CN109133621B - Titanium color glaze for enamel - Google Patents
Titanium color glaze for enamel Download PDFInfo
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- CN109133621B CN109133621B CN201810523866.9A CN201810523866A CN109133621B CN 109133621 B CN109133621 B CN 109133621B CN 201810523866 A CN201810523866 A CN 201810523866A CN 109133621 B CN109133621 B CN 109133621B
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- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000010936 titanium Substances 0.000 title claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 20
- 238000010304 firing Methods 0.000 claims abstract description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 15
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910011255 B2O3 Inorganic materials 0.000 claims abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000010494 opalescence Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000004017 vitrification Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a titanium enamel glaze, which comprises the following components in percentage by mass: SiO 2230‑38％；B2O315‑19％；Al2O35‑8％；CaO 3‑5％；TiO212‑18％；BaO 7‑10％；Na2O 10‑15％；K2O 3‑5％；MgO 0.5‑0.8％；P2O52‑4％；SO30.05‑0.1％；ZnO 2‑5％；Cr2O30.1 to 0.3 percent; 0.3 to 0.5 percent of CuO; the invention has stable color, small color difference and good porcelain surface quality at different firing temperatures.
Description
Technical Field
The invention relates to an enamel glaze, in particular to a titanium colored enamel glaze with stable color.
Background
At present, most titanium glazes used in the world are white, color titanium glazes with relatively stable colors do not exist at home and abroad temporarily, and the requirement on the color stability of the titanium glazes means that the color change is small under different firing processes, and the color difference value is calculated to be within 2.5 according to a Hunter color difference formula.
With the continuous progress and development of enamel, enamel products are applied in a large number of different fields, such as the facade decoration of tunnels and subways; outer protection and decoration of curtain walls, etc. With the development of the times, the requirements of customers on color difference are more and more strict, the larger the plate is, the more difficult the color difference is to guarantee. Under different firing technologies, the chromaticity of the same glaze material can be greatly changed, the quality of the obtained enamel is influenced, the color difference value of the currently marketed titanium glaze under different firing technologies can reach more than 5, and the color is unstable.
Disclosure of Invention
The invention aims to provide a titanium enamel glaze material which has stable color, small color difference and good porcelain surface quality at different firing temperatures.
In order to solve the technical problem, the technical scheme of the invention is as follows: the titanium enamel color glaze comprises the following components: SiO 22，B2O3，Al2O3，CaO，TiO2，BaO，Na2O，K2O，MgO，P2O5，SO3， ZnO，Cr2O3，CuO。
The mass fractions of the components are preferably as follows:
SiO2 30-38％；B2O3 15-19％；Al2O3 5-8％；CaO 3-5％；TiO2 12-18％；BaO 7-10％；Na2O 10-15％；K2O 3-5％；MgO 0.5-0.8％；P2O5 2-4％；SO3 0.05-0.1％；ZnO 2-5％；Cr2O3 0.1-0.3％；CuO 0.3-0.5％。
SiO in glaze2Is a main component, is a main glass network forming body, and SiO in the glaze2The higher the amount of (A), the higher the firing temperature. In SiO2The content of (A) is increased within the range of 30-38%, so that the mechanical strength and hardness of the glaze can be improved, and the whiteness, chemical stability and thermal stability of the glaze can also be improved.
In the glaze provided by the invention, B2O3Not only the enamel solvent but also the network former of the enamel promotes the formation of the glassy phase at low temperature. B is2O3The increased content increases the mechanical strength of the enamel and improves the abrasion resistance. B is2O3Has good fluxing action, can reduce the softening temperature, viscosity, surface tension and expansion coefficient of the porcelain glaze, is beneficial to melting metal oxide and is beneficial to Cr2O3And CuO coloring.
Al in glaze provided by the invention2O3Is an intermediate oxide which can be combined with not only silica but also basic oxides. The vitrification capability of the porcelain glaze can be improved, the devitrification can be inhibited, the elasticity, the hardness and the chemical stability of the glaze can be obviously improved, and the chemical corrosion resistance can be improved.
The CaO in the glaze provided by the invention is a main solvent in the glaze, so that the viscosity of glaze melt is reduced, the fluidity of the glaze and the glossiness of the glaze are improved, the expansion coefficient of the glaze can be reduced, and the mechanical strength of the porcelain glaze is improved. The CaO content is increased (within the range of 3-5 percent by mass), so that the melting temperature of the porcelain glaze is increased, the viscosity is increased, the content is too high and reaches 6 percent, and the glossiness of the glaze surface is reduced.
TiO in the glaze provided by the invention2It can increase the opacifying action, acid resistance and luster of the porcelain glaze. Because of good opacification, the enamel only needs a thin coating layer, so the enamel layer has high thermal stability, impact resistance and breaking strength, has good color stability, and prevents the color from changing under different firing conditions.
BaO in the glaze provided by the invention is a fluxing agent, barium has the largest ionic radius in alkali metal, and the strongest alkalinity is the best fluxing effect in alkali metal oxidation, and the organic acid corrosion resistance of the glaze surface can be improved.
