CN104671664A - Method for preparing wear-resistant corrosion-resistant glass ceramics - Google Patents
Method for preparing wear-resistant corrosion-resistant glass ceramics Download PDFInfo
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Abstract
The invention discloses a method for preparing wear-resistant corrosion-resistant glass ceramics. The method comprises the following steps: dosing the following components in percentage by mass: 25-60 percent of coal ash, 20-40 percent of blast furnace smelting slag and 15-35 percent of refining slag; carrying out ball milling and mixing the materials for 10-200 minutes; melting in a high-temperature furnace at the melting temperature of 1450-1550 DEG C, and preserving the temperature for 60-150 minutes; pouring the melted molten glass into a rotating disc which rotates at a high speed, performing centrifugal graining, and finishing sensible heat recovery and glass granule preparation under the action of compressed air; grinding the glass granules into glass powder with the granularity of not more than 200 meshes, and pressing and molding under the pressure of 70-150MPa; stepwise heating the pressed and molded glass sample in a high-temperature muffle furnace, and crystallizing, cooling, and sintering; and grinding and polishing. The blast furnace smelting slag, coal ash and refining slag are taken as raw materials for performing preparation, the cost of the raw materials is high, and exploitation of natural resources is reduced; and moreover, the rotating disc method is combined with the compressed air for performing preparation. The preparation method has the characteristics of simple process, high energy utilization rate and low energy consumption, emission of harmful gases can be reduced, and the environmental load is reduced.
Description
Technical field
The invention belongs to solid waste resource recycling technical field, be specifically related to one and utilize blast-furnace smelting slag, flyash, refining slag for raw material, prepare the technique of wear-and corrosion-resistant devitrified glass.
Background technology
In steel industry, water is generally utilized to process melting waste slag as heat-eliminating medium.Water can realize metallurgical slag as heat-eliminating medium and cool fast, obtains the glassy phase particle of high level, increases its added value.But, adopt this technique not only to waste a large amount of water resourcess, and the high-quality sensible heat that metallurgical slag stores can not get effective recycling, can produce SO simultaneously
2, H
2the gases such as S, contaminate environment.Therefore, with spining disk method be representational quenching dry type shotting process metallurgical slag become current industrialization application trend.In addition, along with improving constantly of people's quality of life, heat power plant instead of the boiler of high energy consumption high pollution.But a large amount of flyash has become again the pollutent that thermoelectricity industry is new.The solid waste of all kinds of accumulation not only land occupation, contaminate environment but also there is potential safety hazard.
On the other hand, in industries such as chemical industry, metallurgy, nuclear power, mine, building, pharmacy, wear-and corrosion-resistant type product has a wide range of applications.Especially, the various products run under conveying coexists operating mode containing the corrosion such as corrosive liquid and the wearing and tearing of solid particulate, demand is huge.Correspondingly, 2% ~ 4% of national GDP is accounted for by material corrosion direct, the indirect economic loss caused that lost efficacy every year.Because conventional metal inner lining pipeline is vulnerable to chemical corrosion and mechanical wear, and the multiple-unit tube of conventional inorganic non-metallic material and polymer materials liner, as structured material usually premature failure because shock resistance is poor when engineering component is applied.Therefore, research and develop abrasionproof corrosion resistant type matrix material of new generation and there are significant economic results in society.
