CN1180672A - Recipe of glass ceramics and manufacturing technology thereof - Google Patents
Recipe of glass ceramics and manufacturing technology thereof Download PDFInfo
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- CN1180672A CN1180672A CN 97121931 CN97121931A CN1180672A CN 1180672 A CN1180672 A CN 1180672A CN 97121931 CN97121931 CN 97121931 CN 97121931 A CN97121931 A CN 97121931A CN 1180672 A CN1180672 A CN 1180672A
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- Prior art keywords
- glass
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Classifications
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- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
Abstract
The formula of microcrystal glass can be divided into two kinds. One is slag class, that is, slags, quartz sand, feldspar, limestone, fluorite, dolomite and talc are used as raw materials. Another is silt class, that is, silt, quartz sand, feldspar, sodium carbonate, limestone, dolomite, barite and fluorite are used as raw materials. The process for preparing the microcrystal glass is integral crystallization or sinter crystallization. Obtained microcrystal glass features high crystallizing rate, not deforming easily, no cracking, less surficial pores and high strength.
Description
The present invention relates to the relevant class made from high-compactness, it is the heterogeneous devitrified glass finishing material of characteristics that low porosity reaches not easy to crack, belongs to building material field.
In microcrystal glass material is produced, often contain pore more or less in the sintering glass ceramics sheet material that makes, reduced the performances such as intensity of finished product; Its surperficial pore will have a strong impact on its outward appearance and decorative effect after polishing polishing, and has reduced the yield rate of material.How to reduce the void content of devitrified glass product; improve its density and become one of main difficult problem that faces in the sintering glass ceramics production in fact; on the other hand; devitrified glass to the production of integrally crystallization method; often for reach allow the glass matrix crystallization purpose and add a large amount of network adjustment and modify the body ion and a large amount of nucleus agent, cause the glass network short texture, material property shortens; thereby wayward in crystallization process, the time regular meeting because of the too fast unbalanced stress of crystallization cause the cracking.
The prescription that the purpose of this invention is to provide a kind of devitrified glass, glass is not easy to crack in process of production to make devitrified glass, and reduces the void content of glass.
The objective of the invention is to realize by the component prescription of adjusting glass.The prescription of devitrified glass of the present invention is to make the glass matrix of making devitrified glass have two crystallization peak (Tc at least
1, Tc
2) and two crystallization peaks between and and glass transformation temperature (Tg) between the temperature interval all bigger.
Specifically, microcrystalline glass formula of the present invention has two classes:
First kind slag class: its component is (weight %):
SiO
2?44～60， Al
2O
3?3～10， CaO 10～21
MgO?3～7， ZnO?0.5～3.0， R
2O(Na
2O+K
2O)3～7
FeO+Fe
2O
3 0.1～24.0 S?0.2～1.5
B
2O
30～8, the reductive agent charcoal: 0～1, F
21～3
Cr
2O
3?0～1.5 Sb
2O
3 0～1
Wherein RO (CaO+MgO+ZnO+FeO) should account for 25～38%.
The Cr of Jia Ruing wherein
2O
3Or ZnS is as tinting material and nucleus agent.
Raw materials usedly be: slag, quartz sand, feldspar, Wingdale, fluorite, rhombspar, talcum.
The second class silt class: its component is (weight %)
SiO
2?44～65 Al
2O
3?4～11 CaO 10～20
MgO?0～4 ZnO?0～2.5 B
2O
3?0～6
R
2O(Na
2O+K
2O) 10～18 FeO+Fe
2O
3 0.1～2.0
Can add a certain amount of ZnS or TiO by the color and luster requirement
2Be tinting material and nucleus agent.Raw materials used is silt, quartz sand, feldspar, soda ash, Wingdale, rhombspar, barite, fluorite.
Technological process with microcrystalline glass formula of the present invention is produced devitrified glass is respectively by integrally crystallization or sinterization:
1, integrally crystallization method
By the raw material of above-mentioned prescription, make sheet glass through fusing, calendering, die mould or cast technique, then in 550～620 ℃ of annealing, cool to room temperature gradually again.
The sheet glass that obtains is raised to T with 150～350 ℃/hour speed
C1Near near 0.5～1 hour (do not get rid of glass softening point be incubated for some time earlier) of insulation, then be raised to and be higher than Tc with the speed that is not more than 300 ℃/hour
250～200 ℃ are incubated about 1.5 hours, and cooling cooling then promptly obtains crystallizing glass sheet material.
