CN103224415B - One-time sintered cobalt blue frit dry particles and preparation method thereof - Google Patents
One-time sintered cobalt blue frit dry particles and preparation method thereof Download PDFInfo
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- CN103224415B CN103224415B CN201310153086.7A CN201310153086A CN103224415B CN 103224415 B CN103224415 B CN 103224415B CN 201310153086 A CN201310153086 A CN 201310153086A CN 103224415 B CN103224415 B CN 103224415B
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Abstract
The invention discloses one-time sintered cobalt blue frit dry particles and a preparation method thereof. The frit dry particle preparation raw materials comprise boric acid, borax, feldspar, quartz, dolomite, barium carbonate, non-calcined alumina, zirconium silicate, fluorspar, and cobalt oxide. The frit dry particles have an intrinsic cobalt blue color and good gloss, and are semitransparent. The particles are shiny under light. The frit dry particles has high initial melting temperature, low high-temperature viscosity, appropriate expansion coefficient, wide sintering range, and good combination with a ceramic blank. The particles can be sintered in one time, such that energy consumption is reduced by approximately 15% than that of twice sintering.
Description
Technical field
The invention belongs to preparing ceramic clinker production technical field, particularly a kind of cobalt blue frit dry granular and preparation method thereof that once burns.
Background technology
Natural stone texture is soft elegant in appearance, elegant style.Yet large specification lithotome is extremely rare, have certain radioactivity.Devitrified glass is the mixture of a kind of microcrystal being formed through coalescent and crystallization by the glass of certain grain composition and glass.Quality is hard, glittering and translucent.But yet devitrified glass is relatively single in design process.And Antique Imitation Tiles can make up this point, thereby meet more human consumer by the design that micro mist cloth, silk screen, cylinder or ink-jet technology can obtain thousands of kinds.But it does not possess space multistory sense and the glittering and translucent property of stone material and devitrified glass.And crystallite brick is a kind of novel product that integrates stone material, glass and Antique Imitation Tiles advantage.
On the surface of biscuit, on cloth, have certain granules to the compound frit powder of joining, the crystallite brick obtaining after twice firing is throws brilliant brick, claims again two degree to burn and throws brilliant brick, secondary burning microcrystal composite board.Throw brilliant brick after polishing, the thickness of clear frit can reach 1～2mm, and the lines that therefore surface prints has more gradation sense, stereoscopic sensation to the more common polished tile of people's artistic effect.Yet because the low temperature sinter cycle is generally 160min left and right, the high temperature biscuiting time of burning till more for the first time (cycle 50～70min) is wanted slow several times, will make thus production occur inconvenience.First, burn till the once burning that cost is more general and want high; In addition, the adobe that biscuiting line is supplied is greater than the demand of glaze firing line, and unnecessary brick need to manually be removed and unload down, after move back to again glaze firing line, this has not only increased employee's labor capacity and has taken warehouse storage space, has increased handling cost; The more important thing is, biscuiting line can not empty kiln in the idle time, thereby can impel the biscuiting line other products of often changing the line of production, and has increased again employee's labor capacity, and has caused the unstable of kiln, and then reduce conforming product rate when changing the line of production.
If secondary is burnt to change into once, burn, so above problem just can fundamentally be resolved.Crystallite brick once burns, and refers to that wall floor tile green compact are after glazing, stamp, need have certain granules to the compound frit powder of joining at surperficial cloth last layer, then enter the process that kiln burns till.
Due to the maximum feature of once-firing, to be that base glaze reacts together ripe, and this just requires base substrate before glaze maturation, gets rid of all volatile components, especially crystal water.General volatile component is just got rid of completely 950 ℃ of left and right, and this just requires cullet of glaze to have high beginning fusing point, reduces or avoids glaze to generate pore.So the special-purpose frit of once burning crystallite brick that development is excellent, the excellence rate of assurance crystallization brick, is the sector technical barrier urgently to be resolved hurrily.
The present invention once burns coloured frit dry granular and itself carries cobalt blue, therefore can remove silk screen, cylinder or the ink-jet printing process of ceramics factory's glaze line from, so reduced greatly glaze line length, reduced the employee of related fields, improved production efficiency, promote modularization set degree, for Ceramics Enterprises has reduced cost, and promoted quality controllable degree.Compared to other technologies, frit dry granular of the present invention can be used in once-firing legal system for the principle of crystallite brick, and once burns special-purpose frit with other and compare, and performance is more superior.Once burn the microcrystal composite board that coloured frit dry granular is produced in conjunction with ceramic body, there is high rigidity, corrosion-resistant, resistance to compression, shock resistance, be stained with dirt, the feature such as radiationless less.Coloured frit dry granular of several different colours, the different effect of also can arranging in pairs or groups out, produces colorful crystallite brick.Coloured crystallite brick after polishing has unique artistic effect.