Devitrified glass is by the parent glass of specific composition, and a class obtained by controlling crystallizing in heat-processed contains the polycrystalline solids material of a large amount of crystallite phase and glassy phase.Different with performance according to composition, devitrified glass can be divided into different system.Wherein, CaO-MgO-SiO
2-Al
2o
3microcrystalline glass in series has that bending resistance, resistance to compression and shock resistance are excellent, chemical stability good, wear resistance and corrosion resistance is strong etc. and is the important substitute of traditional corrosion-proof wear-resistant material.And the main component of blast-furnace smelting slag, flyash, refining slag is all the oxide compound of Ca, Mg, Al, Si, it is the important source material forming devitrified glass.And refining slag is rich in rare earth, fluorite.As the Composite Nucleation Agents of devitrified glass, thus the overall performance of devitrified glass can be improved.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of wear-and corrosion-resistant devitrified glass, be prepared for raw material with blast-furnace smelting slag, flyash, refining slag, spining disk method is adopted to be prepared in conjunction with pressurized air, have that raw materials cost is low, technique is simple, energy utilization rate is high and the feature that energy consumption is low, the discharge of obnoxious flavour can be reduced simultaneously, reduce carrying capacity of environment.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of wear-and corrosion-resistant devitrified glass, is characterized in that comprising the following steps:
1) with blast-furnace smelting slag, flyash, refining slag for raw material, the chemical constitution according to devitrified glass is prepared burden: flyash 25 ~ 60%, blast-furnace smelting slag 20 ~ 40%, refining slag 15 ~ 35%, and above-mentioned per-cent is mass percent;
2) batch mixing: the above-mentioned raw material prepared is placed in high energy ball mill ball mill mixing 10 ~ 200min;
3) found: the powder after ball milling is put into crucible, be placed in High Temperature Furnaces Heating Apparatus and melt, temperature of fusion is 1450 ~ 1550 DEG C, soaking time 60 ~ 150min;
4) rotating disk granulation: the glass metal melted is poured in the rotating disk of high speed rotating, by centrifugal granulation effect, utilizes pressurized air as heat exchange communication medium recycling glass particle heat, obtain being rich in CaO-MgO-SiO
2-Al
2o
3it is glass particle;
5) shaping: to become granularity to be not more than 200 object glass powders in grinding in ball grinder glass particle, and the glass powder after grinding is loaded in mould, make type at 70 ~ 150MPa pressure;
6) crystallization and sintering: the glass sample of compression moulding is put into high temperature Muffle furnace, first be warmed up to 300 ~ 400 DEG C with the heat-up rate of 3 ~ 8 DEG C/min, then be warming up to 750 ~ 810 DEG C with the temperature rise rate of 8 ~ 20 DEG C/min, be incubated 30 ~ 120min at this temperature; Then be heated to 850 ~ 950 DEG C with the temperature rise rate of 5 ~ 10 DEG C/min, and be incubated 30 ~ 120min, after completing crystallization and sintering, furnace cooling;
7) sanding and polishing: the devitrified glass obtained furnace cooling is polished, polishing is prepared into final devitrified glass product.
As improvement, the chemical constitution of described final devitrified glass is: SiO
2: 45 ~ 60%, CaO:10 ~ 20%, MgO:8 ~ 10%, Al
2o
3: 6 ~ 18%, CaF
2: 2 ~ 8%, CeO
2: 0.5 ~ 2%, K
2o:0.5 ~ 1.5%, Na
2o:0.5 ~ 1.5%, TiO
2: 1 ~ 2%, Cr
2o
3: 0.4 ~ 1%, above-mentioned per-cent is mass percent.
As improvement, described step 1) in refining slag come from smelting electroslag melt steel.
As improvement, described step 1) in blast-furnace smelting slag, flyash, refining slag is through step 2) granularity of powder is not more than 200 orders after ball milling.
Improve again, described step 4) material of turntable adopts high temperature steel, and the rotating speed of rotating disk is 500 ~ 2500rpm, and the diameter of rotating disk is 100 ~ 500mm.
Improve again, described step 4) in compressed-air actuated pressure be 0.6 ~ 0.8MPa.
Further improvement, described step 4) amount of glassy phase is 97 ~ 99% in obtained glass particle, size-grade distribution is at 0.1 ~ 0.5mm.
Compared with prior art, the invention has the advantages that:
1, wear-and corrosion-resistant devitrified glass is prepared using blast-furnace smelting slag, flyash, refining slag as main raw material, can digestion of solid waste in a large number, greatly reduce the cost of devitrified glass, obtained product can be widely used in the traditional industries such as chemical industry, metallurgy, building, nuclear power, mine, pharmacy, substitute the like product adopting natural resources to prepare, reduce the exploitation of natural resources;
2, adopt spining disk method in conjunction with pressurized air quenching glass melt, the high-quality sensible heat that can discharge in efficient recovery devitrified glass production process, improves energy utilization rate, reduces SO
2, H
2the discharge of the obnoxious flavoures such as S, reduces carrying capacity of environment.Obtained glass particle, without the need to drying, can be directly used in and prepare devitrified glass product, decrease energy consumption;
3, refining slag is not only containing the main chemical compositions preparing devitrified glass, and is rich in and refining slag is rich in rare earth, fluorite, as the Composite Nucleation Agents of devitrified glass, can promote the crystallization of devitrified glass, thus improve the overall performance of devitrified glass.
