CN103466948A - Leadless environmentally-friendly glass glaze, preparation method thereof, and glazed surface preparation method - Google Patents
Leadless environmentally-friendly glass glaze, preparation method thereof, and glazed surface preparation method Download PDFInfo
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- CN103466948A CN103466948A CN2013103552822A CN201310355282A CN103466948A CN 103466948 A CN103466948 A CN 103466948A CN 2013103552822 A CN2013103552822 A CN 2013103552822A CN 201310355282 A CN201310355282 A CN 201310355282A CN 103466948 A CN103466948 A CN 103466948A
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Abstract
The invention relates to a leadless environmentally-friendly glass glaze. The leadless environmentally-friendly glass glaze comprises base glaze, and the base glaze comprises 25-60wt% of SiO2, 5-30wt% of ZnO, 1-8wt% of CaO + MgO, 0-10wt% of BaO, 0-10wt% of SrO, 5-33wt% of B2O3, 0.5-11wt% of Al2O3, 0.5-10wt% of TiO2, 0-10wt% of ZrO2, 1-22wt% of K2O +Na2O and 1-10wt% of Li2O. The environmentally-friendly glass glaze contains no lead, can avoid damages to human bodies and the environment, can substitute traditional lead-containing glazes, has a lower price than leadless bismuth-containing glazes, is suitable for common flat glass, and can be toughened or sintered.
Description
Technical field
The present invention relates to a kind of glass enamel and preparation method thereof, but but relate to especially and a kind ofly be applicable to ordinary plate glass tempering or sintered leadless free environmental protection glass enamel and preparation method thereof and prepared the method for glaze by it.
Background technology
Colored glazed glass is wear-resisting, have certain resistance to acids and bases, also has the characteristics such as functional and ornamental, is widely used in the aspects such as architectural decoration, family property glass, electronic glass.Glass enamel is the important source material for preparing colored glazed glass, and the leaded toxic heavy metal that waits of the color glaze used traditionally, poor chemical stability, be subject to the erosion of Atmospheric Sulfur compound and turn black, and plumbous oxide can reduce the ability of glaze chemical resistance of concrete, in addition, in leaded glass and sour contact process, easily separate out lead, harmful to HUMAN HEALTH.Traditional color glaze many times is difficult to meet the requirement of modern environmental protection, therefore, and in the urgent need to being adapted to prepare the novel lead-free environmental protection color glaze of colored glazed glass.
Alternative lead glaze bismuth glaze, molybdenum glaze, zinc glaze arranged, although wherein bismuth glaze and molybdenum glaze excellent property, the glass enamel cost is difficult to reduce, and affects applying of this system glaze.
In view of this, need a kind of leadless environment-friendly glass enamel of invention, it possesses the advantage that preparation cost is cheap.
Summary of the invention
Technical problem to be solved of the present invention is to provide a kind of glass glaze and preparation method thereof and the method for preparing glaze, this glass enamel possesses leadless environment-friendly, advantage that raw material is cheap, this preparation method possesses simple, energy-conservation advantage, when this glass enamel prepares glaze, step is simple, and ratio of briquetting is high.
In order to solve the problems of the technologies described above, one aspect of the present invention provides a kind of glass enamel, and concrete technical scheme is as follows:
A kind of leadless environment-friendly glass glaze, it comprises parent glaze, described parent glaze comprises the component of following weight percent:
25-60%SiO
2；
5-30%ZnO；
1-8%CaO+MgO；
0-10%BaO；
0-10%SrO；
5-33%B
2O
3；
0.5-11%Al
2O
3；
0.5-10%TiO
2；
0-10%ZrO
2；
1-22%K
2O+Na
2O；
1-10%Li
2O。
Further, described parent glaze comprises the component of following weight percent:
31-60%SiO
2；
5-25%ZnO；
1-8%CaO+MgO；
0-8%BaO；
0-8%SrO；
5-33%B
2O
3；
0.5-9%Al
2O
3；
0.5-8%TiO
2；
0-7%ZrO
2；
2-22%K
2O+Na
2O；
1-8%Li
2O。
As the present invention, further improve, described glass glaze also comprises tinting material.
Described tinting material is 0.1-30% by weight percentage.
As the present invention, further improve, described tinting material is selected from following raw material: titanium white toner, cobalt blue toner, chrome green toner, copper-chrome black toner and haematochrome.
