CN103224415A - 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 PDF

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CN103224415A
CN103224415A CN2013101530867A CN201310153086A CN103224415A CN 103224415 A CN103224415 A CN 103224415A CN 2013101530867 A CN2013101530867 A CN 2013101530867A CN 201310153086 A CN201310153086 A CN 201310153086A CN 103224415 A CN103224415 A CN 103224415A
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parts
frit dry
dry granular
cobalt blue
frit
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CN103224415B (en
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詹经
王永健
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GUANGDONG DOWSTONE TECHNOLOGY Co Ltd
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GUANGDONG DOWSTONE TECHNOLOGY Co Ltd
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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

A kind of cobalt blue frit dry granular and preparation method thereof that once burns
Technical field
The invention belongs to the 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 material texture is soft elegant in appearance, elegant style.Yet big specification lithotome is extremely rare, have certain radioactivity.The devitrified glass microcrystal that to be a kind of glass by certain grain composition form through sintering and crystallization and the mixture of glass.Quality is hard, glittering and translucent.Yet but devitrified glass is single relatively in the design process.And brick modelled after an antique can remedy this point, thereby satisfies 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 the 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 brick advantage modelled after an antique.
On cloth on the surface of biscuit, have certain granules and give the compound frit powder of joining, be through the crystallite brick that obtains behind the twice firing and throw brilliant brick, claim that again two degree burnings are thrown brilliant brick, secondary burns the crystallite composition board.Throw brilliant brick through after polishing, the thickness of clear frit can reach 1~2mm, and the therefore surperficial lines that is printed has more gradation sense, stereoscopic sensation for people's the more common polished tile of artistic effect.Yet because the low temperature glaze firing cycle is generally about 160min, (cycle 50~70min) is wanted slow several times, will make thus to produce inconvenience to occur the high temperature biscuiting time of burning till for the first time.At first, burn till the more general once burning of cost and want high; In addition, the adobe that the biscuiting line is supplied is greater than the demand of glaze firing line, and unnecessary brick need manually be removed and unload down, after move back to the glaze firing line again, this has not only increased employee's labor capacity and has taken the warehouse storage space, has increased handling cost; The more important thing is that the 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, increased employee's labor capacity when changing the line of production again, and caused the instability of kiln, and then reduced product percent of pass.
If change the secondary burning into once burning, so Yi Shang problem just can fundamentally be resolved.Crystallite brick once burns, and refers to wall floor tile green compact through after the glazing, stamp, needs have certain granules at surperficial cloth last layer and gives the compound frit powder of joining, and enters the process that kiln burns till again.
React ripe together because the maximum characteristics of once-firing are the base glaze, this just requires base substrate before the glaze maturation, gets rid of all volatile components, especially crystal water.General volatile component is just got rid of about 950 ℃ fully, and this just requires the glaze frit 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 premium grads rate of assurance crystallization brick is the technical barrier that the sector needs 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 the glaze line length greatly, reduced the employee of related fields, improved production efficiency, promoted modularization set degree,, and promoted quality controllable degree for ceramic enterprise has reduced cost.Compared to other technologies, frit dry granular of the present invention can be used in the principle that the once-firing legal system is equipped with crystallite brick, and once burns special-purpose frit with other and compare, and performance is more superior.Once burn the crystallite composition board that coloured frit dry granular is produced in conjunction with ceramic body, have high rigidity, corrosion-resistant, resistance to compression, shock resistance, be stained with dirt, characteristics 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:
A kind of cobalt blue frit dry granular that once burns, 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 with 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 by the feedstock production of following mass parts: 2~6 parts of boric acid, 2~6 parts of boraxs, 8~15 parts of potassium felspar sands, quartzy 30~40 parts, 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 in fluorite, 0.3~1.0 part of cobalt oxide.
More excellent, this frit is by the feedstock production of following mass parts: 4~6 parts of boric acid, 3~4 parts of boraxs, 8~15 parts of potassium felspar sands, quartzy 30~35 parts, 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 in fluorite, 0.3~0.6 part of cobalt oxide.
Preferably, this frit dry granular is by the feedstock production of following mass parts: 4 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, quartzy 33 parts, 25 parts of rhombspars, 4 parts of barium carbonates, 11 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 5 parts in fluorite, 0.5 part of cobalt oxide.