2, sintering crystallization method:
The glass melt that will make by above-mentioned prescription flows in the water, and shrend becomes the disintegrating slag shape, and the glass disintegrating slag of getting granularity 1～15mm is put into and preserved to be had in the mould of ideal form, rises to a little less than T with the speed that is not higher than 400 ℃/hour
C1Near insulation 0.5～1 hour, (do not get rid of and near glass softening point, be incubated for some time earlier), the temperature insulation that rises between 1000 ℃～1120 ℃ with the speed that is not higher than 300 ℃/hour then is about 1.5 hours, make the softening and distortion of frit and adhere is in aggregates each other, simultaneously, crystal is separated out from glass slag surface, thereby obtains crystal glass.
According to the composition of raw materials of the inventive method design, because the glass that obtains contains at least two crystallization peaks, and between the crystallization peak and the interval between the glass transformation temperature Tg is bigger, thereby when we carry out the crystallization processing to it, at Tc
1Near after the insulation because the effect of suitable nucleus agent, in sheet glass, will occur the nucleation of first kind of crystalline phase and separate out, after continuing to heat up, glass inside grows second, third kind crystal on the interface of first kind of crystalline phase, the formation multiphase structure.Owing to avoid generating a large amount of crystal simultaneously in glass inside, glass all has a relaxation process in the crystallization and thermal treatment process in each stage, and the crystalline phase that generates has constituted the multiphase structure that is complementary, therefore the microcrystal glass plate that obtains has the percent crystallization in massecuite height, not yielding, do not ftracture the characteristic that intensity is high.
Under the situation of sintering crystallization, the inherent T of glass slag
C1Formed a part of crystalline phase 1 during near the processing, but owing to be inner homogeneous nucleation growth, simultaneously proportion is less, still is glass so keep the interior major part of slag charge, still can flow during afterwards intensification sintering, thereby in sintering process, can fuse each other by flowing mass transfer between the particle, the pore between the eliminating particle, and avoided sintering glass ceramics often because the particle premature setting that its at first surperficial crystallization face causes, the sintering difficulty, pore is difficult for the problem of eliminating.Simultaneously, the crystalline phase that grows on crystalline phase that grows on the embryos of Xing Chenging and the surface has formed compact multiphase structure in sintering crystallization process in advance, has reached the percent crystallization in massecuite height, and pore is few, the sintering glass ceramics of appearance looks elegant.
Embodiment 1:
With following mixture of ingredients 1450 ℃ of following fusion 100min with the preparation melten glass:
Plumbous zinc ore slag quartz sand feldspar fluorite C
2O
3CuO calcite weight % 56 20 10 6≤1 16
With the glass that makes 600 ℃ of annealing.It is carried out stage thermal treatment, and the fs holding temperature is 780 ℃, is incubated half an hour, and separate out a certain amount of chromite and augite crystalline phase in the glass this moment.Be warming up to 1040 ℃ and be incubated 1 hour, after cooling annealing is cooled to room temperature again, obtain the microcrystal glass plate that principal crystalline phase is pyroxene and wollastonite.Under Electronic Speculum, can be observed at subordinate phase insulation back wollastonite crystal and the staggered multiphase structure of various pyroxene.After surperficial grinding and polishing processing, promptly present pitch-dark shinny similar pitch black marmorean beautiful outward appearance, can be used as the fancy finishes material.
Embodiment 2:
With following mixture of ingredients 1530 ℃ of fusions 3 hours with preparation glass:
Shandong Yellow River mud feldspar calcite Na
2CO
3Weight % 66 10 16 8
In admixtion, add a certain amount of ZnS and TiO
2As the nucleus agent, the melten glass shrend is obtained little frit.The frit of 1～15mm preserved to send in moulding box make it in the tunnel furnace to keep 45min at 800 ℃, being warming up to 1100 ℃ then again kept 1 hour, cool to room temperature gradually again polishes the patterned glass that there is pore hardly in the surface that obtains green brilliant flower after the polishing.The crystalline phase that the analysis revealed fs separates out is devitrite and sub-fraction lime feldspar, and subordinate phase has been separated out a large amount of wollastonites, also some nepheline after handling in the plate.The wollastonite of the radial and short cylinder of separating out from the surface and nepheline and the short cylinder of before having separated out, part crystalline phases such as needle-like devitrite have formed the crystallite composite diphase material of high-compactness together.When crystal is separated out in the fs glass, because it is inner evenly crystallization substantially, the slag particle major part still remains vitreous state, has avoided mobile poor in the subordinate phase high-temperature process, easy-sintering is not eliminated the difficulty of pore, has obtained the very high microcrystal glass material of density.