Summary of the invention
The object of the present invention is to provide a kind of cobalt blue frit dry granular and preparation method thereof that once burns.
The technical solution used in the present invention is:
Once burn a cobalt blue frit dry granular, by mass percentage, main chemical constitution is as follows: SiO
244～50%, Al
2o
314～16%, Fe
2o
30.08～0.15%, TiO
2<0.02%, CaO 12～15%, and MgO 5～7%, K
2o 0.5～1.5%, Na
2o 1～1.5%, B
2o
31～4%, CoO 0.2～1.2%, ZrO
23～5%, Ba
2o
31～5%, F 1～4%.
This frit dry granular is usingd boric acid, borax, potassium felspar sand, quartz, rhombspar, barium carbonate, non-Calcined polishing aluminum oxide, zirconium silicate, fluorite, cobalt oxide as raw material.
Preferably, this frit dry granular is prepared by the raw material of following mass parts: 2～6 parts of boric acid, 2～6 parts of boraxs, 8～15 parts of potassium felspar sands, 30～40 parts, quartz, 18～28 parts of rhombspars, 2～6 parts of barium carbonates, 7～15 parts of non-Calcined polishing aluminum oxides, 4～6 parts of zirconium silicates, 3～8 parts, fluorite, 0.3～1.0 part of cobalt oxide.
More excellent, this frit is prepared by the raw material of following mass parts: 4～6 parts of boric acid, 3～4 parts of boraxs, 8～15 parts of potassium felspar sands, 30～35 parts, quartz, 20～25 parts of rhombspars, 3～4 parts of barium carbonates, 11～15 parts of non-Calcined polishing aluminum oxides, 4～5 parts of zirconium silicates, 3～6 parts, fluorite, 0.3～0.6 part of cobalt oxide.
Preferably, this frit dry granular is prepared by the raw material of following mass parts: 4 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 33 parts, quartz, 25 parts of rhombspars, 4 parts of barium carbonates, 11 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 5 parts, fluorite, 0.5 part of cobalt oxide.
Preferably, this frit dry granular is prepared by the raw material of following mass parts: 6 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 30 parts, quartz, 25 parts of rhombspars, 3 parts of barium carbonates, 15 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 6 parts, fluorite, 0.3 part of cobalt oxide.
A preparation method who once burns cobalt blue frit dry granular, comprises the following steps:
1) take raw material, mix;
2) melting at 1450～1550 ℃ of temperature, is incubated 2～3 hours;
3) blowing shrend, dries, and granulation, obtains cobalt blue frit dry granular;
Wherein, as mentioned above raw materials used.
Preferably, the particle fineness of frit dry granular is 10～30 orders.
The invention has the beneficial effects as follows:
Of the present inventionly once burn that cobalt blue frit dry granular beginning fusing point is high, temperature flowing is good, be layered on ceramic board and can make its base substrate have enough time exhaust at oxidation stage, thereby reach, glaze bubble is few, the object of once-firing; Once-firing can save energy reduction of discharging, and energy consumption reduces by 15% left and right compared with twice firing;
The cobalt blue frit dry granular itself that once burns of the present invention carries cobalt blue, can remove the typography of ceramics factory's glaze line from, reduced glaze line length, reduce the employee of related fields, promoted modularization set degree, improve production efficiency, for Ceramics Enterprises reduces cost, and promoted quality controllable degree;
Of the present invention once burn cobalt blue frit dry granular glossiness good, be translucent, glittering under the irradiation of light, there is good artistic effect.
Accompanying drawing explanation
Fig. 1 is the photo that once burns cobalt blue frit dry granular of embodiment 1 preparation;
Fig. 2 is the photo that once burns cobalt blue crystallite brick of embodiment 7 preparations.
Embodiment
Below in conjunction with example, further illustrate the present invention.
