CN104045357B - One is composite refractory and preparation method thereof cheaply - Google Patents
One is composite refractory and preparation method thereof cheaply Download PDFInfo
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- CN104045357B CN104045357B CN201410233115.5A CN201410233115A CN104045357B CN 104045357 B CN104045357 B CN 104045357B CN 201410233115 A CN201410233115 A CN 201410233115A CN 104045357 B CN104045357 B CN 104045357B
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Abstract
The invention discloses one composite refractory and preparation method thereof cheaply, the method comprises the following steps: the raw material that comprises the waste material in carbon, aluminium and crystalline silicon cutting technique is pressed into green compact by (1), wherein, waste material in crystalline silicon cutting technique comprises the oxide of carborundum, silicon, iron, and aluminium is by extracting in the industrial waste ROLLING OIL in aluminium foil thermal rolling production process; (2) green compact are nitridation sintered, obtain composite refractory, this material comprises carborundum phase, ferro-silicon nitride phase and aluminium nitride phase, and carborundum phase, ferro-silicon nitride phase are interosculated mutually with aluminium nitride. Because the oxide of above-mentioned aluminium, carborundum and iron is all from industrial waste, realize effective utilization of secondary resource, reduce the pollution to environment, reduce cost. In crystalline silicon cutting technique, along with the particle diameter of oxide of carborundum, silicon and iron in the waste material that makes to obtain of cutting abrasive material is all less, stock yard is fully contacted, the good uniformity of material, has improved material property.
Description
Technical field
The invention belongs to technical field of refractory materials, is about secondary resource comprehensive utilization,Be specifically related to one composite refractory and preparation method thereof cheaply.
Background technology
Along with people improve the requirement of environmental protection, greatly develop renewable money in the whole worldUnder the background in source, solar energy industry has entered the period of high speed development. And as solar energyThe crystal silicon chip of one of photoelectric conversion device of battery is by multi-wire saw crystal silicon rod technologyObtain, its main flow process using is with the water-based cutting of polyethylene glycol, silicon carbide micro-powder compositionThe liquid production of cutting into slices, the granularity scope of the carborundum in water-based cutting liquid is1～12 μ m. In section production process, approximately 50% crystal silicon particle is because of grinding loss quiltBring in cutting slug, silicon carbide micro-powder constantly reduces sharp keen degree in friction,Even the sharpness of silicon carbide micro-powder weakens to the ability of losing cutting, and brown iron oxideCan constantly accumulation in cutting slug in the time of steel wire grinding silicon rod. At present, crystalline silicon is cutCut the super-fine silicon micro-powder that most carborundum in the waste material in technique and grinding are got off,Its granularity is less than 5mm, and temporarily without too large purposes, what have sells even at a low price, the heap havingAccumulate and put, contaminated environment, becomes the burden of enterprise.
In aluminium foil hot rolling is produced, in ROLLING OIL, can take away a large amount of aluminium powders on aluminium foil, forMake ROLLING OIL keep clean to produce high-quality sheet material, used in filter-cloth filtering ROLLING OILAluminium powder particulate, filtration product is the mixture of aluminium powder particulate and greasy dirt, aluminium powder particulate tableFace has adsorbed the ROLLING OIL that contains additive. In production process, need regularly will filter productThe mixture of thing aluminium powder particulate and greasy dirt is thrown away, and has caused great waste.
Compared with pure nitride material, it is good that ferro-silicon nitride has agglutinating property, thermal conductivity high andThe advantages such as thermal coefficient of expansion is low, can be used as refractory raw material and high temperature bond phase. At present, nitrogenIn the preparation technology of SiClx iron carborundum refractory material, adopt the larger carbonization of granularitySilicon grain and ferrosilicon powder, easily cause the uneven distribution of element, reduces the merit of refractory materialCan property. And adopt the less feed particles of particle diameter can cause the increase of cost, be unfavorable forIndustry is promoted. Taking ferrosilicon as raw material synthesizing silicon nitride iron, synthetic cost is higher.
At present, no matter be in life or production, huge for the demand of refractory material,But refractory material cost of material used is high, synthesis technique complexity, causes final syntheticThe cost of the refractory material going out is always high.
Summary of the invention
Technical problem to be solved by this invention is above-mentioned for what exist in prior artFoot, provides one composite refractory and preparation method thereof cheaply, in the method, usesThe oxide of raw material aluminium, carborundum and iron all come from industrial waste, realized secondaryEffective utilization of resource, has reduced the pollution to environment. In crystalline silicon cutting technique, withThe carrying out of cutting abrasive material, the oxide of carborundum, silicon and iron in the waste material that makes to obtainParticle diameter all less, make can fully contact between raw material, the good uniformity of material, carriesThe high performance of material.
