CN104556688A - Emulsion opal glass and preparation method thereof - Google Patents

Emulsion opal glass and preparation method thereof Download PDF

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Publication number
CN104556688A
CN104556688A CN201410822472.5A CN201410822472A CN104556688A CN 104556688 A CN104556688 A CN 104556688A CN 201410822472 A CN201410822472 A CN 201410822472A CN 104556688 A CN104556688 A CN 104556688A
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parts
emulsion opal
opal glass
glass
cao
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CN104556688B (en
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杜晓欧
彭志钢
楼贤春
程金树
袁坚
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Hebei shahe glass technology research institute
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Abstract

The invention discloses a piece of emulsion opal glass and a preparation method thereof. The piece of emulsion opal glass adopts a low-alkali and high-calcium component system and particularly comprises the following components: 66 to 70 parts of SiO2, 5.5 to 8.5 parts of Al2O3, 0.5 to 4.0 parts of B2O3, 2.5 to 3.5 parts of Na2O, 0 to 3.0 parts of K2O, 0 to 3.0 parts of ZnO, 13 to 22 parts of CaO, 0 to 4.0 parts of MgO, 0.5 to 5.0 parts of P2O5, and 0.2 part of Sb2O3. The prepared emulsion opal glass has the expansion factor of 53-59*10<-7>/DEG C, is freon-free and harmless, is excellent in heat resistance, and can be taken as a raw material particularly suitable for production of dishware, and the preparation method provided by the invention is energy-saving and environment-friendly, can effectively lower manufacturing cost and can create excellent economic benefits for manufacturers.

Description

A kind of emulsion opal glass and preparation method thereof
Technical field
The invention belongs to the technical field of emulsion opal glass, be specifically related to a kind of emulsion opal glass and preparation method thereof being suitable for making tableware.
Background technology
Tableware is all in all age the important tool that in daily life, people exchange with food, and the development of development to human civilization of tableware plays vital effect.Society, along with the raising of people's living standard, has had higher pursuit to taste of food, and the consequent is the demand more harsh to daily tableware.
Emulsion opal glass, owing to having the color and luster of graceful air, is extensively subject to liking of human consumer.In addition, compared with traditional ceramics tableware, emulsion opal glass has the moulded manufacturability of near-zero water suction, smooth surface easy to clean and excellence, is more and more applied in tableware manufacture field.
As everyone knows, not only there is the problems such as erosion of refractory, crystallization be wayward in Fluoride Opal Glass production process, a large amount of volatilizations also can endanger the health of workman and the environment of surrounding, more can there is fluorochemical stripping dangerous in use procedure.But current emulsion opal glass tableware is on the market most or fluorine-containing product.The fluorine-containing dinner glass lay-up method that Corning Incorporated sells solves the stripping problem of fluorine, and namely product middle layer is designed to fluorine-containing emulsion opal glass, and inside and outside two sides is heat resistant transparent glass, but this technique is comparatively complicated, wayward, production cost is high, is unsuitable for promoting on a large scale.
Chinese patent CN102910818 discloses the heat-resisting emulsion opal glass of a kind of zinc borosilicate, and its goods are not fluorine-containing, and thermal expansivity is low, and whiteness is higher, but the B containing 10-15% in its composition 2o 3, a large amount of B 2o 3highly volatile, causes glass ingredient to change, and affects its opacity and whiteness, and causes infringement to melting furnaces, shortens its work-ing life, in addition, containing a large amount of ZnO and a small amount of Li in disclosed emulsion opal glass 2o, in glass system, these two kinds of component materials prices are relatively costly, and the production cost of emulsion opal glass is significantly increased.
In addition, on the moulding process of dinner glass goods, most producer continues to use traditional compression moulding mode, and this molding mode production efficiency is low, generally also needs to carry out polished finish, can increase production cost further after product molding.
