CN108585513A - A kind of heat-proof corrosion resistant erosion building nucleated glass - Google Patents
A kind of heat-proof corrosion resistant erosion building nucleated glass Download PDFInfo
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- CN108585513A CN108585513A CN201810758628.6A CN201810758628A CN108585513A CN 108585513 A CN108585513 A CN 108585513A CN 201810758628 A CN201810758628 A CN 201810758628A CN 108585513 A CN108585513 A CN 108585513A
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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
- C03C10/0063—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 waste materials, e.g. slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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Abstract
The invention discloses a kind of heat-proof corrosion resistants to lose building nucleated glass, is related to devitrified glass technical field, including following raw material：Siliceous shale, limonite, vanadium plumbum floatation tailing, lime stone, witherite, cullet, Na2CO3Powder, Yb2O3Powder, compound clarifier.The devitrified glass of the present invention prepares simple and convenient, and heat resistance is excellent, high mechanical strength, and chemical stability is good, and service life is long, and application scenario field is extensive.
Description
Technical field
The present invention relates to devitrified glass technical fields, and in particular to a kind of heat-proof corrosion resistant erosion building nucleated glass.
Background technology
Devitrified glass is also known as glass-ceramic, the double grading with glass and ceramics；Devitrified glass is made of crystal,
Atomic arrangement is regular, and therefore, devitrified glass is higher and stronger than glass toughness than the brightness of ceramics.Devitrified glass has concentrated glass
Triple advantages of glass, ceramics and lithotome are better than lithotome and ceramics, can be used for building curtain wall and indoor high-grade decoration,
As the substitute products of ideal high-grade stone.Current existing crystallized glass article high rejection rate, especially finished product crystallite glass
It is susceptible in glass plate and is not closed stomata and shrinkage cavity phenomenon, cause the mechanical performance of product to reduce, and then affect crystallite glass
Glass plate utilizes space and market efficiency, seriously hinders the development of devitrified glass industry.
The patent application of Publication No. CN107902910A discloses a kind of corrosion-resistant devitrified glass, by following component system
At：Discarded glass 68-80, micron silica 25-32, potassium silicate 3-6, mullite 5-8, forsterite 6-10, ceramics are fine
Tie up 2-5, activation bauxite 5-9, andalusite powder 3-5, magnesia chrome spinel 2-4, prodan 1-5；This kind of devitrified glass have compared with
Good acid-resistant corrosion and impact resistance, but its heat resistance is poor, and application is restricted.
The patent application of Publication No. CN104016589B discloses a kind of iron tailings devitrified glass and preparation method thereof,
Raw material includes：By weight, iron tailings 40-70 parts, 15-35 parts of quartz sand, 15-25 parts of lime stone, 4-7 parts of soda ash, oxidation
2-5 parts of zinc, 2-6 parts of barium carbonate, 0.5-1 parts of borax, 0-10 parts of ferroso-ferric oxide, 1-2 parts of fining agent；Preparation method is：It will
Raw material is uniformly mixed, and heats and glass metal is made；By glass metal water quenching, frit is obtained；Crystallization after frit is heated, after crystallization
Iron tailings devitrified glass is made in furnace cooling.This kind of devitrified glass has good mechanical strength and acid-alkali-corrosive-resisting, but its
Fire resistance is poor, and application is restricted.
Invention content
The purpose of the present invention is to provide a kind of heat-proof corrosion resistants to lose building nucleated glass, this kind of devitrified glass comprehensive performance
Excellent, application field occasion is extensive.
In order to achieve the above object, the present invention is achieved through the following technical solutions：
A kind of heat-proof corrosion resistant erosion building nucleated glass, including following raw material by weight：
68-84 parts of siliceous shale；
37-49 parts of limonite；
24-36 parts of vanadium plumbum floatation tailing；
27-35 parts of lime stone；
18-26 parts of witherite；
15-25 parts of cullet；
Na2CO310-15 parts of powder；
Yb2O36-10 parts of powder；
3-7 parts of compound clarifier.
Further, above-mentioned devitrified glass is made of following raw material by weight：
68 parts of siliceous shale；
37 parts of limonite；
24 parts of vanadium plumbum floatation tailing；
27 parts of lime stone；
18 parts of witherite；
15 parts of cullet；
Na2CO310 parts of powder；
Yb2O36 parts of powder；
3 parts of compound clarifier；
Above-mentioned compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 3:4:1:2 close
And obtain.
