CN108863084A - A kind of high-strength corrosion-resisting devitrified glass and preparation method thereof - Google Patents
A kind of high-strength corrosion-resisting devitrified glass and preparation method thereof Download PDFInfo
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- CN108863084A CN108863084A CN201810856409.1A CN201810856409A CN108863084A CN 108863084 A CN108863084 A CN 108863084A CN 201810856409 A CN201810856409 A CN 201810856409A CN 108863084 A CN108863084 A CN 108863084A
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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
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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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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Abstract
The invention discloses a kind of high-strength corrosion-resisting devitrified glasses, and by mass percentage, which becomes：Ferrochrome slag 88-92wt%, fluxing agent 5-7wt%, clarifying agent 2.2-4.4wt%, KOH 0.5-1.5wt%.The present invention also provides the preparation method of above-mentioned high-strength corrosion-resisting devitrified glass, this method by mixing, heating melting, moulding by casting, annealing, Crystallizing treatment and etc. be prepared.Devitrified glass produced by the present invention has preferable intensity, corrosion resistance and shock resistance, and solves the environmental pollution of existing ferrochrome tailing, security problems.
Description
Technical field
The present invention relates to microcrystal glass material technical fields, and in particular to a kind of high-strength corrosion-resisting devitrified glass and its system
Preparation Method.
Background technique
Devitrified glass is also known as microcrystalline jade or glass-ceramic, is comprehensive glass, and it is novel to be that a kind of foreign country has just developed
Construction material, its scientific name are called glass quartz.Devitrified glass and our common glass seem to differ widely.It has glass
The double grading of glass and ceramics, the atomic arrangement inside simple glass be do not have the reason of well-regulated, this is also Glass breadks easily it
One, and devitrified glass is made of, that is to say, that its atomic arrangement is regular as ceramics crystal.So crystallite
Glass is higher than the brightness of ceramics, stronger than glass toughness, and composition includes silicate.
Tailing is one of the product of separation operation in ore dressing, and in the product of this operation, the content of useful component is minimum,
It is the mine that should not be further sorted under current condition of technology and economy.Most composition is silicic acid in general tailing
Ingredient required for salt, with cast stone and devitrified glass is much like, thus is possible to add part chemical industry as raw material using tailing
Raw material and prepare high abrasion, acid and alkali-resistance corrode, impact-resistant devitrified glass replace cast stone.The country is had using rare earth tail
Mine, flyash, iron tailings etc. prepare the report of devitrified glass.
As CN101024554A is disclosed, a kind of rich rare earth, niobium, fluorite is dilute selects tailing microcrystal glass and manufacturing method, belongs to
In the comprehensive utilization of trade waste.Feature is：The raw material for preparing of the devitrified glass selects tailing, quartz sand, chemical group to be dilute
At being by weight percentage：SiO2 30-70%, CaO 5-20%, Al2O35-15%, CaF2 3-15%, ReO 3-15%, Nb2O5
0-5%, TiO2 0-10%。
And a kind of microcrystalline glass prepared from desulphurized and preparation method thereof is disclosed in CN102167516A, it is to use desulfurized powder
Coal ash (30-65wt%), through ingredient, mixing, be melted, molding, annealing, nucleus crystallization, be cold worked.Product main component
For：SiO2(50-60%), Fe2O3(1-2.5%), Al2O3(3-10%), CaO (20-30%), MgO (1-9%), Na2O(5-
10%).
And devitrified glass is prepared using the tailing of slag containing ferrochrome and is not yet reported that.And ferrochrome slag belongs to weight toxicity waste,
A large amount of soils are not only taken up, and cause seriously to pollute.Therefore by preparing high-strength corrosion-resisting devitrified glass using ferrochrome slag
Have great importance.
Summary of the invention
The present invention provides a kind of high-strength corrosion-resisting devitrified glass and preparation method thereof, devitrified glass obtained have compared with
Good intensity, corrosion resistance and shock resistance, and solve the environmental pollution of existing ferrochrome tailing, security problems.