Accompanying drawing explanation
Fig. 1 is that spining disk method of the present invention prepares the principle schematic of glass particle in conjunction with pressurized air;
Fig. 2 is process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
The preparation technology of the devitrified glass of the present embodiment, step is as follows:
1, prepare burden: by weight batching: flyash 50%, blast-furnace smelting slag 35%, refining slag 15% is prepared burden.
2, batch mixing: the raw material of weighing by weight ratio is adopted the mixing of high-performance ball mill, and mixing time is 50min;
3, melting: the powder after above-mentioned ball milling is entered crucible, is placed in High Temperature Furnaces Heating Apparatus and melts, and temperature of fusion is 1450 DEG C, soaking time 150min.
4, rotating disk granulation: glass melt being poured into rotating speed is 1500rpm, and diameter is that the rotating disk of 200mm carries out centrifugal granulation, and under the pressurized air effect of 0.6MPa, complete Exposure degree and glass particle preparation; The glass particle amount of glassy phase of gained is 97%, and size-grade distribution is at 0.3 ~ 0.5mm; The principle of rotating disk granulating as shown in Figure 1;
5, shaping: glass particle to be placed in high-performance ball mill and to be milled to 200 mesh sieves, and the glass powder after grinding is loaded in mould, at 80MPa forming under the pressure;
6, crystallization and sintering: the glass sample of compression moulding is placed in retort furnace, elder generation to 300 DEG C with the heat-up rate of 3 DEG C/min, is then warming up to 750 DEG C with the temperature rise rate of 8 DEG C/min, is incubated 60min at this temperature; Then be heated to 850 DEG C with the temperature rise rate of 5 DEG C/min, and be incubated 60min, complete crystallization and sintering after, cool to room temperature with the furnace, and devitrified glass sample is polished, polishing.
The devitrified glass performance index obtained under above-mentioned processing condition are: hardness 1050HV, folding strength 123MPa, volume density 2.65g/cm
3, the acid resistance in sulphuric acid soln is 96.8%, and the alkali resistance in sodium hydroxide solution is 98.5%, and the sulphuric acid soln in experiment and concentration of sodium hydroxide solution are 1% volumetric concentration.
Embodiment 2:
The preparation technology of the devitrified glass of the present embodiment, step is as follows:
1, prepare burden: by weight batching: flyash 55%, blast-furnace smelting slag 25%, refining slag 20% is prepared burden;
2, batch mixing: the raw material of weighing by weight ratio is adopted the mixing of high-performance ball mill, and mixing time is 80min;
3, melting: the powder after above-mentioned ball milling is entered crucible, is placed in High Temperature Furnaces Heating Apparatus and melts, and temperature of fusion is 1500 DEG C, soaking time 120min;
4, rotating disk granulation: glass melt being poured into rotating speed is 2000rpm, diameter is that the rotating disk of 300mm carries out centrifugal granulation, and under the pressurized air effect of 0.7MPa, completing Exposure degree and glass particle preparation, the glass particle amount of glassy phase of gained is 98%, and size-grade distribution is at 0.2 ~ 0.4mm; The principle of rotating disk granulating as shown in Figure 1;
5, shaping: glass particle to be placed in high-performance ball mill and to be milled to 200 mesh sieves, and the glass powder after grinding is loaded in mould, at 100MPa forming under the pressure;
6, crystallization and sintering: the glass sample of compression moulding is placed in retort furnace, elder generation to 400 DEG C with the heat-up rate of 5 DEG C/min, is then warming up to 780 DEG C with the temperature rise rate of 15 DEG C/min, is incubated 120min at this temperature; Then be heated to 900 DEG C with the temperature rise rate of 8 DEG C/min, and be incubated 90min, complete crystallization and sintering after, cool to room temperature with the furnace, and devitrified glass sample is polished, polishing.