Summary of the invention
The object of the invention is to provide a kind of not fluorine-containing heat-resisting emulsion opal glass, to human body and environmentally friendly, Heat stability is good, and production cost is low, is particularly useful for manufacturing tableware.
To achieve these goals, following technical scheme is inventor provided.
A kind of emulsion opal glass, with weight parts, consists of the following composition: SiO 266-70 part, Al 2o 35.5-8.5 part, B 2o 30.5-4.0 part, Na 2o 2.5-3.5 part, K 2o 0-3.0 part, ZnO0-3.0 part, CaO 13-22 part, MgO 0-4.0 part, P 2o 50.5-5.0 part, Sb 2o 30.2 part.
Above-mentioned emulsion opal glass, during it becomes to be grouped into, P 2o 5be preferably 0.5-2.0 part.Work as P 2o 5during for 0.5-2.0 part, emulsion opal glass goods are in 850-950 DEG C in annealing process, and preferably 900 DEG C, insulation 5-15min, can make milkiness particulate fine and smooth, even; Work as P 2o 5during for 2.0-5.0 part, only need normarzing annealing just can realize even milkiness, but during these parts by weight, the viscosity of glass is higher, glass mobility is deteriorated, and can cause certain difficulty to production, so preferred 0.5-2.0 part.
Above-mentioned emulsion opal glass, by weight percentage, preferably consists of the following composition: SiO 269.5 parts, Al 2o 36 parts, B 2o 32 parts, Na 2o 2.5 parts, K 2o 1 part, ZnO 2 parts, CaO16.5 part, MgO 0 part, P 2o 50.5 part, Sb 2o 30.2 part.
Above-mentioned emulsion opal glass, by weight percentage, preferably consists of the following composition: SiO 267.5 parts, Al 2o 38.5 parts, B 2o 30.5 part, Na 2o 2.5 parts, K 2o 1.5 parts, ZnO 2.7 parts, CaO 15.5 parts, MgO 0 part, P 2o 51.3 parts, Sb 2o 30.2 part.
Above-mentioned emulsion opal glass, by weight percentage, preferably consists of the following composition: SiO 266.5 parts, Al 2o 35.5 parts, B 2o 34.0 parts, Na 2o 3.0 parts, K 2o 1.2 parts, ZnO 1.0 parts, CaO 13 parts, MgO 3.8 parts, P 2o 52.0 parts, Sb 2o 30.2 part.
Above-mentioned emulsion opal glass, Na described in becoming to be grouped into 2o is with the Na of equimolar amount 2cO 3form is introduced, described K 2o is with the K of equimolar amount 2cO 3form is introduced, and described CaO is with the CaCO of equimolar amount 3form is introduced, described P 2o 5can with P 2o 5form directly prepare burden, also can select the Ca with equimolar amount 3(PO 4) 2form is introduced, with Ca 3(PO 4) 2when form is introduced, owing to generating CaO, therefore in composition, the need of original CaO adjust accordingly.
Invention also provides a kind of preparation method of above-mentioned emulsion opal glass, comprise following operation steps:
A. each composition is mixed to obtain admixtion;
B. admixtion is founded 3 hours at 1530-1580 DEG C of temperature;
C. the glass metal after founding is poured into the die for molding of 500 DEG C;
D. the glass after shaping is placed in the resistance furnace insulation 2 hours of 550-600 DEG C, is cooled to normal temperature after annealing, namely obtains emulsion opal glass.
The present invention additionally provides a kind of preparation method of above-mentioned emulsion opal glass simultaneously, comprises following operation steps:
A. each composition is mixed to obtain admixtion;
B. admixtion is founded 3 hours at 1530-1580 DEG C of temperature;
C. the glass metal after founding is cooled to 1100-1350 DEG C through punishment in advance road, inject mould shaping in centrifugal shaper, the glass temperature after shaping is 950-1000 DEG C;
D. the glass after shaping is sent in annealing furnace and carry out anneal, and be cooled to normal temperature with stove, namely obtain emulsion opal glass.