Further, the preparation process of above-mentioned devitrified glass is as follows：
(1) it stocks up：Raw material is obtained by the weight, and by raw material attrition grinding, be mixed uniformly to obtain batch；
(2) it is melted：6h first is preheated to glass melting furnace, preheating temperature is 760 DEG C；Cullet are added in glass melting furnace and are added
Heat fusing, then glass melting temperature in glass melting furnace is gradually increased to 1370 DEG C, by batch blanket type in such a way that thin layer feeds intake
Be delivered on the melt of glass melting furnace, glass melting temperature in glass melting furnace be gradually increased to 1510 DEG C later, under heat-retaining condition until
Batch penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, it, will be in glass melting furnace after mechanical agitation 85min
Temperature be gradually increased to the clarifications of 1565 DEG C of progress glass melts, settling time is set as 115min, later will be in glass melting furnace
Temperature be gradually decreased to 1425 DEG C progress glass melts homogenizing；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1275 DEG C of progress glass melts, viscosity reaches
To after requirement, the molding of glass melts is completed；
(5) crystallization：Crystallizing treatment 4.5h under the conditions of temperature is 830-970 DEG C；
(6) it anneals：9h is made annealing treatment under the conditions of temperature is 420-780 DEG C, it is finally air-cooled with stove.
Further, the granularity of above-mentioned batch is sieved for 150 mesh.
Further, above-mentioned crystallization is that glassware will be placed in glass melting furnace after being molded, and is protected at being first 970 DEG C in temperature
Warm 1.5h；It is again that 8 DEG C/min is cooled to 830 DEG C, and keeps the temperature 3h with rate.
Further, above-mentioned annealing is that glassware after crystallization is placed in annealing furnace, is kept the temperature at being first 570 DEG C in temperature
4h；It is again that 6 DEG C/min is warming up to 780 DEG C, and keeps the temperature 2h with rate；It is later that 6 DEG C/min is cooled to 420 DEG C, and protects with rate
Warm 3h.
Further, above-mentioned devitrified glass is made of following raw material by weight：
84 parts of siliceous shale；
49 parts of limonite；
36 parts of vanadium plumbum floatation tailing；
35 parts of lime stone；
26 parts of witherite；
25 parts of cullet；
Na2CO315 parts of powder；
Yb2O310 parts of powder；
7 parts of compound clarifier；
Above-mentioned compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 5:6:3:4 close
And obtain.
Further, the preparation process of above-mentioned devitrified glass is as follows：
(1) it stocks up：Raw material is obtained by the weight, and raw material attrition grinding to granularity is sieved for 250 mesh, is blended
It is uniform to obtain batch；
(2) it is melted：7h first is preheated to glass melting furnace, preheating temperature is 770 DEG C；Cullet are added in glass melting furnace and are added
Heat fusing, then glass melting temperature in glass melting furnace is gradually increased to 1380 DEG C, by batch blanket type in such a way that thin layer feeds intake
Be delivered on the melt of glass melting furnace, glass melting temperature in glass melting furnace be gradually increased to 1520 DEG C later, under heat-retaining condition until
Batch penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, it, will be in glass melting furnace after mechanical agitation 95min
Temperature be gradually increased to the clarifications of 1575 DEG C of progress glass melts, settling time is set as 125min, later will be in glass melting furnace
Temperature be gradually decreased to 1435 DEG C progress glass melts homogenizing；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1285 DEG C of progress glass melts, viscosity reaches
To after requirement, the molding of glass melts is completed；
(5) crystallization：Crystallizing treatment 6.5h under the conditions of temperature is 840-985 DEG C；
(6) it anneals：12h is made annealing treatment under the conditions of temperature is 430-790 DEG C, it is finally air-cooled with stove.
Further, above-mentioned crystallization is that glassware will be placed in glass melting furnace after being molded, and is protected at being first 985 DEG C in temperature
Warm 2.5h；It is again that 12 DEG C/min is cooled to 840 DEG C, and keeps the temperature 4h with rate.
Further, above-mentioned annealing is that glassware after crystallization is placed in annealing furnace, is kept the temperature at being first 580 DEG C in temperature
5h；It is again that 10 DEG C/min is warming up to 790 DEG C, and keeps the temperature 3h with rate；With rate it is later that 10 DEG C/min is cooled to 430 DEG C, and
Keep the temperature 4h.
The present invention has following advantageous effect：The devitrified glass of the present invention by ingenious selection to raw materials for production and its
The inventive improvements of preparation process, siliceous shale, limonite, vanadium plumbum floatation tailing, witherite, Yb in raw material2O3The compositions such as powder
Cooperative interaction, make building glass product obtained have it is following a little：
(1) without chip, unfilled corner, crack problem；
(2) plate face presentation quality is high, and stomata, impurity content are low, and glossiness and visible transmission are than high；
(3) good mechanical property, hardness is high, and shock resistance, brittleness is small, anti-folding resist bending；
(4) heat resistance is excellent, and under high and low temperature environment transformation, the problems such as not will produce crack, burst, fire resistance rating is high；
(5) chemical stability is good, acid-alkali-corrosive-resisting, and fire-retardant sound insulation, capability of electromagnetic shielding is good, and service life is long, application
Occasion field is extensive.