Preferably, this frit dry granular is by the feedstock production of following mass parts: 6 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, quartzy 30 parts, 25 parts of rhombspars, 3 parts of barium carbonates, 15 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 6 parts in fluorite, 0.3 part of cobalt oxide.
A kind of preparation method who once burns cobalt blue frit dry granular may further comprise the steps:
1) takes by weighing raw material, mix;
2) fusion under 1450~1550 ℃ of temperature is incubated 2~3 hours;
3) blowing shrend, oven dry, 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 cobalt blue frit dry granular beginning fusing point height, temperature flowing is good, is layered on to make its base substrate at oxidation stage enough time exhausts be arranged on the ceramic board, the glaze bubble is few, the purpose of once-firing thereby reach; Once-firing can save energy reduction of discharging, and energy consumption reduces about 15% than 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 the glaze line length, reduce the employee of related fields, promoted modularization set degree, improved production efficiency,, and promoted quality controllable degree for ceramic enterprise reduces cost;
Of the present invention once burn cobalt blue frit dry granular glossiness good, be translucent, glittering under the irradiation of light, have good artistic effect.
Description of drawings
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 the cobalt blue crystallite brick of embodiment 7 preparations.
Embodiment
Below in conjunction with example, further specify the present invention.
In following examples, if no special instructions, described umber all refers to mass parts.Calculate proportioning (mass percent) by following chemical constitution, take by weighing raw material, be used for preparation and once burn 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 by weighing 4 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 33 parts in 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 in fluorite, 0.5 part of cobalt oxide, mix, fusion under 1460 ℃ of temperature is incubated 3 hours, the blowing shrend, oven 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, and is glittering under the irradiation of light.
Embodiment 2
Take by weighing 4 parts of boric acid, 2 parts of boraxs, 15 parts of potassium felspar sands, 33 parts in 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 in fluorite, 0.8 part of cobalt oxide, mix, fusion under 1480 ℃ of temperature, be incubated 2.5 hours, the blowing shrend, oven dry, it is 10~30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
Embodiment 3
Take by weighing 3 parts of boric acid, 4 parts of boraxs, 8 parts of potassium felspar sands, 35 parts in 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 in fluorite, 1.0 parts of cobalt oxides, mix, fusion under 1450 ℃ of temperature, be incubated 3 hours, the blowing shrend, oven dry, it is 10~30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
Embodiment 4
Take by weighing 4 parts of boric acid, 6 parts of boraxs, 10 parts of potassium felspar sands, 40 parts in 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 in fluorite, 0.8 part of cobalt oxide, mix, fusion under 1520 ℃ of temperature, be incubated 2 hours, the blowing shrend, oven dry, it is 10~30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
Embodiment 5
Take by weighing 6 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 30 parts in 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 in fluorite, 0.3 part of cobalt oxide, mix, fusion under 1480 ℃ of temperature, be incubated 2 hours, the blowing shrend, oven dry, it is 10~30 orders that granulation makes particle fineness, obtains cobalt blue frit dry granular.
Embodiment 6
Take by weighing 3 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, 30 parts in 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 in fluorite, 0.6 part of cobalt oxide, mix, fusion under 1550 ℃ of temperature, be incubated 2 hours, the blowing shrend, oven 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 the foregoing description 1 preparation, consumption is 6000 ± 5g/m 2The adobe of having executed glaze and frit dry granular is fired 130min in 1200 ℃ kiln, obtain the cobalt blue crystallite brick.
Sintering character: the crystallite brick cover-coat enamel is as bright as a sixpence, is sparkling and crystal-clear soft cobalt blue, and is glittering and translucent under the irradiation of light, bright shinny, the visible pore of no 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, has certain base glaze key coat, combines better with adobe and cover-coat enamel.
The cobalt blue frit dry granular that once burns of the present invention is by a large amount of tests, prove out ground reduces boric acid component and increases alumina component, frit beginning fusing point is increased to about 1050 ℃, and before temperature rose to the beginning fusing point, the moisture in the green compact, organism had volatilized fully.By fluorite and rhombspar, reduce the high temperature viscosity of frit and reduce the beginning fusing point slowly, be beneficial to that bubble is gathered into air pocket under the high temperature, increase the buoyancy of bubble floating, thereby bubble is drained as far as possible fully, free of pinholes soil pick-up not after the throwing.Therefore the cobalt blue frit dry granular beginning fusing point height that once burns of the present invention, temperature flowing is good, is layered on to make its base substrate at oxidation stage enough time exhausts be arranged on the ceramic board, and the glaze bubble is few, the purpose of once-firing thereby reach, energy-saving and emission-reduction, energy consumption reduces about 15% than twice firing;
The cobalt blue frit dry granular itself that once burns of the present invention carries cobalt blue, so the typography that can remove ceramics factory's glaze line from, reduced the glaze line length, reduce the employee of related fields, promoted modularization set degree, improved production efficiency,, and promoted quality controllable degree for ceramic enterprise reduces cost.