In the preparation method of above-mentioned two kinds of emulsion opal glasses, in each composition described in step a, Na 2o is with the Na of equimolar amount 2cO 3form is introduced, described K 2o is with the K of equimolar amount 2cO 3form is introduced, and described CaO is with the CaCO of equimolar amount 3form is introduced, described P 2o 5with P 2o 5form directly prepare burden, or with the Ca of equimolar amount 3(PO 4) 2form is introduced.
Sb in the present invention 2o 3for finings, the bubble produced in emulsion opal glass melting process can be removed.
In the preparation process of emulsion opal glass system of the present invention, phase-splitting can not be there is in high temperature section (1300 DEG C-1550 DEG C), easily there is phase-splitting in middle-temperature section (800 DEG C-950 DEG C), only needs to reach 5-15min in this temperature section soaking time and can obtain phase-splitting exquisiteness, uniform emulsion opal glass in shaping, annealing process.
Beneficial effect of the present invention is:
1. emulsion opal glass adopts the component system of low alkali high calcium, obtains 53-59 × 10 -7/ DEG C the coefficient of expansion, resistance toheat is good, floride-free pollution-free, can be used in multiple fields such as glassware for drinking water, artwork, illumination and decoration product, is specially adapted to the production of tableware.
2. the component system at high temperature not easily phase-splitting of emulsion opal glass employing, found and viscosity B coefficent can not occur by during material road and block supply channel, moulding process (800 DEG C-950 DEG C) easily phase-splitting, do not need second heat treatment can form fine and smooth uniform opaque effect, more energy-conserving and environment-protective.
3. the material property feature of emulsion opal glass is suitable for centrifugal molding process, and namely the glasswork after shaping has smooth surface, without the need to polishing, reduces production cost, and this technique is also convenient to the shaping of shaped piece simultaneously, and working efficiency is high.
4. the one-tenth of emulsion opal glass is grouped into middle B 2o 3for 0.5-4.0 part, content is lower, can effectively avoid it to volatilize, can not cause infringement to melting furnaces.
5. the one-tenth of emulsion opal glass is grouped into middle ZnO is 0-3.0 part, and content is lower, obviously can reduce the production cost of emulsion opal glass.
Embodiment
Below in conjunction with specific embodiment, content of the present invention is described in further detail.
Embodiment 1
The one-tenth of emulsion opal glass is grouped into as shown in table 1, all with weight parts.
Table 1
SiO 2 Al 2O 3 B 2O 3 Na 2O K 2O ZnO CaO MgO P 2O 5 Sb 2O 3
66.8 6.4 1.15 3.15 0 2.35 13.85 2.8 3.5 0.2
Preparation method is:
A. each composition is done charge calculation, weighing mixing according to table 1 composition, obtain admixtion;
B. admixtion is placed in High Temperature Furnaces Heating Apparatus and founds 3 hours in 1530 DEG C;
C. pour in the preheated copper-made mould of 500 DEG C be shaped to bulk by founding rear uniform glass metal;
D. be incubated in the resistance furnace shaping bulk sample being placed in 570 DEG C and anneal for 2 hours, naturally cool to normal temperature and namely obtain emulsion opal glass.
Embodiment 2
The one-tenth of emulsion opal glass is grouped into as shown in table 2, all with weight parts.
Table 2
SiO 2 Al 2O 3 B 2O 3 Na 2O K 2O ZnO CaO MgO P 2O 5 Sb 2O 3
70 6 2.1 3 0 2.85 13.25 0 2.8 0.2
Preparation method is:
A) each composition is done charge calculation, weighing mixing according to table 2 composition.
B) admixtion is placed in High Temperature Furnaces Heating Apparatus to found 3 hours in 1580 DEG C;
C) pour in the preheated copper-made mould of 500 DEG C be shaped to bulk by founding rear uniform glass metal;
D) be incubated in the resistance furnace shaping bulk sample being placed in 600 DEG C and anneal for 2 hours, be cooled to normal temperature and namely obtain emulsion opal glass.