The technical scheme that solution the technology of the present invention problem adopts is to provide one cheaplyThe preparation method of composite refractory, comprises the following steps:
(1) raw material that comprises the waste material in carbon, aluminium and crystalline silicon cutting technique is pressed intoGreen compact, wherein, the waste material in described crystalline silicon cutting technique comprises carborundum, silicon, ironOxide, described aluminium is by carrying in the industrial waste ROLLING OIL in aluminium foil thermal rolling production processGet;
(2) by nitridation sintered described green compact, obtain composite refractory cheaply, shouldComposite refractory comprises carborundum phase, ferro-silicon nitride phase and aluminium nitride phase cheaply,And described carborundum phase, described ferro-silicon nitride phase are interosculated mutually with described aluminium nitride.
Preferably, in described step (1), the particle diameter of described carbon is 0.2～0.5 μ m,The particle diameter of described aluminium is 1～5 μ m, and the particle diameter of described carborundum is 0.5～10 μ m, described inThe particle diameter of silicon is 0.5～10 μ m. The present invention is best suited in the crystalline silicon cutting waste material of employingSuperfine silicon carbide grain graininess below 10 μ m, wherein mainly taking 1～5 μ m as main,Compare with conventional carbon silicon carbide particle, have surface area large, active high, heat treatment takesBetween short, greatly reduce energy resource consumption and manufacturing cost.
Preferably, the waste material in the described crystalline silicon cutting technique in described step (1)In the mass ratio of oxide of carborundum, silicon and iron be (70～85) wt%:(8～20)wt％：(7～10)wt％。
Preferably, the described aluminium in described step (1) and the mass ratio of described carbon are(2～2.5)：1。
Preferably, the matter of the oxide of the described aluminium in described step (1) and described ironAmount is than being (3.5～5): 1.
Preferably, described by the industrial waste ROLLING OIL in aluminium foil thermal rolling production processThe method of extracting aluminium is specially: by the industrial waste ROLLING OIL in aluminium foil thermal rolling production processFiltration obtains leaching thing, and this is leached to thing under inert gas atmosphere, at 570～620 DEG C,Calcine 2～3 hours, obtain the aluminium of surface without ROLLING OIL.
Preferably, in the industrial waste hot-rolling oil from aluminium foil thermal rolling production process, extractAfter aluminium to surface without ROLLING OIL, also comprise the ball milling step for this aluminium: by surperficial nothingThe aluminium of ROLLING OIL is put in ball mill, opens vacuum system, is evacuated down to 0.1Pa, closesClose vacuum system, pass into high pure nitrogen to 10～20Pa that purity is greater than 99wt%, continueWhen passing into nitrogen, carry out ball milling, nitrogen flow rate is 50～80ml/min, Ball-milling Time6～8 hours, the aluminum powder particle size scope obtaining after ball milling was 1～5 μ m.
Preferably, the preparation process of the described raw material in described step (1) is specially:In the waste material in described crystalline silicon cutting technique, allocate described aluminium and described carbon into, then addBonding agent obtains described raw material.
Preferably, described bonding agent comprises dextrin, polyethylene glycol and ethanol, described pasteEssence account for described green compact quality 0.5～1%, described polyethylene glycol accounts for the quality of described green compact1～2%, described ethanol account for described green compact quality 1.5～2%.
Preferably, the nitridation sintered concrete grammar in described step (2) for: by instituteState green compact and put into nitriding furnace, open vacuum system, heating system when continuing to vacuumizeSystem is to 900～1000 DEG C, and temperature is evacuated down to 0.1～0.01Pa after arriving 900～1000 DEG C,Close vacuum system; Then pass into high pure nitrogen to 10～20Pa that purity is 99wt%,Open drain tap and continue to pass into nitrogen 5～10 minutes, close liquid passage inlet and outlet,900～1000 DEG C are incubated 3～4 hours; After waiting for that thermit reaction fully occurs, by temperature from900～1000 DEG C rise to 1100～1200 DEG C, and opening gas circuit import and outlet, pass into nitrogen5～10 minutes, air pressure to 10～20Pa, was incubated 1～2 hour, continued logical when insulationEnter nitrogen; After waiting for that aluminium powder changes into aluminium nitride, temperature is risen to from 1100～1200 DEG C1450～1550 DEG C, when being incubated 4～6 hours, keep nitrogen to continue to pass into; Naturally coldBut to room temperature, composite refractory cheaply described in obtaining.
