | 肖特股份公司 | Lead-free and cadmium-free glass for glazing, enameling and decoration of glasses or glass-ceramics |
| CN1827544A (en) * | 2005-03-01 | 2006-09-06 | 王德强 | Leadless cadmium-free high-stability low-melting-point glass for glass colored glaze |
| CN101263004A (en) * | 2005-09-14 | 2008-09-10 | 费罗公司 | Extended firing range enamels to produce frost effects |
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