Specific implementation mode
The specific implementation mode of the present invention is further described with reference to embodiment, following embodiment is only used for more
Technical scheme of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
It all raw materials in embodiment and its produces composition and can be obtained by disclosed commercially available channel；
Embodiment 1
The present embodiment is related to a kind of heat-proof corrosion resistant erosion building nucleated glass and its preparation process, and the devitrified glass is by following
Raw material composition by weight：
68 parts of siliceous shale；
37 parts of limonite；
24 parts of vanadium plumbum floatation tailing；
27 parts of lime stone；
18 parts of witherite；
15 parts of cullet；
Na2CO310 parts of powder；
Yb2O36 parts of powder；
3 parts of compound clarifier；
Above-mentioned compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 3:4:1:2 close
And obtain.
The preparation process of this kind of devitrified glass substantially follows the steps below：
(1) it stocks up：Raw material is obtained by the weight, and raw material attrition grinding to granularity is sieved for 150 mesh, is blended
It is uniform to obtain batch；
(2) it is melted：6h first is preheated to glass melting furnace, preheating temperature is 760 DEG C；Cullet are added in glass melting furnace and are added
Heat fusing, then glass melting temperature in glass melting furnace is gradually increased to 1370 DEG C, by batch blanket type in such a way that thin layer feeds intake
Be delivered on the melt of glass melting furnace, glass melting temperature in glass melting furnace be gradually increased to 1510 DEG C later, under heat-retaining condition until
Batch penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, it, will be in glass melting furnace after mechanical agitation 85min
Temperature be gradually increased to the clarifications of 1565 DEG C of progress glass melts, settling time is set as 115min, later will be in glass melting furnace
Temperature be gradually decreased to 1425 DEG C progress glass melts homogenizing；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1275 DEG C of progress glass melts, viscosity reaches
To after requirement, the molding of glass melts is completed；
(5) crystallization：Glassware after molding is placed in glass melting furnace, 1.5h is kept the temperature at being first 970 DEG C in temperature；Again with
Rate is that 8 DEG C/min is cooled to 830 DEG C, and keeps the temperature 3h；
(6) it anneals：Glassware after crystallization is placed in annealing furnace, 4h is kept the temperature at being first 570 DEG C in temperature；Again with rate
780 DEG C are warming up to for 6 DEG C/min, and keeps the temperature 2h；Be later that 6 DEG C/min is cooled to 420 DEG C with rate, and keep the temperature 3h, finally with
Stove is air-cooled；
(7) subsequent operations such as cutting, polishing, deburring.
Embodiment 2
The present embodiment is related to a kind of heat-proof corrosion resistant erosion building nucleated glass and its preparation process, and the devitrified glass is by following
Raw material composition by weight：
72 parts of siliceous shale；
40 parts of limonite；
28 parts of vanadium plumbum floatation tailing；
29 parts of lime stone；
20 parts of witherite；
18 parts of cullet；
Na2CO312 parts of powder；
Yb2O37 parts of powder；
4 parts of compound clarifier；
Above-mentioned compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 3.5:4.5:
1.5:What 2.5 merging obtained.
The preparation process of this kind of devitrified glass substantially follows the steps below：
(1) it stocks up：Raw material is obtained by the weight, and raw material attrition grinding to granularity is sieved for 180 mesh, is blended
It is uniform to obtain batch；
(2) it is melted：6.2h first is preheated to glass melting furnace, preheating temperature is 764 DEG C；Cullet are added in glass melting furnace
Heating melting, then glass melting temperature in glass melting furnace is gradually increased to 1372 DEG C, by batch carpet in such a way that thin layer feeds intake
Formula is delivered on the melt of glass melting furnace, and glass melting temperature in glass melting furnace is gradually increased to 1512 DEG C later, straight under heat-retaining condition
To batch penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, it, will be in glass melting furnace after mechanical agitation 88min
Temperature be gradually increased to the clarifications of 1567 DEG C of progress glass melts, settling time is set as 116min, later will be in glass melting furnace
Temperature be gradually decreased to 1428 DEG C progress glass melts homogenizing；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1278 DEG C of progress glass melts, viscosity reaches
To after requirement, the molding of glass melts is completed；
(5) crystallization：Glassware after molding is placed in glass melting furnace, 1.8h is kept the temperature at being first 974 DEG C in temperature；Again with
Rate is that 9 DEG C/min is cooled to 832 DEG C, and keeps the temperature 3.3h；
(6) it anneals：Glassware after crystallization is placed in annealing furnace, 4.2h is kept the temperature at being first 572 DEG C in temperature；Again with speed
Rate is that 7 DEG C/min is warming up to 782 DEG C, and keeps the temperature 2.3h；It is later that 7 DEG C/min is cooled to 424 DEG C, and keeps the temperature 3.2h with rate,
It is finally air-cooled with stove；
(7) subsequent operations such as cutting, polishing, deburring.
