CN114213014B - Nitrate-free environment-friendly steel plate enamel matt glaze and preparation method thereof - Google Patents
Nitrate-free environment-friendly steel plate enamel matt glaze and preparation method thereof Download PDFInfo
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- CN114213014B CN114213014B CN202210104456.7A CN202210104456A CN114213014B CN 114213014 B CN114213014 B CN 114213014B CN 202210104456 A CN202210104456 A CN 202210104456A CN 114213014 B CN114213014 B CN 114213014B
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- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 70
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 32
- 239000010959 steel Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010453 quartz Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- 229910021538 borax Inorganic materials 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 15
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 239000005388 borosilicate glass Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000005553 drilling Methods 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000001038 titanium pigment Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 74
- 229910002651 NO3 Inorganic materials 0.000 abstract description 43
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 43
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000010309 melting process Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 ferrous metal oxide Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- MJWMNCORAUQGIX-UHFFFAOYSA-N sodium nitric acid nitrate Chemical compound [Na+].O[N+]([O-])=O.[O-][N+]([O-])=O MJWMNCORAUQGIX-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D5/00—Coating with enamels or vitreous layers
-
- 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
- C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
- C03C2207/04—Compositions specially applicable for the manufacture of vitreous enamels for steel
Abstract
The invention discloses nitrate-free environment-friendly steel plate enamel matt glaze and a preparation method thereof. The enamel comprises the following components in parts by mass: 29-31 parts of quartz, 13-15 parts of borax zero water, 2-4 parts of potassium carbonate, 2-3 parts of titanium dioxide, 2-4 parts of sodium fluosilicate, 18-21 parts of sodium carbonate, 6-8 parts of calcium carbonate, 2-3 parts of barium carbonate and 20-22 parts of alumina. The raw materials are uniformly mixed according to the proportion, and are melted under the conditions of 1260+/-10 ℃ and pure oxygen, and the sintering temperature of the finished product is 800-840 ℃. The formula of the invention does not contain nitrate, thus fundamentally solving the problem that the existing steel plate enamel matt glaze generates Nitrogen Oxides (NO) in the production process x ) The gas discharge pollutes the environment.
Description
Technical Field
The invention belongs to the technical field of enamel, and particularly relates to nitrate-free environment-friendly steel plate enamel matt glaze and a preparation method thereof.
Background
The enamel glaze is prepared with refractory feldspar, quartz and other material, borax, sodium nitrate, potassium nitrate, sodium carbonate and other fusible chemical material, non-ferrous metal oxide and other characteristic material, and through compounding in certain proportion, high temperature smelting, and rapid cooling into granular or sheet borosilicate glass.
The introduction of nitrate (sodium nitrate, potassium nitrate, etc.) as an oxidizing agent and a fluxing agent into enamel has been a common knowledge for the industry and is an indispensable raw material for enamel in the traditional enamel theory. Up to now, no safe, colorless, reasonably priced raw material with both oxidizing and fluxing properties has been available to replace nitrate. Production practices have long proven that nitrates (especially alkali metal nitrates) are indeed indispensable raw materials in enamel glazes.
In the high-temperature melting process of enamel glaze, a series of complex physical and chemical reactions are carried out between the raw materials. Nitrate has good effect in enamel glaze, but can decompose to generate a large amount of nitrogen oxides at high temperature, so as to pollute the atmosphere. The nitrogen oxide exceeds the national emission standard by more than 40 times, and if the converter is adopted for production, the instantaneous release concentration of the nitrogen oxide exceeds the national standard by hundreds of thousands times. It is known that nitrogen oxides are a main factor of acid rain generated in air, and as environmental awareness of people is enhanced, the harm of nitrogen oxides released by nitrate in enamel production to the environment is increasingly attracting high attention from all parties.
Therefore, the standard emission of the nitrogen oxides and the improvement of the environment are the indistinct social responsibility and the necessary trend of the social and economic development of enterprises, and are the necessary choice for the survival of the enterprises. The applicant starts to research the nitrate removal amount in the enamel glaze from 2018, ensures that nitrate is not used or is less used as much as possible on the premise of not affecting the product performance, and ensures that the waste gas in the enamel glaze production process reaches the standard and is discharged by other measures.
The reduction of the emission of nitrogen oxides in the enamel production process mainly comprises three technical routes: firstly, nitrate is removed or reduced from the source, secondly, nitrogen oxides generated by air in the high-temperature state in the melting process are removed, and thirdly, the emission of the nitrogen oxides is reduced from treatment facilities, so that the national emission standard is achieved.