The present invention also provides one composite refractory cheaply, and it is by above-mentioned methodPreparation.
The beneficial effect that technical solution of the present invention is brought
Compared with prior art, feature of the present invention and beneficial effect thereof are:
1. silicon carbide micro-powder used in the present invention comes from crystalline silicon cutting techniqueWaste material, the handling principle of waste material is that impurity is removed, and leaves silicon carbide powder, technique letterDan Yihang, wide material sources, low price, make full use of resource, turns waste into wealth, and realizesThe rational and efficient use of secondary resource.
2. aluminium powder used in the present invention is from the Industry Waste in aluminium foil thermal rolling production processMaterial ROLLING OIL, manufacturing process is simple, is the recycling to industrial waste.
3. strong adaptability of the present invention. According to the performance requirement of product, can by contain silica flour andThe silicon carbide micro-powder of ferriferous oxide powder, taking the content of ferriferous oxide powder as standard, mixes differenceThe aluminium powder of content, the carborundum that obtains different performance is tied in conjunction with aluminium nitride in conjunction with ferro-silicon nitrideClose carbon refractory.
4. strong adaptability of the present invention. According to the performance requirement of product, can be by containing silica flourWith the aluminium powder of allocating in the silicon carbide micro-powder of ferriferous oxide powder be standard, mix different contentCarbon dust, the carborundum that obtains different performance in conjunction with ferro-silicon nitride in conjunction with aluminium nitride in conjunction with carbonRefractory material.
Detailed description of the invention
For making those skilled in the art understand better technical scheme of the present invention, knot belowClosing detailed description of the invention is described in further detail the present invention.
Embodiment 1
The present embodiment provides a kind of preparation method of composite refractory cheaply, comprisesFollowing steps:
(1) first the industrial waste ROLLING OIL in aluminium foil thermal rolling production process is filtered and obtainedAluminium powder, then carries out removing a large amount of greasy dirts after conventional centrifugal treating, then puts into high annealingIn stove, 600 DEG C of calcinings 2 hours, vapor away the ROLLING OIL between aluminium powder. Naturally after cooling,The aluminium powder of oven dry is put into ball mill, open vacuum system, be evacuated down to 0.1Pa, closeClose vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 10Pa, continueWhen passing into nitrogen, carry out ball milling, nitrogen flow rate is 50mL/min, and Ball-milling Time 6 is littleTime. The aluminum powder particle size scope obtaining after ball milling is 1～5 μ m. By this step for aluminium foil thermalThe aluminium powder rolling in the ROLLING OIL in generating process has carried out again reclaiming.
Select and comprise that carborundum accounts for that 70wt%, silicon account for 20wt%, ferriferous oxide accounts for 9wt%Crystalline silicon cutting technique in waste material, wherein, the particle diameter of carborundum is 3 μ m, siliconParticle diameter is 6 μ m. The ratio that is 3.5:1 according to the mass ratio of aluminium powder and ferriferous oxide powder (alsoWith this ratio-dependent and take the waste material in crystalline silicon cutting technique), take aluminium powder. PressThe ratio that is 2:1 according to the mass ratio of aluminium powder and carbon dust, takes the carbon that D50 is 200nmPowder. After carbon dust is fully mixed with aluminium powder, allocate in the waste material in crystalline silicon cutting technique,All powders are mixed, obtain comprising silica flour, ferriferous oxide powder, aluminium powder, carbon dustMixture with silicon carbide powder. In mixture, add bonding agent, obtain preparing low one-tenthThe raw material of this composite refractory, fully mix and blend, mixing time is no less than 30min.Above-mentioned raw materials is adopted to high tonnage tablet press machine (as ZP-17 type rotary tablet machine) or itsHis conventional method is compressing, then dries 150 DEG C of bake out temperatures, drying time12 hours, obtain green compact, wherein, bonding agent comprises dextrin, polyethylene glycol and ethanol,Dextrin account for green compact quality 1%, polyethylene glycol account for green compact quality 1%, ethanol accounts for2% of the quality of green compact.