Embodiment 3
The present embodiment is related to a kind of heat-proof corrosion resistant erosion building nucleated glass and its preparation process, and the devitrified glass is by following
Raw material composition by weight：
75 parts of siliceous shale；
43 parts of limonite；
30 parts of vanadium plumbum floatation tailing；
31 parts of lime stone；
22 parts of witherite；
20 parts of cullet；
Na2CO313 parts of powder；
Yb2O38 parts of powder；
5 parts of compound clarifier；
Above-mentioned compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 4:5:2:3 close
And obtain.
The preparation process of this kind of devitrified glass substantially follows the steps below：
(1) it stocks up：Raw material is obtained by the weight, and raw material attrition grinding to granularity is sieved for 200 mesh, is blended
It is uniform to obtain batch；
(2) it is melted：6.5h first is preheated to glass melting furnace, preheating temperature is 765 DEG C；Cullet are added in glass melting furnace
Heating melting, then glass melting temperature in glass melting furnace is gradually increased to 1375 DEG C, by batch carpet in such a way that thin layer feeds intake
Formula is delivered on the melt of glass melting furnace, and glass melting temperature in glass melting furnace is gradually increased to 1515 DEG C later, straight under heat-retaining condition
To batch penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, it, will be in glass melting furnace after mechanical agitation 90min
Temperature be gradually increased to the clarifications of 1570 DEG C of progress glass melts, settling time is set as 120min, later will be in glass melting furnace
Temperature be gradually decreased to 1430 DEG C progress glass melts homogenizing；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1280 DEG C of progress glass melts, viscosity reaches
To after requirement, the molding of glass melts is completed；
(5) crystallization：Glassware after molding is placed in glass melting furnace, 2h is kept the temperature at being first 978 DEG C in temperature；Again with speed
Rate is that 10 DEG C/min is cooled to 835 DEG C, and keeps the temperature 3.5h；
(6) it anneals：Glassware after crystallization is placed in annealing furnace, 4.5h is kept the temperature at being first 575 DEG C in temperature；Again with speed
Rate is that 8 DEG C/min is warming up to 785 DEG C, and keeps the temperature 2.5h；It is later that 8 DEG C/min is cooled to 425 DEG C, and keeps the temperature 3.5h with rate,
It is finally air-cooled with stove；
(7) subsequent operations such as cutting, polishing, deburring.
Embodiment 4
The present embodiment is related to a kind of heat-proof corrosion resistant erosion building nucleated glass and its preparation process, and the devitrified glass is by following
Raw material composition by weight：
78 parts of siliceous shale；
46 parts of limonite；
32 parts of vanadium plumbum floatation tailing；
33 parts of lime stone；
24 parts of witherite；
22 parts of cullet；
Na2CO314 parts of powder；
Yb2O39 parts of powder；
6 parts of compound clarifier；
Above-mentioned compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 4.5:5.5:
2.5:What 3.5 merging obtained.
The preparation process of this kind of devitrified glass substantially follows the steps below：
(1) it stocks up：Raw material is obtained by the weight, and raw material attrition grinding to granularity is sieved for 220 mesh, is blended
It is uniform to obtain batch；
(2) it is melted：6.8h first is preheated to glass melting furnace, preheating temperature is 768 DEG C；Cullet are added in glass melting furnace
Heating melting, then glass melting temperature in glass melting furnace is gradually increased to 1379 DEG C, by batch carpet in such a way that thin layer feeds intake
Formula is delivered on the melt of glass melting furnace, and glass melting temperature in glass melting furnace is gradually increased to 1518 DEG C later, straight under heat-retaining condition
To batch penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, it, will be in glass melting furnace after mechanical agitation 92min
Temperature be gradually increased to the clarifications of 1572 DEG C of progress glass melts, settling time is set as 123min, later will be in glass melting furnace
Temperature be gradually decreased to 1432 DEG C progress glass melts homogenizing；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1282 DEG C of progress glass melts, viscosity reaches
To after requirement, the molding of glass melts is completed；
(5) crystallization：Glassware after molding is placed in glass melting furnace, 2.4h is kept the temperature at being first 980 DEG C in temperature；Again with
Rate is that 11 DEG C/min is cooled to 838 DEG C, and keeps the temperature 3.7h；
(6) it anneals：Glassware after crystallization is placed in annealing furnace, 4.6h is kept the temperature at being first 578 DEG C in temperature；Again with speed
Rate is that 9 DEG C/min is warming up to 788 DEG C, and keeps the temperature 2.6h；It is later that 9 DEG C/min is cooled to 427 DEG C, and keeps the temperature 3.8h with rate,
It is finally air-cooled with stove；
(7) subsequent operations such as cutting, polishing, deburring.