Prior art has also been developed to date for the simple removal of nitrate in enamel formulations, but if nitrate is removed purely for the purpose of nitrate removal, the immediate face is the need to sacrifice to some extent the quality of the product, since the fluxing and oxidizing properties of the corresponding nitrate are not correspondingly complemented, namely: on one hand, the fluxing agent in the porcelain glaze formula is reduced, and the flatness, leveling property and expansion coefficient of the porcelain surface of the porcelain glaze product are directly affected; on the other hand, since nitrate is oxidative, removal of nitrate during enamel melting results in reduction of part of the metal oxides in the enamel formulation, and thus enamel color development and adhesion properties are affected.
From the perspective of fluxing agent, the compound salt is used for replacing nitrate to be used as a raw material formula of the porcelain glaze, and the traditional melting process is used for melting, so that the fluxing effect is hopefully replaced. However, the use of nitrate removal results in a reduction of the oxidizing atmosphere during the melting of the enamel, which results in a reduction of the corresponding metal oxide fraction, which has an effect on both the hue and the adhesion of the enamel product. Therefore, after nitrate is removed, the original performance of the enamel product is maintained, and the fluxing effect and the oxidation effect are supplemented simultaneously.
The specific application of nitrate in enamel is mainly sodium nitrate and potassium nitrate, and under the condition of high temperature, the nitrate has good oxidation effect, so that the oxide can be ensured not to be reduced into simple substance in the melting process, and meanwhile, common nitrate sodium nitrate and potassium nitrate are decomposed at high temperature to obtain product Na 2 O and K 2 O has good fluxing action.
Taking sodium nitrate commonly used in the traditional nitrate-containing steel plate enamel glaze as an example, the chemical reaction of nitrate in the enamel glaze production is as follows:
the nitrate is decomposed to generate nitrite when heating and releases oxygen, thus preventing the metal oxide from generating reduction reaction when melting, leading the metal oxide to be converted into low valence state and even reduced into simple substance metal, thereby changing the components, physical and chemical properties and technological properties of the enamel glaze.
There have been studies and studies on partial nitrate removal. Chinese invention CN201810677390.4 provides a preparation technique of phosphosilicate enamel, chinese invention CN201010608133.9 discloses a high toughness enamel glaze, which is represented by them, and all are obtained by directly mixing various oxides and melting, so as to avoid nitrate use. This may be feasible for theoretical studies. However, under the prior art conditions, na 2 O and K 2 O has no industrial product, and has extremely active activity, poor stability and difficult storage stability. Thus, directly using sodium oxide and oxygenOxides such as potassium oxide are not practical because industrial production cannot be realized at present. The invention CN201310166353.4 discloses a high-low temperature resistant porcelain glaze for enamel, the use of nitrate is not involved in the formula, but the invention introduces the use of heavy metal lead for improving the product quality and reducing sintering points, which completely violates the safety requirement of daily application and is forbidden in industry, and simultaneously, the invention also involves the use of a large amount of sulfate, and the existence of sulfate even if the sulfate is very low, can cause explosion of a quenching link, thereby violating the basic requirement of safe production. In addition, the borate content in the formula is low, and the basic requirements of the enamel industry are not met. That is, the invention claims to be applicable to enamels, and in practice, the conditions of enamels are not reached even if the aforementioned drawbacks are not considered. The invention CN201711361365.7 discloses a matte sand-lined enamel core glaze and a production method thereof, wherein the core glaze does not seem to involve the use of nitrate, but is essentially a matting agent, and the matting purpose of the glaze is achieved by combining with the real glaze, so that the core glaze is not an independent glaze and cannot be used independently. Furthermore, in the "preliminary practice of nitrate-free enamel glaze" (Xie Xuexin, glass and enamel 2007.35 (1)) this document uses a method of increasing the air flow rate for the purpose of enhancing the oxidation, although the use of nitrate is not involved, the starting point is not to reduce nitrogen oxides but to solve the problem of sufficient oxidation of Ti-containing overglazes, for which purpose it is achieved by means of a technique of increasing the air flow rate. However, the air flow rate is increased, so that the melting furnace has obvious cooling effect, the reaction temperature of the melting furnace needs to be increased by increasing energy consumption in order to meet the requirement of the melting furnace, and a large amount of nitrogen is contained in the air, so that more nitrogen oxides can be generated by introducing a large amount of air under the high-temperature effect. Research practice shows that the empty firing melting furnace can cause the content of nitrogen oxides to exceed the national emission standard by more than 2 times. The result is even more conceivable if a large flow of air is introduced. Thus, although this document avoids the use of nitrates, eventually exacerbating the nitrogen oxidesIs contrary to the aim of reducing or eliminating nitrogen oxides.