K in glaze provided by the invention2O and Na2O is a strong fluxing agent of the glaze, can obviously reduce the melting temperature and high-temperature viscosity of the glaze, and increases the refractive index of the glaze, thereby improving the glossiness of the glaze surface, and being beneficial to obtaining the enamel with high gloss after the glaze in the invention is fired. K2O and Na2The melting point of O is low, and the O is easy to be fused with SiO in the process of melting the porcelain glaze2The chemical reaction takes place, which gives off a large amount of heat, thereby lowering the heating temperature of the outside, and lowering the viscosity at high temperature.
The MgO is also a fluxing agent of the glaze, so that the viscosity of a melt can be reduced, the expansion coefficient of the glaze can be reduced, the cracking of the glaze surface is reduced, and the quality of the porcelain surface is improved.
P in glaze provided by the invention2O5The opalescence of the porcelain glaze can be increased, the reflection coefficient of the porcelain layer is increased, and the color stability of the glaze is improved by matching with titanium dioxide.
The ZnO in the glaze provided by the invention can play a good fluxing role in a larger range, reduce the expansion coefficient of the glaze and improve the glossiness. However, the mass fraction of zinc oxide is selected to be 2-5% because excessive use of the zinc oxide causes devitrification of the glaze and loss of permeability of the glaze.
The Cr in the glaze provided by the invention2O3And CuO as a colorant to impartThe color of the enamel glaze is used to achieve the effect of color decoration. Wherein Cr is2O3The main display green color can be from bright green to dark green, and the coating has excellent light resistance, heat resistance, chemical corrosion resistance and the like and high covering power. CuO is generally considered to appear blue when copper has a valence of + 2; the copper is green when the valence is + 1; when the copper is in the valence of 0, the colloid is colored and red, so that blue copper oxide is added to cooperate with Cr2O3Has the function of adjusting the color of glaze
Further preferably, the mass fractions of the components are as follows: SiO 22 38％；B2O3 15％；Al2O3 6.28％； CaO 3％；TiO2 12％；BaO 7％；Na2O 10％；K2O 3.2％；MgO 0.66％；P2O5 2.21％； SO3 0.06％；ZnO 2.12％；Cr2O3 0.12％；CuO 0.35％。
By adopting the technical scheme, the invention has the beneficial effects that: according to the invention, the titanium dioxide and the phosphorus pentoxide which have good opalescence are utilized according to the integral proportion of the components, and the components are matched with Cr2O3The coloring effect of the CuO is matched with other components, the enamel obtained by using the glaze in the invention under different firing processes has the color difference value Delta E within 2.5, small color difference value and stable color; meanwhile, the glaze obtained after firing has the gloss G value of 89.6-97.2, and has good color on the premise of no addition of other pigments, the surface of the obtained enamel has no pinholes or glazes, the porcelain surface is smooth and has good quality, and the acid resistance can reach the national standard level 2; the alkali resistance can reach the national standard and the grade of no light loss is achieved; therefore, the glaze material obtained by the invention has stable color, small color difference and good porcelain surface quality.
Thereby achieving the above object of the present invention.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
A titanium enamel glaze comprises the following components: SiO 22，B2O3，Al2O3，CaO，TiO2，BaO， Na2O，K2O，MgO，P2O5，SO3，ZnO，Cr2O3CuO, the specific mass fractions of the components are shown in Table 1; the glaze obtained in example 1 was fired under the following three process conditions:
firing at 790 ℃ for 4.5 min;
firing at 820 ℃ for 4.5 min;
firing at 840 ℃ for 4.5 min;
the enamel fired under the process conditions is respectively tested for the values of L, a, b and G by using a color difference meter with the model number of CD-6834/6836 produced by Germany BYK, the specific numerical values are shown in Table 2, and the chroma values obtained under the firing condition of 820 ℃ are respectively marked as L0、a0、b0The colorimetric values obtained under the conditions of 790 ℃ and 840 ℃ firing were respectively designated as Li、ai、biBy hunter color difference formula:
the glaze of example 1 was obtained for the difference in colour Δ E at different firing temperatures and the difference in colour was recorded in table 2.
The results of the tests on the visual inspection of the enamels obtained in example 1 at different firing temperatures for the presence of pinholes, glazes, quality of the enamel surface, acid resistance and alkali resistance are shown in Table 3.
Wherein the test means and test results of acid resistance refer to GB/T9989-.
Example 2
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Example 3
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Example 4
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Example 5
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Example 6
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Example 7
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Example 8
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Example 9
The main difference between the present embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in table 1; the results of the tests at different firing temperatures of this example are shown in tables 2 and 3.