It is of the existing technology in order to solve the problems, such as, it adopts the following technical scheme that：
A kind of high-strength corrosion-resisting devitrified glass, by mass percentage, the glass raw material group become：It is ferrochrome slag 90wt%, fluxing
Agent 6wt%, clarifying agent 3wt%, KOH 1wt%, and prepared using following methods：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 30-40min at 650 DEG C, is added in high temperature furnace and is melted
Change, fusion temperature is 1300-1400 DEG C, keeps the temperature 40-60min, and KOH is then added, is first warming up to 1500 with the speed of 5 DEG C/min
DEG C, 30-50min is kept the temperature, is then cooled to 1350 DEG C again with the speed of 8 DEG C/min, keeps the temperature 20-30min, it is uniform to melt, clear
Qualified glass metal is formed after clear；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：In 520-650 DEG C of furnace
Inside holding 1-2h；Then it is warming up to 740-780 DEG C with≤5 DEG C/min, keeps the temperature 2-4h；Then 820- is warming up to≤5 DEG C/min
850 DEG C, keep the temperature 1-2h；Then it is warming up to 930-950 DEG C with 10-14 DEG C/min, keeps the temperature 0.5-1h；Then with 15-20 DEG C/min
It is cooled to 520-650 DEG C, keeps the temperature 1-2h；Then 100 DEG C or less are cooled to 10-14 DEG C/min to come out of the stove, devitrified glass hair is made
Blanket；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the devitrified glass blank flat of preparation, obtain devitrified glass.
Preferably, the ferrochrome slag ingredient is by mass percentage：0.5%MoO3, 0.7%NiO, 1.5%
TiO2, 4.5%Na2O, 1.2%Cr2O3, 5.3%ZnO, 6.8%Fe2O3, 6.5%Al2O3, 19.0%CaO, 12.3%MgO,
41.7%SiO2。
Preferably, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight between them
Than being 15:8:3:1.
Preferably, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
Preferably, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Preferably, the step（3）In, the temperature of mold preheating is 800 DEG C.
Preferably, the step（3）Middle annealing condition：80- is made annealing treatment in 650 DEG C of Muffle furnace
100min。
Preferably, the step（4）In, the technical process of crystallization is as follows：In 540 DEG C of furnace inside holding 1.5h；So
760 DEG C are warming up to≤5 DEG C/min afterwards, keeps the temperature 3h；Then 835 DEG C are warming up to≤5 DEG C/min, keep the temperature 1.5h；Then with 12
DEG C/min is warming up to 940 DEG C, keep the temperature 0.8h；Then 535 DEG C are cooled to 18 DEG C/min, keep the temperature 1.5h；Then with 12 DEG C/min
It is cooled to 100 DEG C or less to come out of the stove, devitrified glass blank flat is made.
Compared with prior art, the present invention it has the advantages that：
（1）The present invention uses ferrochrome slag, and by addition fluxing agent, clarifying agent, KOH, prepares with preferable intensity, wearability
Energy, corrosion resistance and impact-resistant devitrified glass, while also solving the environmental pollution of ferrochrome tailing, security problems.
（2）Not only containing main chemical compositions needed for preparing devitrified glass in ferrochrome slag of the invention, simultaneously containing tune
Control the Cr of devitrified glass institutional framework2O3、TiO2、NiO、MoO3Etc. micro constitutents, it is brilliant to make the more tiny of crystal development
Body eduction rate is high, and then improves intensity, wearability, acid-alkali-corrosive-resisting and the excellent shock resistance of devitrified glass.
（3）Invent addition fluxing agent can the fusion temperature of system reduce, while the crystallization of devitrified glass can be effectively improved
Rate and principal crystalline phase percentage；And the addition of clarifying agent can eliminate the bubble in glass metal, improve devitrified glass quality；And
KOH can be used as the oxidant and activator of high-strength corrosion-resisting devitrified glass, can not only be oxidized to K at high temperature2O has and helps
Molten effect, meanwhile, KOH activity becomes strong under high temperature, the Cr in adsorbable ferrochrome slag, so that Cr is fixed in devitrified glass,
Prevent its dissolution pollution environment.
（4）For the present invention by constantly regulation fusing, molding and crystallization process parameter, can obtain as diopside is principal crystalline phase
Devitrified glass and crystal content can arrive 70-76%, and be that the devitrified glass of principal crystalline phase has excellent mechanical property using diopside
Energy, wearability and corrosion resistance, to make devitrified glass obtained that there is preferable intensity, wearability, corrosion resistance and resist
Impact property.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Clear, complete description.Obviously, the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.
Based on the embodiments of the present invention, those of ordinary skill in the art obtained institute without making creative work
There are other embodiments, belongs to the range that the present invention is protected.