The devitrified glass performance index obtained under above-mentioned processing condition are: hardness 1250HV, folding strength 142MPa, volume density 2.73g/cm
3, the acid resistance in sulphuric acid soln is 97.2%, and the alkali resistance in sodium hydroxide solution is 98.2%, and the sulphuric acid soln in experiment and concentration of sodium hydroxide solution are 1% volumetric concentration.
Embodiment 3:
The preparation technology of the devitrified glass of the present embodiment, step is as follows:
1, prepare burden: by weight batching: flyash 40%, blast-furnace smelting slag 35%, refining slag 25% is prepared burden;
2, batch mixing: the raw material of weighing by weight ratio is adopted the mixing of high-performance ball mill, and mixing time is 150min;
3, melting: the powder after above-mentioned ball milling is entered crucible, is placed in High Temperature Furnaces Heating Apparatus and melts, and temperature of fusion is 1550 DEG C, soaking time 150min;
4, rotating disk granulation: glass melt being poured into rotating speed is 2500rpm, and diameter is that the rotating disk of 500mm carries out centrifugal granulation, and under the pressurized air effect of 0.8MPa, complete Exposure degree and glass particle preparation.The glass particle amount of glassy phase of gained is 99%, and size-grade distribution is at 0.1 ~ 0.2mm; The principle of rotating disk granulating as shown in Figure 1;
5, shaping: glass particle to be placed in high-performance ball mill and to be milled to 200 mesh sieves, and the glass powder after grinding is loaded in mould, at 120MPa forming under the pressure;
6, crystallization and sintering: the glass sample of compression moulding is placed in retort furnace, elder generation to 350 DEG C with the heat-up rate of 8 DEG C/min, is then warming up to 800 DEG C with the temperature rise rate of 20 DEG C/min, is incubated 100min at this temperature; Then be heated to 950 DEG C with the temperature rise rate of 10 DEG C/min, and be incubated 120min, complete crystallization and sintering after, cool to room temperature with the furnace, and devitrified glass sample is polished, polishing.
The devitrified glass performance index obtained under above-mentioned processing condition are: hardness 1280HV, folding strength 155MPa, volume density 2.78g/cm
3, the acid resistance in sulphuric acid soln is 98.5%, and the alkali resistance in sodium hydroxide solution is 98.2%, and the sulphuric acid soln in experiment and concentration of sodium hydroxide solution are 1% volumetric concentration.
Claims (7)
1. a preparation method for wear-and corrosion-resistant devitrified glass, is characterized in that comprising the following steps:
1) with blast-furnace smelting slag, flyash, refining slag for raw material, the chemical constitution according to devitrified glass is prepared burden: flyash 25 ~ 60%, blast-furnace smelting slag 20 ~ 40%, refining slag 15 ~ 35%, and above-mentioned per-cent is mass percent;
2) batch mixing: the above-mentioned raw material prepared is placed in high energy ball mill ball mill mixing 10 ~ 200min;
3) found: the powder after ball milling is put into crucible, be placed in High Temperature Furnaces Heating Apparatus and melt, temperature of fusion is 1450 ~ 1550 DEG C, soaking time 60 ~ 150min;
4) rotating disk granulation: be poured in the rotating disk of high speed rotating by the glass metal melted, by centrifugal granulation effect, and completes Exposure degree and glass particle preparation, obtains being rich in CaO-MgO-SiO under pressurized air effect
2-Al
2o
3it is the glass particle of glassy phase;
5) shaping: to become granularity to be not more than 200 object glass powders in grinding in ball grinder glass particle, and the glass powder after grinding is loaded in mould, make type at 70 ~ 150MPa pressure;
6) crystallization and sintering: the glass sample of compression moulding is put into high temperature Muffle furnace, first be warmed up to 300 ~ 400 DEG C with the heat-up rate of 3 ~ 8 DEG C/min, then be warming up to 750 ~ 810 DEG C with the temperature rise rate of 8 ~ 20 DEG C/min, be incubated 30 ~ 120min at this temperature; Then be heated to 850 ~ 950 DEG C with the temperature rise rate of 5 ~ 10 DEG C/min, and be incubated 30 ~ 120min, after completing crystallization and sintering, furnace cooling;
7) sanding and polishing: the devitrified glass obtained furnace cooling is polished, polishing is prepared into final devitrified glass product.