Embodiment 3
The one-tenth of emulsion opal glass is grouped into as shown in table 3, all with weight parts.
Table 3
SiO 2 Al 2O 3 B 2O 3 Na 2O K 2O ZnO CaO MgO P 2O 5 Sb 2O 3
67.5 8.5 0.5 2.5 1.5 2.7 15.5 0 1.3 0.2
Preparation method is:
A) each composition is done charge calculation, weighing mixing according to table 3 composition.
B) admixtion is placed in High Temperature Furnaces Heating Apparatus to found 3 hours in 1550 DEG C;
C) pour in the preheated copper-made mould of 500 DEG C be shaped to bulk by founding rear uniform glass metal;
D) be cooled to 550 DEG C of insulations bolt down procedure after 1 hour after being incubated 5min in the electric furnace shaping bulk sample being placed in 900 DEG C, be cooled to normal temperature and namely obtain emulsion opal glass.
Embodiment 4
The one-tenth of emulsion opal glass is grouped into as shown in table 4, all with weight parts.
Table 4
SiO 2 Al 2O 3 B 2O 3 Na 2O K 2O ZnO CaO MgO P 2O 5 Sb 2O 3
69.5 6 2 2.5 1 2 16.5 0 0.5 0.2
Preparation method is:
A) each composition is done charge calculation, weighing mixing according to table 4 composition.
B) admixtion is placed in High Temperature Furnaces Heating Apparatus to found 3 hours in 1550 DEG C;
C) pour in the preheated copper-made mould of 500 DEG C shaping by founding rear uniform glass metal;
D) be cooled to 550 DEG C of insulations bolt down procedure after 1 hour after being incubated 10min in the electric furnace shaping bulk sample being placed in 950 DEG C, be cooled to normal temperature and namely obtain emulsion opal glass.
Embodiment 5
The one-tenth of emulsion opal glass is grouped into as shown in table 5, all with weight parts.
Table 5
SiO 2 Al 2O 3 B 2O 3 Na 2O K 2O ZnO CaO MgO P 2O 5 Sb 2O 3
66.5 5.5 4.0 3.0 1.2 1.0 13 3.8 2.0 0.2
Preparation method is:
A) each composition is done charge calculation, weighing mixing according to table 5 composition.
B) admixtion is placed in High Temperature Furnaces Heating Apparatus to found 3 hours in 1580 DEG C;
C) pour in the preheated copper-made mould of 500 DEG C be shaped to bulk by founding rear uniform glass metal;
D) be cooled to bolt down procedure after 550 DEG C of insulations 1 as a child after being incubated 10min in the electric furnace shaping bulk sample being placed in 850 DEG C, be cooled to normal temperature and namely obtain emulsion opal glass.
Embodiment 6
The one-tenth of emulsion opal glass is grouped into as shown in table 6, all with weight parts.
Table 6
SiO 2 Al 2O 3 B 2O 3 Na 2O K 2O ZnO CaO MgO P 2O 5 Sb 2O 3
66 5.5 0.5 2.5 0 0 13 0 0.5 0.2
Preparation method is:
A. each composition is done charge calculation, weighing mixing according to described ratio;
B. in electric smelter, found admixtion, glass melting temperature is 1580 DEG C;
C. rear uniform glass metal is founded shaping in centrifugal shaper through expecting to inject bowl-type mould after road is cooled to 1100 DEG C;
D. the glass of forming is sent into annealing furnace and carry out anneal, keep 5-15min at 950 DEG C of-800 DEG C of temperature sections, 600 DEG C-550 DEG C keep 1h, then with stove Temperature fall.
Embodiment 7
The one-tenth of emulsion opal glass is grouped into as shown in table 7, all with weight parts.