In summary, in enamel research, nitrate is removed to improve environmental benefit, and meanwhile, the excellent quality of enamel products can be maintained, so that the method is significant and difficult in task.
Disclosure of Invention
The first aim of the invention is to provide the nitrate-free environment-friendly steel plate enamel matt glaze without reducing various performance indexes of the product aiming at the environmental protection problem existing in the traditional nitrate-containing steel plate enamel glaze.
The nitrate-free environment-friendly steel plate enamel matt glaze disclosed by the invention comprises the following formula: quartz, borax zero water, potassium carbonate, titanium pigment, sodium fluosilicate, sodium carbonate, calcium carbonate, barium carbonate and alumina; wherein, the mass parts of each component are respectively: 29-31 parts of quartz, 13-15 parts of borax zero water, 2-4 parts of potassium carbonate, 2-3 parts of titanium dioxide, 2-4 parts of sodium fluosilicate, 18-21 parts of sodium carbonate, 6-8 parts of calcium carbonate, 2-3 parts of barium carbonate and 20-22 parts of alumina.
Preferably, the mass parts of the components are as follows: 30.5 parts of quartz, 14 parts of borax zero water, 3.5 parts of potassium carbonate, 2.8 parts of titanium dioxide, 2.6 parts of sodium fluosilicate, 20 parts of sodium carbonate, 6.6 parts of calcium carbonate, 3 parts of barium carbonate and 20.5 parts of alumina.
Specifically, in the quartz, sio 2 Comprises the following components in percentage by mass: sio (Sio) 2 ≥99％。
Specifically, in the alumina raw material, the mass percentage of alumina is as follows: al (Al) 2 O 3 ≥98％。
The second object of the invention is to provide a method for preparing the nitrate-free environment-friendly steel plate enamel matt glaze.
The preparation method of the nitrate-free environment-friendly steel plate enamel matt glaze comprises the following steps:
(1) Weighing the following raw materials in parts by mass;
29-31 parts of quartz, 13-15 parts of borax zero water, 2-4 parts of potassium carbonate, 2-3 parts of titanium dioxide, 2-4 parts of sodium fluosilicate, 18-21 parts of sodium carbonate, 6-8 parts of calcium carbonate, 2-3 parts of barium carbonate and 20-22 parts of alumina;
(2) Stirring and mixing the raw materials in the step (1) uniformly;
(3) Adding the uniformly mixed materials into a melting furnace, and melting under the pure oxygen condition, wherein the melting temperature is controlled to be 1260+/-10 ℃;
(4) Obtaining borosilicate glass body after the materials in the step (3) are completely melted, drilling the melted borosilicate glass body, and rapidly drawing glass filaments with the length of 1.2-1.5 m for detection, wherein the detection requirements are as follows: the melting is completed within 1 meter of the glass fiber without knots;
(5) And (5) quenching the melted borosilicate glass body to obtain the product.
Specifically, the quenching in the step (5) is a water quenching or tabletting process method.
The third object of the invention is to provide the application of the nitrate-free environment-friendly steel plate enamel matt glaze, namely the application to blanks taking steel plates as matrixes, wherein the sintering temperature of finished products is 800-840 ℃.
The invention has the beneficial effects that:
at high temperature or by discharge, nitrogen and oxygen can be combined into NO x . Regarding NO x The generation mechanism of (2) is N in air at high temperature 2 NO is formed by oxidation, and the rate of formation is greatly dependent on the gas concentration and combustion temperature. Practice shows that the temperature reaches above 1000 ℃, and the empty firing melting furnace can also lead to the generation of nitrogen oxides with higher content. Therefore, pure oxygen is adopted to replace air, so that on one hand, the oxidizing atmosphere in the melting process can be increased, and on the other hand, the nitrogen oxide generated in the combustion process is emitted in a zero way.
In addition, the components and the dosage of the non-nitrate fluxing agent are adjusted in the formula, so that even if nitrate fluxing is not carried out in the enamel glaze, the melting can be completed according to the requirement. The method is a key technical innovation point in the invention, namely, after nitrate is removed, fluxing property in the enamel can still be ensured.