Claims (8)

1. one kind is once burnt cobalt blue frit dry granular, and 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%.
2. a kind of cobalt blue frit dry granular that once burns according to claim 1 is characterized in that: this frit dry granular with boric acid, borax, potassium felspar sand, quartz, rhombspar, barium carbonate, non-Calcined polishing aluminum oxide, zirconium silicate, fluorite, cobalt oxide as raw material.
3. a kind of cobalt blue frit dry granular that once burns according to claim 2 is characterized in that: this frit dry granular is by the feedstock production of following mass parts: 2~6 parts of boric acid, 2~6 parts of boraxs, 8~15 parts of potassium felspar sands, quartzy 30~40 parts, 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 in fluorite, 0.3~1.0 part of cobalt oxide.
4. according to any described a kind of cobalt blue frit dry granular that once burns of claim 1~3, it is characterized in that: this frit is by the feedstock production of following mass parts: 4~6 parts of boric acid, 3~4 parts of boraxs, 8~15 parts of potassium felspar sands, quartzy 30~35 parts, 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 in fluorite, 0.3~0.6 part of cobalt oxide.
5. a kind of cobalt blue frit dry granular that once burns according to claim 4 is characterized in that: this frit dry granular is by the feedstock production of following mass parts: 4 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, quartzy 33 parts, 25 parts of rhombspars, 4 parts of barium carbonates, 11 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 5 parts in fluorite, 0.5 part of cobalt oxide.
6. a kind of cobalt blue frit dry granular that once burns according to claim 4 is characterized in that: this frit dry granular is by the feedstock production of following mass parts: 6 parts of boric acid, 3 parts of boraxs, 10 parts of potassium felspar sands, quartzy 30 parts, 25 parts of rhombspars, 3 parts of barium carbonates, 15 parts of non-Calcined polishing aluminum oxides, 5 parts of zirconium silicates, 6 parts in fluorite, 0.3 part of cobalt oxide.
7. preparation method who once burns cobalt blue frit dry granular may further comprise the steps:
Take by weighing raw material, mix;
Fusion under 1450~1550 ℃ of temperature is incubated 2~3 hours;
The blowing shrend, oven dry, granulation obtains cobalt blue frit dry granular;
Wherein, raw materials used as described in any one of the claim 2~6.
8. preparation method according to claim 7 is characterized in that: the particle fineness of frit dry granular is 10~30 orders.
CN201310153086.7A 2013-04-27 2013-04-27 One-time sintered cobalt blue frit dry particles and preparation method thereof Active CN103224415B (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
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
CN111087834A (en) * 2020-02-24 2020-05-01 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
CN111218131A (en) * 2019-12-12 2020-06-02 西北永新涂料有限公司 Preparation method for preparing cobalt blue/clay mineral hybrid pigment by solid-phase method
CN112174526A (en) * 2020-10-12 2021-01-05 山东工艺美术学院 Formula of glittering glaze for ceramic art manufacturing

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111218131A (en) * 2019-12-12 2020-06-02 西北永新涂料有限公司 Preparation method for preparing cobalt blue/clay mineral hybrid pigment by solid-phase method
CN111087834A (en) * 2020-02-24 2020-05-01 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
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

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