Embodiment 1
The high-strength corrosion-resisting devitrified glass of the present embodiment, by mass percentage, the glass raw material group become：Ferrochrome slag 88%,
Fluxing agent 6.5wt%, clarifying agent 4.4wt%, KOH 1.1wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 30min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1300 DEG C, keeps the temperature 40min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 30min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 20min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 520 DEG C of furnaces
Warm 1h；Then 740 DEG C are warming up to≤5 DEG C/min, keep the temperature 2h；Then 820 DEG C are warming up to≤5 DEG C/min, keep the temperature 1h；So
930 DEG C are warming up to 10 DEG C/min afterwards, keeps the temperature 0.5h；Then 520 DEG C are cooled to 15 DEG C/min, keep the temperature 1h；Then with 10
DEG C/min is cooled to 100 DEG C or less and comes out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Preferably, the step（3）Middle annealing condition：It is made annealing treatment in 650 DEG C of Muffle furnace
80min。
Embodiment 2
The high-strength corrosion-resisting devitrified glass of the present embodiment, by mass percentage, the glass raw material group become：Ferrochrome slag
90wt%, fluxing agent 5.5wt%, clarifying agent 3.3wt%, KOH 1.2wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 40min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1400 DEG C, keeps the temperature 60min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 50min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 30min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 650 DEG C of furnaces
Warm 2h；Then 780 DEG C are warming up to≤5 DEG C/min, keep the temperature 4h；Then 850 DEG C are warming up to≤5 DEG C/min, keep the temperature 2h；Then
950 DEG C are warming up to 14 DEG C/min, keeps the temperature 1h；Then 650 DEG C are cooled to 20 DEG C/min, keep the temperature 2h；Then with 14 DEG C/min
It is cooled to 100 DEG C or less to come out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Wherein, the step（3）Middle annealing condition：100min is made annealing treatment in 650 DEG C of Muffle furnace.
Embodiment 3
The high-strength corrosion-resisting devitrified glass of the present embodiment, by mass percentage, the glass raw material group become：Ferrochrome slag
90wt%, fluxing agent 6wt%, clarifying agent 3wt%, KOH 1wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 35min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1350 DEG C, keeps the temperature 50min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 40min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 25min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 540 DEG C of furnaces
Warm 1.5h；Then 760 DEG C are warming up to≤5 DEG C/min, keep the temperature 3h；Then 835 DEG C are warming up to≤5 DEG C/min, heat preservation
1.5h；Then 940 DEG C are warming up to 12 DEG C/min, keep the temperature 0.8h；Then 535 DEG C are cooled to 18 DEG C/min, keep the temperature 1.5h；
Then 100 DEG C or less are cooled to 12 DEG C/min to come out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Wherein, the step（3）Middle annealing condition：90min is made annealing treatment in 650 DEG C of Muffle furnace.
Embodiment 4
The high-strength corrosion-resisting devitrified glass of the present embodiment of the present embodiment, by mass percentage, the glass raw material group become：
Ferrochrome slag 89wt%, fluxing agent 7wt%, clarifying agent 3.6wt%, KOH 0.8wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 32min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1330 DEG C, keeps the temperature 45min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 35min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 22min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 560 DEG C of furnaces
Warm 1.3h；Then 750 DEG C are warming up to≤5 DEG C/min, keep the temperature 2.5h；Then 830 DEG C are warming up to≤5 DEG C/min, heat preservation
1.2h；Then 940 DEG C are warming up to 11 DEG C/min, keep the temperature 0.6h；Then 530 DEG C are cooled to 16 DEG C/min, keep the temperature 1.3h；
Then 100 DEG C or less are cooled to 12 DEG C/min to come out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Wherein, the step（3）Middle annealing condition：85min is made annealing treatment in 650 DEG C of Muffle furnace.
Embodiment 5
The high-strength corrosion-resisting devitrified glass of the present embodiment of the present embodiment, by mass percentage, the glass raw material group become：
Ferrochrome slag 91wt%, fluxing agent 6wt%, clarifying agent 2.5wt%, KOH 0.5wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 38min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1380 DEG C, keeps the temperature 55min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 45min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 28min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 620 DEG C of furnaces
Warm 1.8h；Then 770 DEG C are warming up to≤5 DEG C/min, keep the temperature 3.5h；Then 840 DEG C are warming up to≤5 DEG C/min, heat preservation
1.8h；Then 945 DEG C are warming up to 13 DEG C/min, keep the temperature 0.8h；Then 620 DEG C are cooled to 18 DEG C/min, keep the temperature 1.8h；
Then 100 DEG C or less are cooled to 13 DEG C/min to come out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Wherein, the step（3）Middle annealing condition：95min is made annealing treatment in 650 DEG C of Muffle furnace.