According to the nitrate-free environment-friendly steel plate enamel matt glaze and the preparation method thereof, the nitrate of the enamel glaze is removed, industrialization can be realized, the problem that the environment is polluted by nitric oxide discharged in the production process of the enamel glaze is solved, and the original physicochemical properties of the enamel glaze can be kept unchanged. Experimental practice proves that when 80% of the products in the series of enamel glaze manufacturers of the applicant do not contain nitrate, the residual approximately 20% of the products can not completely remove nitrate, but the use amount of nitrate can be reduced by more than 50%. The nitrate consumption is reduced to about 100 tons from 1000 tons in the original year, and the reduction rate is close to 85 percent. Only nitrate removal directly reduces 500 tons of nitrogen oxide discharge per year, and does not include the discharge of nitrogen in air converted into nitrogen oxide. And the performance (porcelain surface, luster, firing temperature) of the product after nitrate removal is unchanged, and the quality detection requirement of the national enamel product is met. Therefore, the implementation and popularization of the invention are beneficial to driving industry to upgrade, protecting ecological environment, and have extremely important environmental benefit, social benefit and popularization and application significance.
Drawings
FIG. 1 is a photograph of the steel sheet enamel matte glaze prepared in example 1 of the present invention applied to a steel sheet enamel glazing panel.
Fig. 2, 3 and 4 are the first, second and third pages of the test report of the application of the enamel matte glaze to the steel sheet prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific experimental examples.
The equipment used in the embodiment of the invention is as follows:
and (3) batching: a full-automatic batching and mixing system is adopted. The system is fully-automatic computer control and has the characteristics of accurate weighing, uniform mixing and high batching efficiency.
Melting: an automatic feeding system, a pure oxygen combustion system and an automatic discharging system are adopted. Since the effect of the oxidizing agent is removed after the nitrate is removed, the combustion condition of the furnace is improved, and pure oxygen combustion is changed, so that the effect of the oxidizing agent meets the requirement even though the nitrate is removed. This is also a key point in the present invention, namely the removal of nitrate, but the performance of the oxidizing agent is not altered.
And (3) packaging: an automatic packaging system is employed.
In the raw materials used in the embodiment of the invention, sio in quartz 2 Comprises the following components in percentage by mass: sio (Sio) 2 99% or more; the alumina raw material comprises the following components in percentage by mass: al (Al) 2 O 3 More than or equal to 98 percent. The purity of other raw materials meets the requirements of industrial grade.
Example 1:
(1) Weighing the following raw materials in parts by mass:
30.5KG of quartz, 13.5KG of borax zero water, 4KG of potassium carbonate, 2.8KG of titanium dioxide, 2.6KG of sodium fluosilicate, 21KG of sodium carbonate, 6.6KG of calcium carbonate, 3KG of barium carbonate and 20.5KG of alumina.
(2) The raw materials are stirred and mixed uniformly.
(3) And adding the uniformly mixed materials into a melting furnace, and melting under the pure oxygen condition, wherein the melting temperature is controlled to be 1260+/-10 ℃ for melting.
(4) Obtaining borosilicate glass body after the materials are completely melted, drilling the melted borosilicate glass body, and rapidly drawing the borosilicate glass body into glass filaments of 1.2-1.5 meters for detection, wherein the detection requirements are as follows: the melting is completed within 1 meter of the glass fiber without knots.
(5) And (3) quenching the melted borosilicate glass body (water quenching) to obtain the product.
Example 2:
the procedure of this example was essentially the same as that of example 1, except that:
the mass parts of the components in the step (1) are as follows: 30.5KG of quartz, 14KG of borax zero water, 3.5KG of potassium carbonate, 2.8KG of titanium dioxide, 2.6KG of sodium fluosilicate, 20KG of sodium carbonate, 6.6KG of calcium carbonate, 3KG of barium carbonate and 20.5KG of alumina.
In the step (5), the melted borosilicate glass body is quenched by adopting a tabletting process.
Example 3:
the procedure of this example was essentially the same as that of example 1, except that:
the mass parts of the components in the step (1) are as follows: 30.5KG of quartz, 15KG of borax zero water, 3KG of potassium carbonate, 2.8KG of titanium pigment, 2.6KG of sodium fluosilicate, 19KG of sodium carbonate, 6.6KG of calcium carbonate, 3KG of barium carbonate and 20.5KG of alumina.
Example 4:
the procedure of this example was essentially the same as that of example 1, except that:
the mass parts of the components in the step (1) are as follows: quartz 29KG, borax zero water 13KG, potassium carbonate 2KG, titanium dioxide 2KG, sodium fluosilicate 2KG, sodium carbonate 18KG, calcium carbonate 6KG, barium carbonate 2KG and alumina 20KG.
Example 5:
the procedure of this example was essentially the same as that of example 1, except that:
the mass parts of the components in the step (1) are as follows: quartz 31KG, borax zero water 15KG, potassium carbonate 4KG, titanium white 3KG, sodium fluosilicate 4KG, sodium carbonate 21KG, calcium carbonate 8KG, barium carbonate 3KG and alumina 22KG.