Control group
The inventor purchases a commercial titanium glaze material and respectively burns the titanium glaze material under the following three process conditions:
firing at 790 ℃ for 4.5 min;
firing at 820 ℃ for 4.5 min;
firing at 840 ℃ for 4.5 min;
the enamel fired under the process conditions is respectively tested for the values of L, a, b and G by using a color difference meter with the model number of CD-6834/6836 produced by Germany BYK, the specific numerical values are shown in Table 2, and the chroma values obtained under the firing condition of 820 ℃ are respectively marked as L0、a0、b0The colorimetric values obtained under the conditions of 790 ℃ and 840 ℃ firing were respectively designated as Li、ai、biBy hunter color difference formula:
the glaze of example 1 was obtained for the difference in colour Δ E at different firing temperatures and the difference in colour was recorded in table 2.
Table 1 tabulation of mass fraction (%) -of each component of examples 1 to 9
Table 2 table showing the chromaticity values, i.e. the color difference values, of examples 1 to 9 and the control under different firing conditions
Table 3 tabulation of results of testing performance indexes of examples 1 to 9
As can be seen from table 1, table 2 and table 3, the titanium glaze materials obtained according to the components and mass fractions of examples 1 to 9 are fired at different temperatures to obtain enamels with a color difference value within 2.5, especially within 1.5 of example 1, so that the titanium glaze obtained in examples 1 to 9 has a small color difference value and stable color without adding pigments; examples 1 to 9 were compared with a control group, which had color difference values of 6.55 and 8.79 respectively under the conditions of three different firing processes, so that the glaze of the present invention had a significantly higher degree of color stability at different firing temperatures than the commercially available titanium glaze of the control group. The value G in table 2 also reflects the high gloss characteristics of the titanium enamel frits prepared in examples 1 to 9 after firing. From table 3, the enamel obtained after firing in each example has no pinholes, no glaze nodules, smooth and fine enamel surface, acid resistance up to national standard level 2, and alkali resistance up to non-gloss level, so the titanium glaze material obtained by the present invention has the characteristic of stable color at different firing temperatures on the premise of maintaining good basic physical and chemical properties.
Claims (2)
1. A titanium color enamel material is characterized in that: the composition comprises the following substances in percentage by mass:
SiO2 30-38％；B2O3 15-19％；Al2O3 5-8％；CaO 3-5％；TiO2 12-18％；BaO 7-10％；Na2O 10-15％；K2O 3-5％；MgO 0.5-0.8％；P2O5 2-4％；SO3 0.05-0.1％；ZnO 2-5％；Cr2O3 0.1-0.3％；CuO 0.3-0.5％；
the glaze is respectively fired under the following three process conditions:
firing at 790 ℃ for 4.5 min;
firing at 820 ℃ for 4.5 min;
firing at 840 ℃ for 4.5 min;
the enamel fired under the process conditions is respectively tested for the values of L, a, b and G by using a color difference meter with the model number of CD-6834/6836 produced by Germany BYK, and the chroma values obtained under the firing condition of 820 ℃ are respectively recorded as L0、a0、b0The colorimetric values obtained under the firing conditions of 790 ℃ and 840 ℃ are respectively recorded as Li、ai、biBy hunter color difference formula:
the color difference value delta E of the glaze material at different sintering temperatures is less than 2.5.
2. The titanium enamel glaze of claim 1, wherein: the mass fraction of each component is as follows: SiO 2238％；B2O3 15％；Al2O3 6.28％；CaO 3％；TiO2 12％；BaO 7％；Na2O 10％；K2O 3.2％；MgO 0.66％；P2O5 2.21％；SO3 0.06％；ZnO 2.12％；Cr2O30.12％；CuO 0.35％。
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|---|---|---|---|
| CN201810523866.9A CN109133621B (en) | 2018-05-28 | 2018-05-28 | Titanium color glaze for enamel |
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| CN201810523866.9A CN109133621B (en) | 2018-05-28 | 2018-05-28 | Titanium color glaze for enamel |
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| CN109133621B true CN109133621B (en) | 2021-04-13 |
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| CN114180839B (en) * | 2021-12-30 | 2024-01-26 | 浙江开尔新材料股份有限公司 | Particle toughened enamel glaze slurry, enamel plate and preparation method |
| CN114163872A (en) * | 2022-01-14 | 2022-03-11 | 英辉（大厂）自动化技术有限公司 | Low-viscosity automobile glass printing ink and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086091A (en) * | 2010-07-08 | 2011-06-08 | 石家庄正中科技有限公司 | Surface glaze, white enamel and preparation method thereof |
| CN102089253A (en) * | 2008-07-10 | 2011-06-08 | 费罗公司 | Zinc containing glasses and enamels |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6831027B2 (en) * | 2002-10-21 | 2004-12-14 | Ferro Corporation | Porcelain enamel having metallic appearance |
| WO2006124415A2 (en) * | 2005-05-12 | 2006-11-23 | Ferro Corporation | Porcelain enamel having a metallic appearance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102089253A (en) * | 2008-07-10 | 2011-06-08 | 费罗公司 | Zinc containing glasses and enamels |
| CN102086091A (en) * | 2010-07-08 | 2011-06-08 | 石家庄正中科技有限公司 | Surface glaze, white enamel and preparation method thereof |
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