The present invention provides a kind of leadless environment-friendly of the present invention glass-glazed preparation method on the other hand, specifically comprises the following steps:
(1) take by weight percentage the parent glaze component of following weight percent: 25-60%SiO
2, 5-30%ZnO, 1-8%CaO+MgO, 0-10%BaO, 0-10%SrO, 5-33%B
2o
3, 0.5-11%Al
2o
3, 0.5-10%TiO
2, 0-10%ZrO
2, 1-22%K
2o+Na
2o, 1-10% Li
2o;
(2) all raw materials that step (1) taken are put into stirrer and are stirred or ball mill ball milling ball milling 10-30 minute, and its rotating speed is 60-100 rev/min, mixes;
(3) the resulting mixture of step (2) is founded under 1000-1300 ℃, made the complete melting of mixture, obtain the glass metal of melting;
(4) by the glass metal shrend of the resulting melting of step (3);
(5) glaze after step (4) shrend is put into to ball mill ball milling 1-6 hour, its rotating speed is 60-100 rev/min, obtains glass powder;
(6) glass powder step (5) obtained is dried in loft drier, and the gained powder is glass enamel.
Further improve as the present invention, also comprise the 0.1%-30% tinting material is joined to ball mill in described step (5), well-mixed step.
Last aspect of the present invention provides a kind of method that is prepared glaze by glass glaze of the present invention, specifically comprises the following steps:
(1) will get leadless environment-friendly glass glaze provided by the present invention, and add blender and be prepared into glaze slip;
(2) by the resulting glaze slip of step (1), glazing on glass basis, drying;
(3) the dried glass basis with glaze of step (2) is sent into to annealing furnace or roller kiln burn till, obtain.
As the present invention, further improve, described glass basis is ordinary plate glass.
As the present invention, further improve, firing temperature is 620-680 ℃.
In the present invention, SiO
2contribute to improve glass-glazed stability.SrO contributes to improve glass-glazed glossiness.Na
2o, this kind of material and K
2o, LiO
2play mixed alkali effect, reduce glass melting temperature and softening temperature.
Compared with prior art, the beneficial effect that the present invention obtains is:
1, the composite and glaze that screening provides of the present invention's process Multiple components does not contain lead, can avoid human body and environment are damaged, and the leaded glaze of the alternative tradition of this glaze, and the unleaded bismuth-containing glaze of cost ratio is cheap.
2, the present invention is by adding zinc oxide in parent glaze, the firing range while having enlarged glass glaze and sheet glass sintering.Zinc oxide makes zinc glaze meltable, and physical strength, elasticity, melting behaviour and the resistance toheat of glaze all had to good effect, zinc oxide add gloss, the whiteness that can also increase glaze, and can make the firing range of glaze increase.
3, glass glaze of the present invention is consistent with the sheet glass coefficient of expansion, has avoided glaze to break, peel off, and uses for a long time glaze can not come off.
4, the colored glazed glass chemical stability that glass glaze of the present invention is made for sheet glass is good.
But the tempering as required that 5, glass glaze of the present invention is made for sheet glass maybe can burn till, and the tempering colored glazed glass is safe, but sintering colored glazed glass secondary processing, as cutting, punching etc.
6, the preparation method's of glass-glazed preparation method provided by the present invention and glaze step is simple, and energy consumption is low, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1
A kind of glass glaze mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 25%SiO
2, 30%ZnO, 2.5%CaO+MgO, 10%BaO, 5.0%B
2o
3, 6.0%Al
2o
3, 10%TiO
2, 2.0%ZrO
2, 6.5%K
2o+Na
2o, 3.0% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in stirrer stir or ball mill in ball milling 10 minutes, its rotating speed is 100 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1000 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 1 hour with 15% blue pigments, its rotating speed is 100 rev/mins, fully is mixed into glaze.
During use, glass enamel and blender ratio are 65:35, after ground and mixed, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 640 ℃, sinter colored glazed glass into.
Embodiment 2
A kind of glass enamel mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 31%SiO
2, 5%ZnO, 3.0%CaO+MgO, 10%SrO, 19%B
2o
3, 11%Al
2o
3, 5%TiO
2, 6.0%K
2o+Na
2o, 10% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in that stirrer stirs or ball mill in ball milling 15 minutes, its rotating speed is 80 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1150 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 5 hours with 19% red pigment, its rotating speed is 70 rev/mins, fully is mixed into glaze.