In following examples, if no special instructions, described umber all refers to mass parts.By following chemical constitution, calculate proportioning (mass percent), take raw material, for the preparation of once burning cobalt blue frit dry granular: SiO
244～50%, Al
2o
314～16%, Fe
2o
30.08～0.15%, TiO
2<0.02%, CaO 12～15%, and MgO 5～7%, K
2o 0.5～1.5%, Na
2o 1～1.5%, B
2o
31～4%, CoO 0.2～1.2%, ZrO
23～5%, Ba
2o
31～5%, F 1～4%.
embodiment 1
Take 4 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 33 parts, quartz, 25 parts of rhombspars, 4 parts of barium carbonates, 11 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 5 parts, fluorite, 0.5 part of cobalt oxide, mix, melting at 1460 ℃ of temperature, is incubated 3 hours, blowing shrend, dry, granulation, making particle fineness is 10～30 orders, obtain cobalt blue frit dry granular, as shown in Figure 1, cobalt blue frit dry granular glossiness is good, be translucent, glittering under the irradiation of light.
embodiment 2
Take 4 parts of boric acid, 2 parts of boraxs, 15 parts of potassium felspar sands, 33 parts, quartz, 25 parts of rhombspars, 2 parts of barium carbonates, 11 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 3 parts, fluorite, 0.8 part of cobalt oxide, mix, melting at 1480 ℃ of temperature, be incubated 2.5 hours, blowing shrend, dry, it is 10～30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
embodiment 3
Take 3 parts of boric acid, 4 parts of boraxs, 8 parts of potassium felspar sands, 35 parts, quartz, 28 parts of rhombspars, 4 parts of barium carbonates, 7 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 8 parts, fluorite, 1.0 parts of cobalt oxides, mix, melting at 1450 ℃ of temperature, be incubated 3 hours, blowing shrend, dry, it is 10～30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
embodiment 4
Take 4 parts of boric acid, 6 parts of boraxs, 10 parts of potassium felspar sands, 40 parts, quartz, 20 parts of rhombspars, 6 parts of barium carbonates, 11 parts of non-Calcined polishing aluminum oxides, 4 parts of zirconium silicates, 5 parts, fluorite, 0.8 part of cobalt oxide, mix, melting at 1520 ℃ of temperature, be incubated 2 hours, blowing shrend, dry, it is 10～30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
embodiment 5
Take 6 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 30 parts, quartz, 25 parts of rhombspars, 3 parts of barium carbonates, 15 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 6 parts, fluorite, 0.3 part of cobalt oxide, mix, melting at 1480 ℃ of temperature, be incubated 2 hours, blowing shrend, dry, it is 10～30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
embodiment 6
Take 3 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 30 parts, quartz, 18 parts of rhombspars, 3 parts of barium carbonates, 13 parts of non-Calcined polishing aluminum oxides, 6 parts of zirconium silicates, 6 parts, fluorite, 0.6 part of cobalt oxide, mix, melting at 1550 ℃ of temperature, be incubated 2 hours, blowing shrend, dry, it is 10～30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
embodiment 7
Green compact apply ground-coat enamel, and consumption is 610 ± 2.5g/m
2, proportion 1.52 ± 0.01; At the cobalt blue frit dry granular of ground-coat enamel surface cloth last layer above-described embodiment 1 preparation, consumption is 6000 ± 5g/m
2; The adobe of having executed glaze and frit dry granular is fired to 130min in the kiln of 1200 ℃, obtain cobalt blue crystallite brick.
Sintering character: crystallite brick cover-coat enamel is as bright as a sixpence, is sparkling and crystal-clear soft cobalt blue, glittering and translucent under the irradiation of light, bright shinny, without the visible pore of naked eyes, pin hole, as shown in Figure 2.
Because this frit is close with the common brick glaze coefficient of expansion modelled after an antique, there is certain base glaze key coat, be combined better with adobe and cover-coat enamel.
The cobalt blue frit dry granular that once burns of the present invention passes through lot of experiments, prove out ground reduces boric acid component and increases alumina component, can make frit beginning Melting point elevation to 1050 ℃ left and right, before temperature rises to beginning fusing point, the moisture in green compact, organism have volatilized completely.By fluorite and rhombspar, the high temperature viscosity and the slow ground that reduce frit reduce beginning fusing point, are beneficial to high temperature bubble and are gathered into air pocket, increase the buoyancy of bubble floating, thereby bubble is drained as far as possible completely, and throwing is free of pinholes soil pick-up not afterwards.It is therefore of the present invention that once to burn cobalt blue frit dry granular beginning fusing point high, temperature flowing is good, is layered on ceramic board and can makes its base substrate have enough time exhaust at oxidation stage, thereby reach, glaze bubble is few, the object of once-firing, energy-saving and emission-reduction, energy consumption reduces by 15% left and right compared with twice firing;
The cobalt blue frit dry granular itself that once burns of the present invention carries cobalt blue, therefore the typography that can remove ceramics factory's glaze line from, reduced glaze line length, reduce the employee of related fields, promoted modularization set degree, improve production efficiency, for Ceramics Enterprises reduces cost, and promoted quality controllable degree.