The product prepared by the invention is applied to a blank taking a steel plate as a matrix, and the sintering temperature of the finished product is 800-840 ℃.
Referring to fig. 1, the steel plate enamel prepared in the embodiment 1 of the invention has flat and fine porcelain surface, uniform and beautiful color and fully meets the requirements of users.
Referring to fig. 2, a test report of the application of the enamel matte glaze to the steel sheet prepared in example 2 of the present invention is shown. The detection unit is national glasses and glass detection center.
Experiments and detection results prove that the nitrate-free environment-friendly steel plate enamel matte glaze produced by the method has NO nitrogen oxide in the preparation process, various properties (porcelain surface, gloss, firing temperature) and the like of the obtained product all meet the requirements of the steel plate enamel matte glaze, the purpose of removing nitrate from the steel plate enamel matte glaze is realized, and the problem that the Nitrogen Oxide (NO) is generated in the production and processing processes of the traditional steel plate enamel matte glaze is fundamentally solved x ) The technical problem of environmental pollution caused by gas discharge.
Claims (7)
1. The nitrate-free environment-friendly steel plate enamel matt glaze is characterized by comprising the following components in percentage by weight: quartz, borax zero water, potassium carbonate, titanium pigment, sodium fluosilicate, sodium carbonate, calcium carbonate, barium carbonate and alumina; wherein, the mass parts of each component are respectively: 29-31 parts of quartz, 13-15 parts of borax zero water, 2-4 parts of potassium carbonate, 2-3 parts of titanium dioxide, 2-4 parts of sodium fluosilicate, 18-21 parts of sodium carbonate, 6-8 parts of calcium carbonate, 2-3 parts of barium carbonate and 20-22 parts of alumina.
2. The nitrate-free environment-friendly steel sheet enamel matt glaze according to claim 1, characterized in that: the weight portions of the components are as follows: 30.5 parts of quartz, 14 parts of borax zero water, 3.5 parts of potassium carbonate, 2.8 parts of titanium dioxide, 2.6 parts of sodium fluosilicate, 20 parts of sodium carbonate, 6.6 parts of calcium carbonate, 3 parts of barium carbonate and 20.5 parts of alumina.
3. The nitrate-free environment-friendly steel sheet enamel matt glaze according to claim 1, characterized in that: in the quartz, siO 2 Comprises the following components in percentage by mass: siO (SiO) 2 ≥99％。
4. The nitrate-free environment-friendly steel sheet enamel matt glaze according to claim 1, characterized in that: the alumina raw material comprises the following components in percentage by mass: al (Al) 2 O 3 ≥98％。
5. A method for preparing nitrate-free environment-friendly steel plate enamel matt glaze according to claim 1, which is characterized by comprising the following steps:
(1) Weighing the following raw materials in parts by mass;
29-31 parts of quartz, 13-15 parts of borax zero water, 2-4 parts of potassium carbonate, 2-3 parts of titanium dioxide, 2-4 parts of sodium fluosilicate, 18-21 parts of sodium carbonate, 6-8 parts of calcium carbonate, 2-3 parts of barium carbonate and 20-22 parts of alumina;
(2) Stirring and mixing the raw materials in the step (1) uniformly;
(3) Adding the uniformly mixed materials into a melting furnace, and melting under the pure oxygen condition, wherein the melting temperature is controlled to be 1260+/-10 ℃;
(4) Obtaining borosilicate glass body after the materials in the step (3) are completely melted, drilling the melted borosilicate glass body, and rapidly drawing glass filaments with the length of 1.2-1.5 m for detection, wherein the detection requirements are as follows: the melting is completed within 1 meter of the glass fiber without knots;
(5) And (5) quenching the melted borosilicate glass body to obtain the product.
6. The method for preparing the nitrate-free environment-friendly steel plate enamel matt glaze, which is characterized by comprising the following steps of: the quenching in the step (5) is a water quenching or tabletting process method.
7. Use of the nitrate-free environment-friendly steel sheet enamel matte glaze according to claim 1, characterized in that: the method is applied to blanks taking steel plates as matrixes, and the sintering temperature of finished products is 800-840 ℃.
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| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
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| CN101967042A (en) * | 2010-06-29 | 2011-02-09 | 蔡文仁 | Electrostatic enamel powder and preparation method thereof |
| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
| CN102659318A (en) * | 2012-04-20 | 2012-09-12 | 湖南信诺颜料科技有限公司 | Cracking preventing porcelain glaze of enamel and preparation of cracking preventing porcelain glaze |
| CN103693850A (en) * | 2013-12-09 | 2014-04-02 | 常熟市永达化工设备厂 | Preparation technology of nanocrystalline enamel |
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