During use, glass enamel and blender ratio are 75:25, after ground and mixed, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 620 ℃, sinter colored glazed glass into.
Embodiment 3
Glass enamel of the present invention mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 42%SiO
2, 30%ZnO, 2.0%CaO+MgO, 3%BaO, 1.0%SrO, 5%B
2o
3, 0.5%Al
2o
3, 2.5%TiO
2, 10%ZrO
2, 1%K
2o+Na
2o, 3.0% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in the stirrer agitating ball mill ball milling 18 minutes, its rotating speed is 73 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1200 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 4 hours with 8% white pigment, its rotating speed is 85 rev/mins, fully is mixed into glaze.
During use, glass enamel and blender ratio are 70:30, after ground and mixed, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 660 ℃, sinter colored glazed glass into.
Embodiment 4
Glass enamel of the present invention mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 58%SiO
2, 9.5%ZnO, 2.7%CaO+MgO, 5.0%BaO, 10.3%B
2o
3, 1.0%Al
2o
3, 0.5%TiO
2, 11%K
2o+Na
2o, 2.0% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in that stirrer stirs or ball mill in ball milling 30 minutes, its rotating speed is 60 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1300 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 2 hours with 23% veridian, its rotating speed is 100 rev/mins, fully is mixed into glaze.
During use, glass enamel and the blender ratio of grinding are 60:40, after mill mixes, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 680 ℃, sinter colored glazed glass into.
Embodiment 5
A kind of glass glaze mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 31%SiO
2, 9.5%ZnO, 8.0%CaO+MgO, 8.0%SrO, 8.0%B
2o
3, 9.0%Al
2o
3, 4.0%TiO
2, 3.5%ZrO
2, 11%K
2o+Na
2o, 8.0% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in stirrer stir or ball mill in ball milling 10 minutes, its rotating speed is 100 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1000 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 1 hour with 0.5% blue pigments, its rotating speed is 100 rev/mins, fully is mixed into glaze.
During use, glass enamel and blender ratio are 60:40, after ground and mixed, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 630 ℃, sinter colored glazed glass into.
Embodiment 6
A kind of glass enamel mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 31%SiO
2, 20%ZnO, 8.0%CaO+MgO, 4.0%BaO, 22%B
2o
3, 0.5%Al
2o
3, 8.0%TiO
2, 2.0%K
2o+Na
2o, 4.5% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in that stirrer stirs or ball mill in ball milling 15 minutes, its rotating speed is 80 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1140 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 5 hours with 28% black pigment, its rotating speed is 70 rev/mins, fully is mixed into glaze.
During use, glass enamel and blender ratio are 70:30, after mill mixes, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 650 ℃, sinter colored glazed glass into.
Embodiment 7
Glass enamel of the present invention mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 42%SiO
2, 5.0%ZnO, 1.0%CaO+MgO, 4.0%SrO, 33%B
2o
3, 4.5%Al
2o
3, 0.5%TiO
2, 7.0ZrO
2, 2.0%K
2o+Na
2o, 1.0% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in the stirrer agitating ball mill ball milling 18 minutes, its rotating speed is 73 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1250 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 4 hours with 10% white pigment, its rotating speed is 85 rev/mins, fully is mixed into glaze.
During use, glass enamel and blender ratio are 65:35, after ground and mixed, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 670 ℃, sinter colored glazed glass into.
Embodiment 8
Glass enamel of the present invention mainly consists of parent glaze and tinting material, and each composition of parent glaze counts by weight percentage as follows: 60%SiO
2, 5.0%ZnO, 1.0%CaO+MgO, 8.0%BaO, 5.0%B
2o
3, 0.5%Al
2o
3, 0.5%TiO
2, 19%K
2o+Na
2o, 1.0% Li
2o; The manufacturing process of glass enamel is as follows:
By the weighing by weight percentage of above-mentioned formula material and be put in that stirrer stirs or ball mill in ball milling 30 minutes, its rotating speed is 60 rev/mins, fully mixes;
To be positioned in smelting furnace to mix admixtion, 1300 ℃ of lower molten batch material;
The good admixtion shrend by melting, obtain parent glaze;
By the parent glaze pulverize, and be positioned in ball mill ball milling 2 hours with 3% veridian, its rotating speed is 100 rev/mins, fully is mixed into glaze.