Claims (7)
1. once burn a cobalt blue frit dry granular, by mass percentage, main chemical constitution is as follows: SiO
244～50%, Al
2o
314～16%, Fe
2o
30.08～0.15%, TiO
2<0.02%, CaO 12～15%, and MgO 5～7%, K
2o 0.5～1.5%, Na
2o 1～1.5%, B
2o
31～4%, CoO 0.2～1.2%, ZrO
23～5%, BaO1～5%, F 1～4%;
This frit dry granular is usingd boric acid, borax, potassium felspar sand, quartz, rhombspar, barium carbonate, non-Calcined polishing aluminum oxide, zirconium silicate, fluorite, cobalt oxide as raw material.
2. a kind of cobalt blue frit dry granular that once burns according to claim 1, is characterized in that: this frit dry granular is prepared by the raw material of following mass parts: 2～6 parts of boric acid, 2～6 parts of boraxs, 8～15 parts of potassium felspar sands, 30～40 parts, quartz, 18～28 parts of rhombspars, 2～6 parts of barium carbonates, 7～15 parts of non-Calcined polishing aluminum oxides, 4～6 parts of zirconium silicates, 3～8 parts, fluorite, 0.3～1.0 part of cobalt oxide.
3. a kind of cobalt blue frit dry granular that once burns according to claim 1 and 2, is characterized in that: this frit is prepared by the raw material of following mass parts: 4～6 parts of boric acid, 3～4 parts of boraxs, 8～15 parts of potassium felspar sands, 30～35 parts, quartz, 20～25 parts of rhombspars, 3～4 parts of barium carbonates, 11～15 parts of non-Calcined polishing aluminum oxides, 4～5 parts of zirconium silicates, 3～6 parts, fluorite, 0.3～0.6 part of cobalt oxide.
4. a kind of cobalt blue frit dry granular that once burns according to claim 3, is characterized in that: this frit dry granular is prepared by the raw material of following mass parts: 4 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 33 parts, quartz, 25 parts of rhombspars, 4 parts of barium carbonates, 11 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 5 parts, fluorite, 0.5 part of cobalt oxide.
5. a kind of cobalt blue frit dry granular that once burns according to claim 3, is characterized in that: this frit dry granular is prepared by the raw material of following mass parts: 6 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 30 parts, quartz, 25 parts of rhombspars, 3 parts of barium carbonates, 15 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 6 parts, fluorite, 0.3 part of cobalt oxide.
6. once burn a preparation method for cobalt blue frit dry granular, comprise the following steps:
1) take raw material, mix;
2) melting at 1450～1550 ℃ of temperature, is incubated 2～3 hours;
3) blowing shrend, dries, and granulation, obtains cobalt blue frit dry granular;
Wherein, raw materials used as described in claim 1～5 any one.
7. preparation method according to claim 6, is characterized in that: the particle fineness of frit dry granular is 10～30 orders.
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| CN107555795A (en) * | 2017-10-13 | 2018-01-09 | 沈阳建筑大学 | A kind of cobalt oxide high temperature purple ceramic glaze and preparation method thereof |
| CN109824270A (en) * | 2019-04-02 | 2019-05-31 | 佛山市禅城区科捷陶瓷原料有限公司 | A kind of decorative brick of diamond flash effect, colored dry granular and preparation method thereof |
| CN110498692A (en) * | 2019-09-30 | 2019-11-26 | 山东雅美特新材料科技股份有限公司 | A kind of colorful dry granular of ceramic plate and preparation method thereof |
| CN111218131B (en) * | 2019-12-12 | 2021-08-03 | 西北永新涂料有限公司 | Preparation method for preparing cobalt blue/clay mineral hybrid pigment by solid-phase method |
| CN111087834B (en) * | 2020-02-24 | 2021-07-13 | 中国科学院兰州化学物理研究所 | Method for preparing high-performance calcium-magnesium co-doped cobalt blue hybrid pigment by using dolomite |
| CN112174526A (en) * | 2020-10-12 | 2021-01-05 | 山东工艺美术学院 | Formula of glittering glaze for ceramic art manufacturing |
| CN116730749B (en) * | 2023-08-14 | 2023-11-03 | 广东大角鹿新材料有限公司 | Matte anti-slip Yi Jiechao wear-resistant diamond glaze, ceramic tile and preparation method thereof |
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Effective date of registration: 20221115 Address after: 529441 Room 102, 1st floor, Daoshi technology complex building, Sanlian fozai'ao, Shengtang Town, Enping City, Jiangmen City, Guangdong Province Patentee after: Guangdong Dow ceramic materials Co.,Ltd. Address before: Sanlian fozai'ao, Shengtang Town, Enping City, Jiangmen City, Guangdong Province 529400 Patentee before: GUANGDONG DOWSTONE TECHNOLOGY Co.,Ltd. |