Table 7
SiO 2 Al 2O 3 B 2O 3 Na 2O K 2O ZnO CaO MgO P 2O 5 Sb 2O 3
70 8.5 4.0 3.5 3 3.0 22 4.0 5.0 0.2
Preparation method is:
A. each composition is done charge calculation, weighing mixing, Na according to described ratio 2o, K 2o introduces with its carbonate, P 2o 5with Ca 3(PO 4) 2introduce, other compositions are all introduced with oxide compound;
B. in electric smelter, found admixtion, glass melting temperature is 1530 DEG C;
C. the glass metal melted injects dish-type mould after punishment in advance road is cooled to 1350 DEG C, shaping in centrifugal shaper;
D. the glass of forming is sent into the anneal of carrying out 1h in the annealing furnace of 550-600 DEG C, then with stove Temperature fall.
Embodiment 8
Contriver has carried out performance test to the emulsion opal glass product that embodiment 1-7 obtains, and result is as shown in table 8.
Table 8
As can be seen from data in table 8, the present invention, the described emulsion opal glass coefficient of expansion is low, the highest temperature difference that can stand 150 DEG C, otherwise namely the temperature of goods is elevated to 160 DEG C or all can not burst from 10 DEG C suddenly.Emulsion opal glass chemical stability of the present invention is good simultaneously, and its tableware made can not only tolerate acid, alkalis, and there will not be the stripping of tableware composition dangerous when packing foods, use safety.

Claims (9)

1. an emulsion opal glass, is characterized in that, consists of the following composition with weight parts: SiO 266-70 part, Al 2o 35.5-8.5 part, B 2o 30.5-4.0 part, Na 2o 2.5-3.5 part, K 2o0-3.0 part, ZnO 0-3.0 part, CaO 13-22 part, MgO 0-4.0 part, P 2o 50.5-5.0 part, Sb 2o 30.2 part.
2. a kind of emulsion opal glass according to claim 1, is characterized in that, P 2o 5for 0.5-2.0 part.
3. a kind of emulsion opal glass according to claim 1, is characterized in that, consist of the following composition by weight percentage: SiO 269.5 parts, Al 2o 36 parts, B 2o 32 parts, Na 2o 2.5 parts, K 2o 1 part, ZnO 2 parts, CaO 16.5 parts, MgO 0 part, P 2o 50.5 part, Sb 2o 30.2 part.
4. a kind of emulsion opal glass according to claim 1, is characterized in that, consist of the following composition by weight percentage: SiO 267.5 parts, Al 2o 38.5 parts, B 2o 30.5 part, Na 2o2.5 part, K 2o 1.5 parts, ZnO 2.7 parts, CaO 15.5 parts, MgO 0 part, P 2o 51.3 parts, Sb 2o 30.2 part.
5. a kind of emulsion opal glass according to claim 1, is characterized in that, consist of the following composition by weight percentage: SiO 266.5 parts, Al 2o 35.5 parts, B 2o 34.0 parts, Na 2o 3.0 parts, K 2o 1.2 parts, ZnO 1.0 parts, CaO 13 parts, MgO 3.8 parts, P 2o 52.0 parts, Sb 2o 30.2 part.
6. Na according to claim 1-5 any one 2o is with the Na of equimolar amount 2cO 3form is introduced, K 2o is with the K of equimolar amount 2cO 3form is introduced, and CaO is with the CaCO of equimolar amount 3form is introduced, P 2o 5with P 2o 5or with the Ca of equimolar amount 3(PO 4) 2form is introduced.
7. the preparation method of a kind of emulsion opal glass as claimed in claim 1, is characterized in that, comprises following operation steps:
A. each composition is mixed to obtain admixtion;
B. admixtion is founded 3 hours at 1530-1580 DEG C of temperature;
C. the glass metal after founding is poured into the die for molding of 500 DEG C;
D. the glass after shaping is placed in the resistance furnace insulation 2 hours of 550-600 DEG C, is cooled to normal temperature with after annealing, namely obtains emulsion opal glass.