During use, glass enamel and blender ratio are 75:25, after mill mixes, can directly use, and silk screen printing, roller printing or thermospray be in glass surface, dryly by tempering or 620 ℃, sinter colored glazed glass into.
Comparative Examples 1
The method provided according to CN101255009 embodiment 2 prepares leadless cadmium-free glass enamel.The glass-glazed performance comparison that the glass glaze that the embodiment of the present invention is prepared and Comparative Examples 1 obtain is in Table 1:
The glass-glazed performance comparison that the glass glaze that table 1 embodiment of the present invention is prepared and Comparative Examples 1 obtain
To sum up, glass glaze provided by the invention possesses stability, opacifying power preferably, good glossiness.Melting altogether fastness is 100%, eutectic temperature 620-680 ℃.
Leadless environment-friendly color glaze of the present invention is comprised of following weight percent raw material: 25-60%SiO
2, 5-30%ZnO, 1-8%CaO+MgO, 0-10%BaO, 0-10%SrO, 5-33%B
2o
3, 0.5-11%Al
2o
3, 0.5-10%TiO
2, 0-10%ZrO
2, 1-22%K
2o+Na
2o, 1-10% Li
2o, 0.1-30% tinting material; By different formulas, found parent glaze under 1000-1300 ℃, tinting material is to add after the parent glaze shrend, after ball milling, oven dry, makes color glaze.But color glaze and the silk screen printing of blender furnishing, roller printing or thermospray glaze slip, glazing is in common float glass, dryly by tempering or 620-680 ℃, sinters colored glazed glass into.But blender is existing toughened glass color glaze blender used, for example the blender of color glaze allotment has frankincense, rosin ester, white oil of camphor, rosinol, arab resin glue, dextrin, agar, methylcellulose gum, polyvinyl alcohol, polymethacrylate, acid modified alcoholic resin, water, kerosene, turps, palmitinic acid, stearic acid, paraffin, hydro carbons paraffin, polyvinyl paraffin wax etc.
The above embodiment is only the preferred embodiments of the present invention, and is not the exhaustive of the feasible enforcement of the present invention.For persons skilled in the art, any apparent change of under the prerequisite that does not deviate from the principle of the invention and spirit, it having been done, within all should being contemplated as falling with claim protection domain of the present invention.
Claims (9)
1. a leadless environment-friendly glass glaze, it is characterized in that: it comprises parent glaze, described parent glaze comprises the component of following weight percent:
25-60%SiO
2；
5-30%ZnO；
1-8%CaO+MgO；
0-10%BaO；
0-10%SrO；
5-33%B
2O
3；
0.5-11%Al
2O
3；
0.5-10%TiO
2；
0-10%ZrO
2；
1-22%K
2O+Na
2O；
1-10%Li
2O。
2. a kind of leadless environment-friendly glass glaze according to claim 1, it is characterized in that: described glass glaze also comprises tinting material.
3. a kind of leadless environment-friendly glass glaze according to claim 2 is characterized in that: described tinting material is 0.1-30% by weight percentage.
4. according to the described a kind of leadless environment-friendly glass glaze of claim 2 or 3, it is characterized in that: described tinting material is selected from following raw material: titanium white toner, cobalt blue toner, chrome green toner, copper-chrome black toner and haematochrome.
5. the glass-glazed preparation method of a kind of leadless environment-friendly as claimed in claim 1 is characterized in that: specifically comprise the following steps:
(1) take by weight percentage the parent glaze component of following weight percent: 25-60%SiO
2, 5-30%ZnO, 1-8%CaO+MgO, 0-10%BaO, 0-10%SrO, 5-33%B
2o
3, 0.5-11%Al
2o
3, 0.5-10%TiO
2, 0-10%ZrO
2, 1-22%K
2o+Na
2o, 1-10% Li
2o;
(2) all raw materials that step (1) taken are put into stirrer and are stirred or ball mill ball milling 10-30 minute, and its rotating speed is 60-100 rev/min, mixes;
(3) the resulting mixture of step (2) is founded under 1000-1300 ℃, made the complete melting of mixture, obtain the glass metal of melting;
(4) by the glass metal shrend of the resulting melting of step (3);
(5) glaze after step (4) shrend is put into to ball mill ball milling 1-6 hour, its rotating speed is 60-100 rev/min, obtains glass powder;
(6) glass powder step (5) obtained is dried in loft drier, and the gained powder is glass enamel.