(2) green compact of oven dry are put into nitriding furnace, open vacuum system, continue to take out trueHeating system to 900 DEG C empty time, temperature is evacuated down to 0.01Pa after arriving 900 DEG C,Close vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 10Pa, beatThe air valve that begins to rehearse continues to pass into nitrogen more than 5 minutes, closes liquid passage inlet and outlet,900 DEG C are incubated 3 hours. After waiting for that thermit reaction fully occurs, by temperature from 900 DEG CRise to 1100 DEG C, opening gas circuit import and outlet, pass into nitrogen more than 5 minutes, air pressureTo 10Pa, be incubated 1 hour, when insulation, continue to pass into nitrogen. Wait aluminium powder transformsBecome after aluminium nitride, temperature is risen to 1450 DEG C from 1100 DEG C, be incubated 4 hours sameTime, keep nitrogen to continue to pass into. Naturally cool to after room temperature, obtain compound cheaplyRefractory material, this cheaply composite refractory comprise carborundum phase, ferro-silicon nitride phaseWith aluminium nitride phase, and described carborundum phase, described ferro-silicon nitride phase and described aluminium nitride phaseInterosculate.
In nitridation sintered process, aluminium powder is through the nitridation sintered aluminium nitride that generated; Carbon dustBe iron by the Reduction of Oxide of iron, iron and silica flour are through nitridation sintered generation ferro-silicon nitride;Part silica flour also reacts and has generated carborundum with carbon, meanwhile, and at high temperature, carborundum phase,Ferro-silicon nitride phase is interosculated mutually with aluminium nitride. Wherein, lattice paprmeter, crystal formation, densityEtc. approaching aluminium nitride and carbofrax material, can form SiC-AlN solid solution phase, nitrogenizeThe interpolation of aluminium can make sintering activity, microstructure, the mechanical property and anti-oxidant of materialProperty is all improved largely.
In the present embodiment, the preparation of composite refractory raw material used comprises cheaply:Aluminium in industrial waste ROLLING OIL in aluminium foil thermal rolling production process, crystalline silicon cutting techniqueIn waste material in the oxide of carborundum, silicon and iron, due to above-mentioned aluminium, carborundum andThe oxide of iron all comes from industrial waste, has shortened manufacturing cycle, has realized secondary moneyThe effective and reasonable utilization in source, has reduced the pollution for environment. And due to crystalline silicon cuttingIn technique, along with carborundum, silicon and iron in the waste material that makes to obtain of cutting abrasive materialThe particle diameter of oxide all less, so without they being broken into less particle, fromAnd further reduced the preparation cost of composite refractory, be conducive to industry promote toolThere is the oxide of carborundum, silicon and the iron of little particle diameter to make the raw material of composite refractoryBetween can fully contact, each other disperse more even, make finally to prepareThe composite refractory coming not only cost reduces greatly, and composite refractory is equalEven property, uniformity are good, have improved the performance of material.
Embodiment 2
The present embodiment provides a kind of preparation method of composite refractory cheaply, comprisesFollowing steps:
(1) first the industrial waste ROLLING OIL in aluminium foil thermal rolling production process is filtered and obtainedAluminium powder, then carries out removing a large amount of greasy dirts after conventional centrifugal treating, then puts into high annealingIn stove, 570 DEG C of calcinings 2 hours, vapor away the ROLLING OIL between aluminium powder. Naturally after cooling,The aluminium powder of oven dry is put into ball mill, open vacuum system, be evacuated down to 0.1Pa, closeClose vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 10Pa, continueWhen passing into nitrogen, carry out ball milling, nitrogen flow rate is 75mL/min, and Ball-milling Time 6 is littleTime. The aluminum powder particle size scope obtaining after ball milling is 1～5 μ m.
Select and comprise that carborundum accounts for that 75wt%, silicon account for 12wt%, ferriferous oxide accounts for 10wt%Crystalline silicon cutting technique in waste material, wherein, the particle diameter of carborundum is 5 μ m, siliconParticle diameter is 3 μ m. The ratio that is 5:1 according to the mass ratio of aluminium powder and ferriferous oxide powder (alsoWith this ratio-dependent and take the waste material in crystalline silicon cutting technique), take aluminium powder. PressThe ratio that is 2:1 according to the mass ratio of aluminium powder and carbon dust, takes the carbon that D50 is 300nmPowder. After carbon dust is fully mixed with aluminium powder, allocate in the waste material in crystalline silicon cutting technique,All powders are mixed, obtain comprising silica flour, ferriferous oxide powder, aluminium powder, carbon dustMixture with silicon carbide powder. In mixture, add bonding agent, obtain preparing low one-tenthThe raw material of this composite refractory, fully mix and blend, mixing time is no less than 30min.By above-mentioned raw materials adopt high tonnage tablet press machine or other conventional methods compressing, then enterRow is dried, 150 DEG C of bake out temperatures, and drying time 12 hours, obtains green compact, wherein,Bonding agent comprises dextrin, polyethylene glycol and ethanol, dextrin account for green compact quality 0.5%,Polyethylene glycol account for green compact quality 2%, ethanol account for green compact quality 1.8%.