Embodiment 5
The present embodiment is related to a kind of heat-proof corrosion resistant erosion building nucleated glass and its preparation process, and the devitrified glass is by following
Raw material composition by weight：
84 parts of siliceous shale；
49 parts of limonite；
36 parts of vanadium plumbum floatation tailing；
35 parts of lime stone；
26 parts of witherite；
25 parts of cullet；
Na2CO315 parts of powder；
Yb2O310 parts of powder；
7 parts of compound clarifier；
Above-mentioned compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 5:6:3:4 close
And obtain.
The preparation process of this kind of devitrified glass substantially follows the steps below：
(1) it stocks up：Raw material is obtained by the weight, and raw material attrition grinding to granularity is sieved for 250 mesh, is blended
It is uniform to obtain batch；
(2) it is melted：7h first is preheated to glass melting furnace, preheating temperature is 770 DEG C；Cullet are added in glass melting furnace and are added
Heat fusing, then glass melting temperature in glass melting furnace is gradually increased to 1380 DEG C, by batch blanket type in such a way that thin layer feeds intake
Be delivered on the melt of glass melting furnace, glass melting temperature in glass melting furnace be gradually increased to 1520 DEG C later, under heat-retaining condition until
Batch penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, it, will be in glass melting furnace after mechanical agitation 95min
Temperature be gradually increased to the clarifications of 1575 DEG C of progress glass melts, settling time is set as 125min, later will be in glass melting furnace
Temperature be gradually decreased to 1435 DEG C progress glass melts homogenizing；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1285 DEG C of progress glass melts, viscosity reaches
To after requirement, the molding of glass melts is completed；
(5) crystallization：Glassware after molding is placed in glass melting furnace, 2.5h is kept the temperature at being first 985 DEG C in temperature；Again with
Rate is that 12 DEG C/min is cooled to 840 DEG C, and keeps the temperature 4h；
(6) it anneals：Glassware after crystallization is placed in annealing furnace, 5h is kept the temperature at being first 580 DEG C in temperature；Again with rate
790 DEG C are warming up to for 10 DEG C/min, and keeps the temperature 3h；It is later that 10 DEG C/min is cooled to 430 DEG C, and keeps the temperature 4h with rate, finally
It is air-cooled with stove；
(7) subsequent operations such as cutting, polishing, deburring.
Comparative example 1
This comparative example is related to a kind of devitrified glass, relative to embodiment 1, there is only the difference of compound clarifier ingredient,
Its raw material and content and the preparation process of devitrified glass are same as Example 1；
The ingredient of compound clarifier is in this comparative example：Calcium chloride, barium sulfate, sodium sulphate, cerium oxide, mass ratio are all 3:
4:1:2。
Comparative example 2
This comparative example is related to a kind of devitrified glass preparation technology, relative to embodiment 2, there is only the difference of step (1),
Raw materials for production and other preparation processes are same as Example 2；
In this comparative example step (1)：Raw material attrition grinding granularity is sieved for 350 mesh.
Comparative example 3
This comparative example is related to a kind of devitrified glass preparation technology, relative to embodiment 3, there is only the difference of step (3),
Raw materials for production and other preparation processes are same as Example 3；
In this comparative example step (3)：The mechanical agitation time is 60min.
Comparative example 4
This comparative example is related to a kind of devitrified glass preparation technology, relative to embodiment 4, there is only the difference of step (5),
Raw materials for production and other preparation processes are same as Example 4；
In this comparative example step (5)：Glassware after molding is placed in glass melting furnace, is protected at being first 1080 DEG C in temperature
Warm 2h；It is again that 15 DEG C/min is cooled to 885 DEG C, and keeps the temperature 3h with rate.
Comparative example 5
This comparative example is related to a kind of devitrified glass preparation technology, relative to embodiment 5, there is only the difference of step (6),
Raw materials for production and other preparation processes are same as Example 5；
In this comparative example step (6)：Glassware after crystallization is placed in annealing furnace, is kept the temperature at being first 620 DEG C in temperature
3h；It is again that 15 DEG C/min is warming up to 520 DEG C, and keeps the temperature 2.5h with rate, it is finally air-cooled with stove.