Embodiment 6
The high-strength corrosion-resisting devitrified glass of the present embodiment, by mass percentage, the glass raw material group become：Ferrochrome slag
88.5wt%, fluxing agent 5.6wt%, clarifying agent 4.4wt%, KOH 1.5wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 35min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1300 DEG C, keeps the temperature 55min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 45min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 25min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 560 DEG C of furnaces
Warm 1.5h；Then 760 DEG C are warming up to≤5 DEG C/min, keep the temperature 3.5h；Then 840 DEG C are warming up to≤5 DEG C/min, heat preservation
1.5h；Then 940 DEG C are warming up to 12 DEG C/min, keep the temperature 0.8h；Then 600 DEG C are cooled to 16 DEG C/min, keep the temperature 1.2h；
Then 100 DEG C or less are cooled to 12 DEG C/min to come out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Wherein, the step（3）Middle annealing condition：85min is made annealing treatment in 650 DEG C of Muffle furnace.
Embodiment 7
The high-strength corrosion-resisting devitrified glass of the present embodiment, by mass percentage, the glass raw material group become：Ferrochrome slag
90.5wt%, fluxing agent 5.5wt%, clarifying agent 2.7wt%, KOH 1.3wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 38min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1330 DEG C, keeps the temperature 45min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 35min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 25min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 550 DEG C of furnaces
Warm 1.8h；Then 750 DEG C are warming up to≤5 DEG C/min, keep the temperature 2.5h；Then 830 DEG C are warming up to≤5 DEG C/min, heat preservation
1.2h；Then 935 DEG C are warming up to 12 DEG C/min, keep the temperature 0.6h；Then 580 DEG C are cooled to 18 DEG C/min, keep the temperature 1.8h；
Then 100 DEG C or less are cooled to 12 DEG C/min to come out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Wherein, the step（3）Middle annealing condition：95min is made annealing treatment in 650 DEG C of Muffle furnace.
Embodiment 8
The high-strength corrosion-resisting devitrified glass of the present embodiment, by mass percentage, the glass raw material group become：Ferrochrome slag
91.5wt%, fluxing agent 5.5wt%, clarifying agent 2.2wt%, KOH 0.8wt%.
Wherein, the cosolvent is fluorite, boron oxide, dolomite and barite, and the weight ratio between them is 15:8:
3:1。
Wherein, the clarifying agent is sodium nitrate, sodium carbonate or antimony oxide.
The present invention also provides the preparation methods of above-mentioned high-strength corrosion-resisting devitrified glass, include the following steps：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 33min at 650 DEG C, is added in high temperature furnace and is melted,
Fusion temperature is 1350 DEG C, keeps the temperature 55min, and KOH is then added, and is first warming up to 1500 DEG C with the speed of 5 DEG C/min, heat preservation
Then 35min is cooled to 1350 DEG C again with the speed of 8 DEG C/min, keep the temperature 22min, forms qualification after, clarification uniform after melt
Glass metal；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：It is protected in 550 DEG C of furnaces
Warm 1.8h；Then 770 DEG C are warming up to≤5 DEG C/min, keep the temperature 3.5h；Then 845 DEG C are warming up to≤5 DEG C/min, heat preservation
1.8h；Then 945 DEG C are warming up to 12 DEG C/min, keep the temperature 0.8h；Then 580 DEG C are cooled to 18 DEG C/min, keep the temperature 1.5h；
Then 100 DEG C or less are cooled to 12 DEG C/min to come out of the stove, devitrified glass blank flat is made；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the high-strength corrosion-resisting devitrified glass blank flat of preparation, obtain high intensity
Corrosion-resistant devitrified glass.
Wherein, the step（1）It further include that ferrochrome slag, fluxing agent and the clarifying agent of crushing are crossed into 50 meshes.
Wherein, the step（3）In, the temperature of mold preheating is 800 DEG C.
Wherein, the step（3）Middle annealing condition：95min is made annealing treatment in 650 DEG C of Muffle furnace.