8. the preparation method of a kind of emulsion opal glass as claimed in claim 1, is characterized in that, comprises following operation steps:
A. each composition is mixed to obtain admixtion;
B. admixtion is founded 3 hours at 1530-1580 DEG C of temperature;
C. mould is injected after the glass metal after founding being cooled to 1100-1350 DEG C shaping in centrifugal shaper;
D. the glass after shaping is sent in annealing furnace and carry out anneal, and be cooled to normal temperature with stove, namely obtain emulsion opal glass.
9. the preparation method of a kind of emulsion opal glass according to claim 7 or 8, is characterized in that, in each composition described in step a, and Na 2o is with the Na of equimolar amount 2cO 3form is introduced, described K 2o is with the K of equimolar amount 2cO 3form is introduced, and described CaO is with the CaCO of equimolar amount 3form is introduced, described P 2o 5with P 2o 5form directly prepare burden, or with the Ca of equimolar amount 3(PO 4) 2form is introduced.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107434356A (en) * 2017-07-26 2017-12-05 江苏杰龙晶瓷科技有限公司 A kind of manufacture method of split-phase milkiness imitation jade of glass
CN109502967A (en) * 2018-11-22 2019-03-22 东华大学 A kind of acid and alkali-resistance free-floride opal glass and its preparation method and application
CN110436786A (en) * 2019-08-19 2019-11-12 淮阴工学院 A method of improving phosphate-opal glass whiteness
CN111039565A (en) * 2020-01-13 2020-04-21 山东晶峰玻璃科技有限公司 Milky white defluorinated glass and preparation method thereof

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RU2321561C1 (en) * 2006-11-02 2008-04-10 Юлия Алексеевна Щепочкина Opaque glass
CN101182117A (en) * 2007-11-09 2008-05-21 浙江大学 Calcium phosphate opaque glass and method for making same
CN102295413A (en) * 2011-06-14 2011-12-28 武汉理工大学 Preparation method of Zr-P fluoride-free opaque glass
CN102910818A (en) * 2012-11-19 2013-02-06 东华大学 Zinc-boron-silicon system heat-resisting environmental-friendly emulsion opal glass and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006052A1 (en) * 1994-08-24 1996-02-29 Glasforskningsinstitutet Opal glass
RU2321561C1 (en) * 2006-11-02 2008-04-10 Юлия Алексеевна Щепочкина Opaque glass
CN101182117A (en) * 2007-11-09 2008-05-21 浙江大学 Calcium phosphate opaque glass and method for making same
CN102295413A (en) * 2011-06-14 2011-12-28 武汉理工大学 Preparation method of Zr-P fluoride-free opaque glass
CN102910818A (en) * 2012-11-19 2013-02-06 东华大学 Zinc-boron-silicon system heat-resisting environmental-friendly emulsion opal glass and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107434356A (en) * 2017-07-26 2017-12-05 江苏杰龙晶瓷科技有限公司 A kind of manufacture method of split-phase milkiness imitation jade of glass
CN109502967A (en) * 2018-11-22 2019-03-22 东华大学 A kind of acid and alkali-resistance free-floride opal glass and its preparation method and application
CN109502967B (en) * 2018-11-22 2021-12-07 东华大学 Acid and alkali resistant fluoride-free opal glass and preparation method and application thereof
CN110436786A (en) * 2019-08-19 2019-11-12 淮阴工学院 A method of improving phosphate-opal glass whiteness
CN111039565A (en) * 2020-01-13 2020-04-21 山东晶峰玻璃科技有限公司 Milky white defluorinated glass and preparation method thereof
CN111039565B (en) * 2020-01-13 2022-07-08 山东晶峰玻璃科技有限公司 Milky white defluorinated glass and preparation method thereof

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