Comparative example 6
This comparative example is related to a kind of commercially available common building materials devitrified glass, including following raw material by weight：Fluorite
65 parts of tailing, 30 parts of quartz sand, 42 parts of dolomite, 12 parts of flyash, 10 parts of lime stone, 3.5 parts of soda ash, 2 parts of clarification.
Performance detection
For the advantageous effect of the verification present invention, the devitrified glass of above-described embodiment 1-5 and comparative example 1-6 is taken to cut model,
The devitrified glass of embodiment 1-5 is corresponding respectively to be named as #1-#5, and correspondence is named as #6-# to the devitrified glass of comparative example 1-6 respectively
11, and carry out the detection of following Tables 1 and 2 performance indicator；
1, the detection method of board surface quality and standard reference《JCT 872-2000》：
Detection content is further as follows：Stomata：Under the conditions of natural light, by model placing flat ground, at model 2m
Visually, it is its full-size of the vernier caliper measurement of 0.02mm to the stomata service precision estimated；
Impurity：Under the conditions of natural light, by model placing flat ground, at model 2m visually, to the impurity estimated
Service precision is its full-size of the vernier caliper measurement of 0.02mm, accuracy of reading to 0.1mm.
2, the detection method of bending strength and standard reference《JCT 872-2000》：
Detection content is further as follows：Natural air drying 4 hours, the stress surface depth of parallelism after the sampling plate clean wiping of tap water
Within 0.08mm, every group 10 pieces, test method and result of calculation are carried out by the regulation of GB 9966.2.
3, the detection method of resistant of high or low temperature and standard reference《JCT 872-2000》：
Detection content is further as follows：It is small that model is placed on constant temperature 4 in 95 DEG C ± 1 DEG C of drying box high compared with room temperature water
When, it places into cooling in no less than 20 times of model volume, the water that temperature is 1 DEG C.Then each position of model is gently tapped with iron hammer
The whether mute change of its sound is listened, and observe specimen surface to have free from flaw, arrisdefect, fall the problems such as side.
4, the detection method of chemical stability and standard reference《JCT 872-2000》：
Detection content is further as follows：Model is soaked in acid-base solution, the mass change of model is weighed, is damaged with quality
Mistake rate k is indicated；Wherein, acid solution is the pure concentrated sulfuric acid of 1% (v/v) chemistry；Aqueous slkali is the chemical pure cerium hydroxide sodium of 1% (m/m).
5, the detection method of impact resistance and standard reference《JCT 2157-2012》：
Detection content is further as follows：Model is positioned on the maintenance level frame of four sides support, it is (straight with quality 535g
Diameter is 50.8mm) solid steel ball, on from 110mm height free-electron model to model center, continuously fall three times, record is broken
Damage situation.
6, the detection method of fire resistance and standard reference《GB 15763.1-2009》：
Detection content is further as follows：Fire endurance grade 0.50h：The fire insulation time >=0.50h, and fire resisting is complete
Property time >=0.50h；Fire endurance grade 1.00h：The fire insulation time >=1.00h, and the fire integrity time >=
1.00h；Fire endurance grade 1.50h：Fire insulation time >=1.50h, and fire integrity time >=1.50h.
7, visible transmission than detection method and standard reference《JCT 2157-2012》：
Detection content is further as follows：Three pieces of models are taken, are measured by the regulation of GB/T 2680-1994, with three pieces of models
Average value is as testing result.
8, the detection method of thermal shock resistance and standard reference《JCT 2157-2012》：
Detection content is further as follows：Three pieces of models are taken, are put into the environment of (750 ± 10) DEG C, it is fast after constant temperature 15min
Speed is put into 0 DEG C of water, and 10min, record is kept to burst situation.
9, Mohs' hardness, the detection method of glossiness and standard reference《JCT 872-2000》；
10, the detection method of electromagnetic shielding detection and standard reference《GB/T 30142-2013》；
Detection content is further as follows：Detection electromagnetic frequency is set as 3GHz.
Table 1
Table 2
It can be obtained by upper Tables 1 and 2, devitrified glass of the invention is in presentation quality, physical property, temperature tolerance, corrosion resistant
It all has on corrosion, electromagnetic wave shielding etc. and is significantly promoted comprehensively, progress is apparent compared with prior art, and technical solution is not
Has apparent property.