Experimental example
To devitrified glass made from above-described embodiment 1-8 according to national standard《GB/T9966-2001》It makes a service test, specifically
The results are shown in Table 1.
Table 1
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Draw strength（MPa） | 67.87 | 69.86 | 75.34 | 71.15 | 65.87 | 64.59 | 73.23 | 70.28 |
| Acid resistance（%） | 0.056 | 0.044 | 0.038 | 0.056 | 0.054 | 0.062 | 0.048 | 0.053 |
| Alkali resistance（%） | 0.001 | 0 | 0 | 0.002 | 0 | 0.003 | 0.002 | 0 |
| Wearability（g/cm2) | 0.039 | 0.035 | 0.032 | 0.037 | 0.033 | 0.034 | 0.036 | 0.033 |
| Vickers hardness | 751 | 767 | 783 | 774 | 778 | 769 | 778 | 780 |
As shown in Table 1, high-strength corrosion-resisting devitrified glass prepared by the present invention has preferable intensity, wearability, acid and alkali-resistance rotten
Corrosion and shock resistance.
To sum up, creativeness of the invention is mainly reflected in the following：
（1）The present invention uses ferrochrome slag, and by addition fluxing agent, clarifying agent, KOH, prepares with preferable intensity, wearability
Energy, corrosion resistance and impact-resistant devitrified glass, while also solving the environmental pollution of ferrochrome tailing, security problems.
（2）Not only containing main chemical compositions needed for preparing devitrified glass in ferrochrome slag of the invention, simultaneously containing tune
Control the Cr of devitrified glass institutional framework2O3、TiO2、NiO、MoO3Etc. micro constitutents, it is brilliant to make the more tiny of crystal development
Body eduction rate is high, and then improves intensity, wearability, acid-alkali-corrosive-resisting and the excellent shock resistance of devitrified glass.
（3）Invent addition fluxing agent can the fusion temperature of system reduce, while the crystallization of devitrified glass can be effectively improved
Rate and principal crystalline phase percentage；And the addition of clarifying agent can eliminate the bubble in glass metal, improve devitrified glass quality；And
KOH can be used as the oxidant and activator of high-strength corrosion-resisting devitrified glass, can not only be oxidized to K at high temperature2O has and helps
Molten effect, meanwhile, KOH activity becomes strong under high temperature, the Cr in adsorbable ferrochrome slag, so that Cr is fixed in devitrified glass,
Prevent its dissolution pollution environment.
（4）For the present invention by constantly regulation fusing, molding and crystallization process parameter, can obtain as diopside is principal crystalline phase
Devitrified glass and crystal content can arrive 70-76%, and be that the devitrified glass of principal crystalline phase has excellent mechanical property using diopside
Energy, wearability and corrosion resistance, to make devitrified glass obtained that there is preferable intensity, wearability, corrosion resistance and resist
Impact property.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. a kind of high-strength corrosion-resisting devitrified glass, which is characterized in that by mass percentage, which becomes：Chromium
Scum 90wt%, fluxing agent 6wt%, clarifying agent 3wt%, KOH 1wt%, and prepared using following methods：
（1）The desired amount of ferrochrome slag, fluxing agent and clarifying agent are crushed and be sieved, and will ferrochrome slag, fluxing agent and clear after sieving
Clear agent investment batch mixer is sufficiently mixed, and obtains devitrified glass basis batch；
（2）Mixed devitrified glass basis batch is preheated into 30-40min at 650 DEG C, is added in high temperature furnace and is melted
Change, fusion temperature is 1300-1400 DEG C, keeps the temperature 40-60min, and KOH is then added, is first warming up to 1500 with the speed of 5 DEG C/min
DEG C, 30-50min is kept the temperature, is then cooled to 1350 DEG C again with the speed of 8 DEG C/min, keeps the temperature 20-30min, it is uniform to melt, clear
Qualified glass metal is formed after clear；
（3）Uniform, clear glass metal is poured into preheated mold, after glass metal molding after after be sent into Muffle furnace in anneal
Processing, obtains parent glass plate；
（4）Molding parent glass plate is sent into resistance furnace and carries out crystallization, the technical process of crystallization is as follows：In 520-650 DEG C of furnace
Inside holding 1-2h；Then it is warming up to 740-780 DEG C with≤5 DEG C/min, keeps the temperature 2-4h；Then 820- is warming up to≤5 DEG C/min
850 DEG C, keep the temperature 1-2h；Then it is warming up to 930-950 DEG C with 10-14 DEG C/min, keeps the temperature 0.5-1h；Then with 15-20 DEG C/min
It is cooled to 520-650 DEG C, keeps the temperature 1-2h；Then 100 DEG C or less are cooled to 10-14 DEG C/min to come out of the stove, devitrified glass hair is made
Blanket；
（5）Thickness, corase grinding, fine polishing, cutting, chamfered edge are determined to the devitrified glass blank flat of preparation, obtain devitrified glass.