2. preparation method according to claim 1, is characterized in that: the chemical constitution of described final devitrified glass is: SiO
2: 45 ~ 60%, CaO:10 ~ 20%, MgO:8 ~ 10%, Al
2o
3: 6 ~ 18%, CaF
2: 2 ~ 8%, CeO
2: 0.5 ~ 2%, K
2o:0.5 ~ 1.5%, Na
2o:0.5 ~ 1.5%, TiO
2: 1 ~ 2%, Cr
2o
3: 0.4 ~ 1%, above-mentioned per-cent is mass percent.
3. preparation method according to claim 1, is characterized in that: described step 1) in refining slag be come from smelting electroslag melt steel.
4. preparation method according to claim 1, is characterized in that: described step 1) in blast-furnace smelting slag, flyash, refining slag is through step 2) granularity of powder is not more than 200 orders after ball milling.
5. preparation method according to claim 1, is characterized in that: described step 4) material of turntable adopts high temperature steel, and the rotating speed of rotating disk is 500 ~ 2500rpm, and the diameter of rotating disk is 100 ~ 500mm.
6. preparation method according to claim 1, is characterized in that: described step 4) in compressed-air actuated pressure be 0.6 ~ 0.8MPa.
7. preparation method according to claim 1, is characterized in that: described step 4) amount of glassy phase is 97 ~ 99% in obtained glass particle, size-grade distribution is at 0.1 ~ 0.5mm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106186702A (en) * | 2016-07-22 | 2016-12-07 | 南通大明玉新材料科技有限公司 | A kind of method utilizing waste residue to prepare micro crystal material |
| CN106514499A (en) * | 2016-12-29 | 2017-03-22 | 富耐克超硬材料股份有限公司 | Microcrystalline glass binder, preparation method thereof, superhard material grinding tool and preparation method thereof |
| CN106904836A (en) * | 2017-03-31 | 2017-06-30 | 合肥图腾龙医疗用品开发有限公司 | A kind of devitrified glass of high grade of transparency wear-and corrosion-resistant and preparation method thereof |
| CN107010839A (en) * | 2017-04-18 | 2017-08-04 | 宋小明 | A kind of micro crystal material of cerium mischmetal containing lanthanum and preparation method thereof |
| CN108483925A (en) * | 2018-04-27 | 2018-09-04 | 中国兵器科学研究院宁波分院 | A method of comprehensive utilization city solid waste efficiently prepares high tough devitrified glass |
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| CN102211874A (en) * | 2011-05-10 | 2011-10-12 | 北京科技大学 | Microcrystalline glass and preparation method thereof |
| CN102826758A (en) * | 2012-08-29 | 2012-12-19 | 内蒙古科技大学 | Industrial microcrystalline glass plate resistant to wear and corrosion and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186702A (en) * | 2016-07-22 | 2016-12-07 | 南通大明玉新材料科技有限公司 | A kind of method utilizing waste residue to prepare micro crystal material |
| CN106514499A (en) * | 2016-12-29 | 2017-03-22 | 富耐克超硬材料股份有限公司 | Microcrystalline glass binder, preparation method thereof, superhard material grinding tool and preparation method thereof |
| CN106904836A (en) * | 2017-03-31 | 2017-06-30 | 合肥图腾龙医疗用品开发有限公司 | A kind of devitrified glass of high grade of transparency wear-and corrosion-resistant and preparation method thereof |
| CN107010839A (en) * | 2017-04-18 | 2017-08-04 | 宋小明 | A kind of micro crystal material of cerium mischmetal containing lanthanum and preparation method thereof |
| CN108483925A (en) * | 2018-04-27 | 2018-09-04 | 中国兵器科学研究院宁波分院 | A method of comprehensive utilization city solid waste efficiently prepares high tough devitrified glass |
| CN108483925B (en) * | 2018-04-27 | 2021-08-10 | 中国兵器科学研究院宁波分院 | Method for efficiently preparing high-strength and high-toughness microcrystalline glass by comprehensively utilizing urban solid wastes |
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