Claims (2)
1, a kind of prescription of devitrified glass is characterized in that its composition is divided into:
First kind slag class: its component is (weight %):
SiO
2?44～60， Al
2O
3?3～10， CaO 10～21
MgO?3～7， ZnO?0.5～3.0， R
2O(Na
2O+K
2O)3～7
FeO+Fe
2O
3?0.1～24.0 S 0.2～1.5
B
2O
30～8, the reductive agent charcoal: 0～1, F
21～3
Cr
2O
3?0～1.5 Sb
2O
3 0～1
Wherein RO (CaO+MgO+ZnO+FeO) should account for 25～38%,
The second class silt class: its component is (weight %)
SiO
2?44～65 Al
2O
3?4～11 CaO 10～20
MgO 0～4 ZnO 0～2.5 B
2O
3?0～6
R
2O(Na
2O+K
2O)10～18 FeO+Fe
2O
3 0.1～2.0。
2, a kind of manufacturing process of devitrified glass is characterized by:
(1) integrally crystallization method
By the raw material of above-mentioned prescription, make sheet glass through fusing, calendering, die mould or cast technique, then in 550～620 ℃ of annealing, cool to room temperature gradually again; The sheet glass that obtains is raised to T with 150～350 ℃/hour speed
C1Near insulation 0.5～1 hour is not got rid of elder generation and be incubated for some time near glass softening point; Then be raised to and be higher than Tc with the speed that is not more than 300 ℃/hour
250～200 ℃ are incubated about 1.5 hours; Cooling cooling then promptly obtains crystallizing glass sheet material;
(2) sintering crystallization method:
The glass melt that will make by above-mentioned prescription flows in the water, and shrend becomes the disintegrating slag shape, and the glass disintegrating slag of getting granularity 1～15mm is put into and preserved to be had in the mould of ideal form, rises to a little less than T with the speed that is not higher than 400 ℃/hour
C1Near insulation 0.5～1 hour, do not get rid of and near glass softening point, be incubated for some time earlier, the temperature insulation that rises between 1000 ℃～1120 ℃ with the speed that is not higher than 300 ℃/hour then is about 1.5 hours, makes the softening and distortion of frit and adhere is in aggregates each other.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97121931 CN1180672A (en) | 1997-11-21 | 1997-11-21 | Recipe of glass ceramics and manufacturing technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97121931 CN1180672A (en) | 1997-11-21 | 1997-11-21 | Recipe of glass ceramics and manufacturing technology thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1180672A true CN1180672A (en) | 1998-05-06 |
Family
ID=5176550
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|---|---|---|---|
| CN 97121931 Pending CN1180672A (en) | 1997-11-21 | 1997-11-21 | Recipe of glass ceramics and manufacturing technology thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759368A (en) * | 2010-03-18 | 2010-06-30 | 凤县三联建材有限责任公司 | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof |
| CN101774762A (en) * | 2010-03-18 | 2010-07-14 | 凤县三联建材有限责任公司 | Black microlite manufactured by using lead and zinc smelting dreg and manufacturing method thereof |
| CN101805128A (en) * | 2010-04-20 | 2010-08-18 | 香港福山实业有限公司 | Jade-type glass-ceramic and preparation method thereof |
| CN101941801A (en) * | 2010-07-30 | 2011-01-12 | 华原风积沙开发有限公司 | Microcrystalline glass plate and producing process thereof |
| CN101718137B (en) * | 2009-11-19 | 2011-07-27 | 荥经县腾达石材开发有限责任公司 | Method for producing microcrystal glass decoration plate material with granite waste material |
| CN102173588A (en) * | 2011-03-10 | 2011-09-07 | 内蒙古科技大学 | Slag glass ceramic pipe and preparation method thereof |
| CN102491641A (en) * | 2011-12-09 | 2012-06-13 | 水经(上海)生物科技有限公司 | Wear-resistant crystallized glass plate and preparation method thereof |
| CN101528620B (en) * | 2006-10-27 | 2012-07-18 | 欧罗克拉公司 | Blue beta-quartz glass-ceramic materials, articles made thereof, and fabrication process |
| CN102617037A (en) * | 2012-03-27 | 2012-08-01 | 中国地质大学（武汉） | Method for preparing crystallized glass by directly sintering albite ore taken as raw material |
| CN102826759A (en) * | 2012-09-25 | 2012-12-19 | 内蒙古科技大学 | Method for directly preparing ferro-magnetic microcrystal glass by thermal state steel slag |