In conjunction with beneficial effects of the present invention, the setting of granularity, clarification is melted to cullet, the raw material in the present invention in applicant
The selection of agent and the preparation process of devitrified glass are illustrated as follows：
(1) setting of granularity is melted in raw material：Applicant has been surprisingly found that during being developed to devitrified glass, when
When production cooperation material granularity is excessive/excessively thick in the present invention, melted efficiency can be caused to be lower, cost is melted and improves；When batch grain
When spending small/meticulous, glass melting and clear quality can be caused to be deteriorated, and will produce premature fusing and generate many small gas
It steeps and can also so that just melt viscosity becomes larger, and keeps the growth rate of bubble slack-off, extends the whole settling time of glass.Cause
This, is worthy of careful study for the bed of material fineness of metal level in the present invention, after batch fineness is more than 250 mesh sieve, can cause
Upper table precoat melts quickly, forms the first melt containing more micro-bubble, and minute bubbles are difficult to mutually tie at a lower temperature
It closes and becomes air pocket and be discharged into cellar for storing things stove space, enter high-temperature region when mixture further moves ahead, half containing a large amount of micro-bubbles
Fusing vitreum forms one layer of heat preservation layer, hinders heat transfer of the flame to lower layer's mixture, not only reduces glass metal convection current, also
Electric boosting burden is aggravated, the entirety to be unfavorable for glass is melted, and therefore, is when sieving when coordinating material granularity to be 150-250 mesh
Optimal.
(2) selection of fining agent：Sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide all have to glass melts compared with
Good clarifying effect, but a combination thereof application is not arbitrarily to obtain or there is originally, is that applicant passes through many experiments
It obtaining, the clarification material for being applied to glass melts after all is also very much, such as：Calcium chloride, barium sulfate, sodium sulphate, antimony oxide,
Cerium oxide etc., only by above-mentioned composition according to mass ratio (3-5):(4-6):(1-3):(2-4), which merges to utilize, can be only achieved glass
Glass melt preferably clarifying effect, the melted system of the more suitable present invention.If the composition of compound clarifier in the present invention
Or/and the change of content, it can cause beneficial effects of the present invention that cannot realize well.
(3) cullet：The reason of why raw material of the present invention uses cullet be：Raw material can be saved, accelerates glass molten
Process processed saves energy consumption, improves thawing rate, is conducive to clarification and homogenization, improves the performance of finished product devitrified glass.
(4) preparation process of devitrified glass：Due to the requirement of the mentality of designing and goal of the invention of devitrified glass of the present invention,
The preparation technology parameter condition right and wrong of the present invention are it will be apparent that those skilled in the art can be easily in conjunction with the prior art absolutely not
Expect.This has further embodiment in comparative example group in the present invention, can see in conjunction with the comparative example of the present invention, batch grain
The change of degree, mixing time, crystallization parameter, annealing parameter can influence the devitrified glass processability of the present invention, and of the invention
The process conditions and parameter of use are that applicant obtains by many experiments, and this technique is the life with devitrified glass of the present invention
What the special proportioning of production raw material components was adapted, this technique is only used, just can guarantee the devitrified glass finally prepared
Excellent specific property.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features.All essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of heat-proof corrosion resistant loses building nucleated glass, which is characterized in that including following raw material by weight：
68-84 parts of siliceous shale；
37-49 parts of limonite；
24-36 parts of vanadium plumbum floatation tailing；
27-35 parts of lime stone；
18-26 parts of witherite；
15-25 parts of cullet；
Na2CO310-15 parts of powder；
Yb2O36-10 parts of powder；
3-7 parts of compound clarifier.
2. a kind of heat-proof corrosion resistant according to claim 1 loses building nucleated glass, which is characterized in that by it is following by weight
The raw material composition of part meter：
68 parts of siliceous shale；
37 parts of limonite；
24 parts of vanadium plumbum floatation tailing；
27 parts of lime stone；
18 parts of witherite；
15 parts of cullet；
Na2CO310 parts of powder；
Yb2O36 parts of powder；
3 parts of compound clarifier；
The compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 3:4:1:2 merge
It arrives.
3. a kind of heat-proof corrosion resistant according to claim 2 loses building nucleated glass, which is characterized in that the devitrified glass
Preparation process it is as follows：
(1) it stocks up：Raw material is obtained by the weight, and by raw material attrition grinding, be mixed uniformly to obtain batch；
(2) it is melted：6h first is preheated to glass melting furnace, preheating temperature is 760 DEG C；Cullet are added to heat in glass melting furnace and are melted
Melt, then glass melting temperature in glass melting furnace is gradually increased to 1370 DEG C, conveys batch blanket type in such a way that thin layer feeds intake
To the melt of glass melting furnace, glass melting temperature in glass melting furnace is gradually increased to 1510 DEG C later, until cooperation under heat-retaining condition
Expect penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, after mechanical agitation 85min, by the temperature in glass melting furnace
Degree is gradually increased to the clarification of 1565 DEG C of progress glass melts, and settling time is set as 115min, later by the temperature in glass melting furnace
Degree is gradually decreased to the homogenizing of 1425 DEG C of progress glass melts；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1275 DEG C of progress glass melts, viscosity, which reaches, to be wanted
After asking, the molding of glass melts is completed；
(5) crystallization：Crystallizing treatment 4.5h under the conditions of temperature is 830-970 DEG C；
(6) it anneals：9h is made annealing treatment under the conditions of temperature is 420-780 DEG C, it is finally air-cooled with stove.