(2) green compact of oven dry are put into nitriding furnace, open vacuum system, continue to take out trueHeating system to 950 DEG C empty time, temperature is evacuated down to 0.05Pa after arriving 950 DEG C,Close vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 10Pa, beatThe air valve that begins to rehearse continues to pass into nitrogen more than 5 minutes, closes liquid passage inlet and outlet,950 DEG C are incubated 4 hours. After waiting for that thermit reaction fully occurs, by temperature from 950 DEG CRise to 1120 DEG C, opening gas circuit import and outlet, pass into nitrogen more than 6 minutes, air pressureTo 15Pa, be incubated 1.5 hours, when insulation, continue to pass into nitrogen. Wait aluminium powder turnsAfter changing into aluminium nitride, temperature is risen to 1500 DEG C from 1120 DEG C, be incubated 5 hoursMeanwhile, keep nitrogen to continue to pass into. Naturally cool to after room temperature, obtain multiple cheaplyClose refractory material, this cheaply composite refractory comprise carborundum phase, ferro-silicon nitridePhase and aluminium nitride phase, and described carborundum phase, described ferro-silicon nitride phase and described aluminium nitrideInterosculate mutually.
Embodiment 3
The present embodiment provides a kind of preparation method of composite refractory cheaply, comprisesFollowing steps:
(1) first the industrial waste ROLLING OIL in aluminium foil thermal rolling production process is filtered and obtainedAluminium powder, then carries out removing a large amount of greasy dirts after conventional centrifugal treating, then puts into high annealingIn stove, 600 DEG C of calcinings 3 hours, vapor away the ROLLING OIL between aluminium powder. Naturally after cooling,The aluminium powder of oven dry is put into ball mill, open vacuum system, be evacuated down to 0.1Pa, closeClose vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 15Pa, continueWhen passing into nitrogen, carry out ball milling, nitrogen flow rate is 80mL/min, and Ball-milling Time 7 is littleTime. The aluminum powder particle size scope obtaining after ball milling is 1～5 μ m.
Select and comprise that carborundum accounts for that 80wt%, silicon account for 10wt%, ferriferous oxide accounts for 8wt%Crystalline silicon cutting technique in waste material, wherein, the particle diameter of carborundum is 0.5 μ m, siliconParticle diameter be 8 μ m. The ratio that is 4.5:1 according to the mass ratio of aluminium powder and ferriferous oxide powder(and with this ratio-dependent and take the waste material in crystalline silicon cutting technique), takes aluminium powder.The ratio that is 2.2:1 according to the mass ratio of aluminium powder and carbon dust, taking D50 is 400nm'sCarbon dust. After carbon dust is fully mixed with aluminium powder, allocate the waste material in crystalline silicon cutting technique intoIn, all powders are mixed, obtain comprising silica flour, ferriferous oxide powder, aluminium powder,The mixture of carbon dust and silicon carbide powder. In mixture, add bonding agent, preparedThe raw material of composite refractory cheaply, fully mix and blend, mixing time is no less than30min. By above-mentioned raw materials adopt high tonnage tablet press machine or other conventional methods compressing,Then dry, 150 DEG C of bake out temperatures, drying time 12 hours, obtains green compact,Wherein, bonding agent comprises dextrin, polyethylene glycol and ethanol, and dextrin accounts for the quality of green compact0.8%, polyethylene glycol account for green compact quality 1.5%, ethanol account for green compact quality 1.5%.
(2) green compact of oven dry are put into nitriding furnace, open vacuum system, continue to take out trueHeating system to 980 DEG C empty time, temperature is evacuated down to 0.1Pa after arriving 980 DEG C,Close vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 20Pa, beatThe air valve that begins to rehearse continues to pass into nitrogen more than 6 minutes, closes liquid passage inlet and outlet,980 DEG C are incubated 3.5 hours. After waiting for that thermit reaction fully occurs, by temperature from 980DEG C rise to 1150 DEG C, opening gas circuit import and outlet, pass into nitrogen more than 8 minutes, gasBe depressed into 15Pa, be incubated 2 hours, when insulation, continue to pass into nitrogen. Wait aluminium powder turnsAfter changing into aluminium nitride, temperature is risen to 1550 DEG C from 1150 DEG C, be incubated 6 hoursMeanwhile, keep nitrogen to continue to pass into. Naturally cool to after room temperature, obtain multiple cheaplyClose refractory material, this cheaply composite refractory comprise carborundum phase, ferro-silicon nitridePhase and aluminium nitride phase, and described carborundum phase, described ferro-silicon nitride phase and described aluminium nitrideInterosculate mutually.