| CN102910827A (en) * | 2012-11-16 | 2013-02-06 | 中国地质科学院 | Novel wear-resisting plate produced by using waste moulding sand and preparation method of plate |
| CN107043217A (en) * | 2017-04-07 | 2017-08-15 | 东莞市银通玻璃有限公司 | A kind of production method of low-porosity micro-crystal glass |
| CN107098591A (en) * | 2017-03-30 | 2017-08-29 | 济南大学 | Franklinite glass ceramics is prepared using zinc-plated industrial residue |
| CN108409143A (en) * | 2018-06-13 | 2018-08-17 | 合肥协耀玻璃制品有限公司 | A kind of warping resistance devitrified glass |
| CN108821599A (en) * | 2018-09-06 | 2018-11-16 | 四川名微晶科技股份有限公司 | A method of devitrified glass is prepared using nepheline tailing as primary raw material |
| CN115745380A (en) * | 2022-10-31 | 2023-03-07 | 苏州大学 | Light sintered microcrystal plate and sintering process thereof |
-
1997
- 1997-11-21 CN CN 97121931 patent/CN1180672A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101528620B (en) * | 2006-10-27 | 2012-07-18 | 欧罗克拉公司 | Blue beta-quartz glass-ceramic materials, articles made thereof, and fabrication process |
| CN101718137B (en) * | 2009-11-19 | 2011-07-27 | 荥经县腾达石材开发有限责任公司 | Method for producing microcrystal glass decoration plate material with granite waste material |
| CN101774762A (en) * | 2010-03-18 | 2010-07-14 | 凤县三联建材有限责任公司 | Black microlite manufactured by using lead and zinc smelting dreg and manufacturing method thereof |
| CN101759368B (en) * | 2010-03-18 | 2011-08-03 | 凤县三联建材有限责任公司 | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof |
| CN101774762B (en) * | 2010-03-18 | 2011-08-03 | 凤县三联建材有限责任公司 | Black microlite manufactured by using lead and zinc smelting dreg and manufacturing method thereof |
| CN101759368A (en) * | 2010-03-18 | 2010-06-30 | 凤县三联建材有限责任公司 | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof |
| CN101805128A (en) * | 2010-04-20 | 2010-08-18 | 香港福山实业有限公司 | Jade-type glass-ceramic and preparation method thereof |
| CN101941801A (en) * | 2010-07-30 | 2011-01-12 | 华原风积沙开发有限公司 | Microcrystalline glass plate and producing process thereof |
| CN102173588B (en) * | 2011-03-10 | 2013-07-10 | 内蒙古科技大学 | Slag glass ceramic pipe and preparation method thereof |
| CN102173588A (en) * | 2011-03-10 | 2011-09-07 | 内蒙古科技大学 | Slag glass ceramic pipe and preparation method thereof |
| CN102491641A (en) * | 2011-12-09 | 2012-06-13 | 水经(上海)生物科技有限公司 | Wear-resistant crystallized glass plate and preparation method thereof |
| CN102617037A (en) * | 2012-03-27 | 2012-08-01 | 中国地质大学（武汉） | Method for preparing crystallized glass by directly sintering albite ore taken as raw material |
| CN102617037B (en) * | 2012-03-27 | 2013-11-27 | 中国地质大学（武汉） | Method for preparing crystallized glass by directly sintering albite ore taken as raw material |
| CN102826759A (en) * | 2012-09-25 | 2012-12-19 | 内蒙古科技大学 | Method for directly preparing ferro-magnetic microcrystal glass by thermal state steel slag |
| CN102910827A (en) * | 2012-11-16 | 2013-02-06 | 中国地质科学院 | Novel wear-resisting plate produced by using waste moulding sand and preparation method of plate |
| CN102910827B (en) * | 2012-11-16 | 2014-10-22 | 中国地质科学院 | Novel wear-resisting plate produced by using waste moulding sand and preparation method of plate |
| CN107098591A (en) * | 2017-03-30 | 2017-08-29 | 济南大学 | Franklinite glass ceramics is prepared using zinc-plated industrial residue |
| CN107098591B (en) * | 2017-03-30 | 2019-10-29 | 济南大学 | Franklinite glass ceramics is prepared using zinc-plated industrial residue |
| CN107043217A (en) * | 2017-04-07 | 2017-08-15 | 东莞市银通玻璃有限公司 | A kind of production method of low-porosity micro-crystal glass |
| CN108409143A (en) * | 2018-06-13 | 2018-08-17 | 合肥协耀玻璃制品有限公司 | A kind of warping resistance devitrified glass |
| CN108821599A (en) * | 2018-09-06 | 2018-11-16 | 四川名微晶科技股份有限公司 | A method of devitrified glass is prepared using nepheline tailing as primary raw material |
| CN115745380A (en) * | 2022-10-31 | 2023-03-07 | 苏州大学 | Light sintered microcrystal plate and sintering process thereof |
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