6. the glass-glazed preparation method of a kind of leadless environment-friendly according to claim 5, is characterized in that: also comprise the 0.1%-30% tinting material is joined to ball mill in described step (5), well-mixed step.
7. a method for preparing glaze is characterized in that: specifically comprise the following steps:
(1) the leadless environment-friendly glass glaze provided to claim 1 or 2, add blender and be prepared into glaze slip;
(2) by the resulting glaze slip of step (1), glazing on glass basis, drying;
(3) the dried glass basis with glaze of step (2) is sent into to annealing furnace or roller kiln burn till, obtain.
8. a kind of method for preparing glaze according to claim 7, it is characterized in that: described glass basis is ordinary plate glass.
9. a kind of method for preparing glaze according to claim 7, it is characterized in that: firing temperature is 620-680 ℃.
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| CN104478217A (en) * | 2014-11-24 | 2015-04-01 | 河北省沙河玻璃技术研究院 | Environment-friendly copper ruby glass glaze, preparation method of environment-friendly copper ruby glass glaze and method for preparing copper ruby glass glaze surface from environment-friendly copper ruby glass glaze |
| CN104403419A (en) * | 2014-12-04 | 2015-03-11 | 河北省沙河玻璃技术研究院 | Glass ink for ink-jet printing and preparation method of glass ink |
| CN105601113B (en) * | 2015-12-29 | 2019-02-19 | 广东美的厨房电器制造有限公司 | Antibacterial enamel material and its preparation method and application |
| CN105601113A (en) * | 2015-12-29 | 2016-05-25 | 广东美的厨房电器制造有限公司 | Antibacterial enamel material and preparation method and application thereof |
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| CN107586031A (en) * | 2017-10-26 | 2018-01-16 | 湖南嘉盛电陶新材料股份有限公司 | Anti-sticking glass glaze and its preparation method and application |
| CN107586031B (en) * | 2017-10-26 | 2020-03-31 | 湖南嘉盛电陶新材料股份有限公司 | Anti-sticking glass glaze and preparation method and application thereof |
| CN107793033A (en) * | 2017-11-06 | 2018-03-13 | 江苏宜翔陶瓷科技有限公司 | Suitable for the sapphire blue glaze repeatedly to flash back |
| CN110950537A (en) * | 2018-09-27 | 2020-04-03 | 湖南嘉业达电子有限公司 | Preparation method of low-expansion low-temperature environment-friendly glass glaze |
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| CN109111118A (en) * | 2018-10-25 | 2019-01-01 | 中山市大盛文化传播有限公司 | ceramic glaze and porcelain |
| CN110776259A (en) * | 2019-11-01 | 2020-02-11 | 湖南嘉盛电陶新材料股份有限公司 | Low-expansion-coefficient medium-low temperature environment-friendly glass powder and preparation method and application thereof |
| CN111453994A (en) * | 2020-05-14 | 2020-07-28 | 东莞市唯美陶瓷工业园有限公司 | White glaze, ceramic tile and preparation method of ceramic tile |
| CN111453994B (en) * | 2020-05-14 | 2021-11-30 | 东莞市唯美陶瓷工业园有限公司 | White glaze, ceramic tile and preparation method of ceramic tile |
| CN112551896A (en) * | 2020-12-08 | 2021-03-26 | 上海华伽电子有限公司 | Lead-free low-temperature glass, preparation method thereof and diode glass bulb prepared from glass |
| CN114379241A (en) * | 2021-08-06 | 2022-04-22 | 山东华菱电子股份有限公司 | Thermal print head substrate with composite lead-free protective layer and manufacturing method thereof |
| CN114379241B (en) * | 2021-08-06 | 2023-01-20 | 山东华菱电子股份有限公司 | Thermal print head substrate with composite lead-free protective layer and manufacturing method thereof |
| CN115337840A (en) * | 2022-07-19 | 2022-11-15 | 安徽沃尔德新材料有限公司 | Production process and production device of acid-base-resistant low-VOCs-emission water-based glass glaze |
| CN116813382A (en) * | 2023-07-05 | 2023-09-29 | 邓念东 | Method for forming crystal color decorative layer on surface of ceramic or glass article |
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Application publication date: 20131225 |