2. high-strength corrosion-resisting devitrified glass according to claim 1, which is characterized in that the ferrochrome slag ingredient presses quality
Percentage is：0.5%MoO3, 0.7%NiO, 1.5%TiO2, 4.5%Na2O, 1.2%Cr2O3, 5.3%ZnO, 6.8%Fe2O3、
6.5%Al2O3, 19.0%CaO, 12.3%MgO, 41.7%SiO2。
3. high-strength corrosion-resisting devitrified glass according to claim 1, which is characterized in that the cosolvent is fluorite, oxygen
Change boron, dolomite and barite, and the weight ratio between them is 15:8:3:1.
4. high-strength corrosion-resisting devitrified glass according to claim 1, which is characterized in that the clarifying agent be sodium nitrate,
Sodium carbonate or antimony oxide.
5. high-strength corrosion-resisting devitrified glass according to claim 1, which is characterized in that the step（1）Further including will
Ferrochrome slag, fluxing agent and the clarifying agent of crushing cross 50 meshes.
6. high-strength corrosion-resisting devitrified glass according to claim 1, which is characterized in that the step（3）In, mold is pre-
The temperature of heat is 800 DEG C.
7. high-strength corrosion-resisting devitrified glass according to claim 1, which is characterized in that the step（3）At middle annealing
Manage bar part：80-100min is made annealing treatment in 650 DEG C of Muffle furnace.
8. high-strength corrosion-resisting devitrified glass according to claim 1, which is characterized in that the step（4）In, crystallization
Technical process is as follows：In 540 DEG C of furnace inside holding 1.5h；Then 760 DEG C are warming up to≤5 DEG C/min, keep the temperature 3h；Then with≤5
DEG C/min is warming up to 835 DEG C, keep the temperature 1.5h；Then 940 DEG C are warming up to 12 DEG C/min, keep the temperature 0.8h；Then with 18 DEG C/
Min is cooled to 535 DEG C, keeps the temperature 1.5h；Then 100 DEG C or less are cooled to 12 DEG C/min to come out of the stove, devitrified glass blank flat is made.
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| CN103224328A (en) * | 2013-05-16 | 2013-07-31 | 承德华富玻璃技术工程有限公司 | Microcrystalline glass and preparation method thereof |
| CN103951193A (en) * | 2014-05-08 | 2014-07-30 | 中国科学院过程工程研究所 | Glass ceramics prepared from tailings obtained by nickel-molybdenum ore dressing and smelting and preparation method thereof |
| CN105924013A (en) * | 2016-04-25 | 2016-09-07 | 四川名微晶科技股份有限公司 | Glass ceramic produced by all electric fused rolling process technique using ferrochrome slags as raw materials and production method therefor |
| CN107417122A (en) * | 2017-07-18 | 2017-12-01 | 武汉理工大学 | A kind of method for comprehensively utilizing vanadium extraction residues and preparing devitrified glass |
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2018
- 2018-07-31 CN CN201810856409.1A patent/CN108863084A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224328A (en) * | 2013-05-16 | 2013-07-31 | 承德华富玻璃技术工程有限公司 | Microcrystalline glass and preparation method thereof |
| CN103951193A (en) * | 2014-05-08 | 2014-07-30 | 中国科学院过程工程研究所 | Glass ceramics prepared from tailings obtained by nickel-molybdenum ore dressing and smelting and preparation method thereof |
| CN105924013A (en) * | 2016-04-25 | 2016-09-07 | 四川名微晶科技股份有限公司 | Glass ceramic produced by all electric fused rolling process technique using ferrochrome slags as raw materials and production method therefor |
| CN107417122A (en) * | 2017-07-18 | 2017-12-01 | 武汉理工大学 | A kind of method for comprehensively utilizing vanadium extraction residues and preparing devitrified glass |
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