4. a kind of heat-proof corrosion resistant according to claim 3 loses building nucleated glass, which is characterized in that the batch
Granularity is sieved for 150 mesh.
5. a kind of heat-proof corrosion resistant according to claim 4 loses building nucleated glass, which is characterized in that the crystallization be by
Glassware is placed in glass melting furnace after molding, and 1.5h is kept the temperature at being first 970 DEG C in temperature；Cooled down again for 8 DEG C/min with rate
To 830 DEG C, and keep the temperature 3h.
6. a kind of heat-proof corrosion resistant according to claim 5 loses building nucleated glass, which is characterized in that the annealing be by
Glassware is placed in annealing furnace after crystallization, and 4h is kept the temperature at being first 570 DEG C in temperature；It is again that 6 DEG C/min is warming up to 780 with rate
DEG C, and keep the temperature 2h；It is later that 6 DEG C/min is cooled to 420 DEG C, and keeps the temperature 3h with rate.
7. a kind of heat-proof corrosion resistant according to claim 1 loses building nucleated glass, which is characterized in that by it is following by weight
The raw material composition of part meter：
84 parts of siliceous shale；
49 parts of limonite；
36 parts of vanadium plumbum floatation tailing；
35 parts of lime stone；
26 parts of witherite；
25 parts of cullet；
Na2CO315 parts of powder；
Yb2O310 parts of powder；
7 parts of compound clarifier；
The compound clarifier is sodium nitrate, calcium sulfate, strontium chloride, antimony-doped stannic oxide according to mass ratio 5:6:3:4 merge
It arrives.
8. a kind of heat-proof corrosion resistant according to claim 7 loses building nucleated glass, which is characterized in that the devitrified glass
Preparation process it is as follows：
(1) it stocks up：Raw material is obtained by the weight, and raw material attrition grinding to granularity is sieved for 250 mesh, is mixed uniformly
Obtain batch；
(2) it is melted：7h first is preheated to glass melting furnace, preheating temperature is 770 DEG C；Cullet are added to heat in glass melting furnace and are melted
Melt, then glass melting temperature in glass melting furnace is gradually increased to 1380 DEG C, conveys batch blanket type in such a way that thin layer feeds intake
To the melt of glass melting furnace, glass melting temperature in glass melting furnace is gradually increased to 1520 DEG C later, until cooperation under heat-retaining condition
Expect penetration；
(3) clarification homogenizing：Compound clarifier is added in glass melts, after mechanical agitation 95min, by the temperature in glass melting furnace
Degree is gradually increased to the clarification of 1575 DEG C of progress glass melts, and settling time is set as 125min, later by the temperature in glass melting furnace
Degree is gradually decreased to the homogenizing of 1435 DEG C of progress glass melts；
(4) it is cooled and shaped：Temperature in glass melting furnace is gradually decreased to the cooling of 1285 DEG C of progress glass melts, viscosity, which reaches, to be wanted
After asking, the molding of glass melts is completed；
(5) crystallization：Crystallizing treatment 6.5h under the conditions of temperature is 840-985 DEG C；
(6) it anneals：12h is made annealing treatment under the conditions of temperature is 430-790 DEG C, it is finally air-cooled with stove.
9. a kind of heat-proof corrosion resistant according to claim 8 loses building nucleated glass, which is characterized in that the crystallization be by
Glassware is placed in glass melting furnace after molding, and 2.5h is kept the temperature at being first 985 DEG C in temperature；Cooled down again for 12 DEG C/min with rate
To 840 DEG C, and keep the temperature 4h.
10. a kind of heat-proof corrosion resistant according to claim 9 loses building nucleated glass, which is characterized in that the annealing is
Glassware after crystallization is placed in annealing furnace, 5h is kept the temperature at being first 580 DEG C in temperature；It is again that 10 DEG C/min is warming up to rate
790 DEG C, and keep the temperature 3h；It is later that 10 DEG C/min is cooled to 430 DEG C, and keeps the temperature 4h with rate.
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| CN113493294A (en) * | 2021-07-23 | 2021-10-12 | 重庆鑫景特种玻璃有限公司 | High-lithium microcrystalline glass production system and production method thereof |
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