Embodiment 4
The present embodiment provides a kind of preparation method of composite refractory cheaply, comprisesFollowing steps:
(1) first the industrial waste ROLLING OIL in aluminium foil thermal rolling production process is filtered and obtainedAluminium powder, then carries out removing a large amount of greasy dirts after conventional centrifugal treating, then puts into high annealingIn stove, 620 DEG C of calcinings 3 hours, vapor away the ROLLING OIL between aluminium powder. Naturally after cooling,The aluminium powder of oven dry is put into ball mill, open vacuum system, be evacuated down to 0.1Pa, closeClose vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 20Pa, continueWhen passing into nitrogen, carry out ball milling, nitrogen flow rate is 70mL/min, and Ball-milling Time 7 is littleTime. The aluminum powder particle size scope obtaining after ball milling is 1～5 μ m.
Select and comprise that carborundum accounts for that 80wt%, silicon account for 8wt%, ferriferous oxide accounts for 5wt%'sWaste material in crystalline silicon cutting technique, wherein, the particle diameter of carborundum is 8 μ m, the grain of siliconFootpath is 10 μ m. The ratio that is 4.5:1 according to the mass ratio of aluminium powder and ferriferous oxide powder (alsoWith this ratio-dependent and take the waste material in crystalline silicon cutting technique), take aluminium powder. PressThe ratio that is 2.5:1 according to the mass ratio of aluminium powder and carbon dust, takes the carbon that particle diameter is 200nmPowder. After carbon dust is fully mixed with aluminium powder, allocate in the waste material in crystalline silicon cutting technique,All powders are mixed, obtain comprising silica flour, ferriferous oxide powder, aluminium powder, carbon dustMixture with silicon carbide powder. In mixture, add bonding agent, obtain preparing low one-tenthThe raw material of this composite refractory, fully mix and blend, mixing time is no less than 30min.By above-mentioned raw materials adopt high tonnage tablet press machine or other conventional methods compressing, then enterRow is dried, 150 DEG C of bake out temperatures, and drying time 12 hours, obtains green compact, wherein,Bonding agent comprises dextrin, polyethylene glycol and ethanol, dextrin account for green compact quality 0.6%,Polyethylene glycol account for green compact quality 1.8%, ethanol account for green compact quality 1.6%.
(2) green compact of oven dry are put into nitriding furnace, open vacuum system, continue to take out trueHeating system to 950 DEG C empty time, temperature is evacuated down to 0.03Pa after arriving 950 DEG C,Close vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 15Pa, beatThe air valve that begins to rehearse continues to pass into nitrogen more than 8 minutes, closes liquid passage inlet and outlet,950 DEG C are incubated 3.8 hours. After waiting for that thermit reaction fully occurs, by temperature from 950DEG C rise to 1200 DEG C, opening gas circuit import and outlet, pass into nitrogen more than 8 minutes, gasBe depressed into 10Pa, be incubated 2 hours, when insulation, continue to pass into nitrogen. Wait aluminium powder turnsAfter changing into aluminium nitride, temperature is risen to 1480 DEG C from 1200 DEG C, be incubated 4 hoursMeanwhile, keep nitrogen to continue to pass into. Naturally cool to after room temperature, obtain multiple cheaplyClose refractory material, this cheaply composite refractory comprise carborundum phase, ferro-silicon nitridePhase and aluminium nitride phase, and described carborundum phase, described ferro-silicon nitride phase and described aluminium nitrideInterosculate mutually.
Embodiment 5
The present embodiment provides a kind of preparation method of composite refractory cheaply, comprisesFollowing steps:
(1) first the industrial waste ROLLING OIL in aluminium foil thermal rolling production process is filtered and obtainedAluminium powder, then carries out removing a large amount of greasy dirts after conventional centrifugal treating, then puts into high annealingIn stove, 600 DEG C of calcinings 2.5 hours, vapor away the ROLLING OIL between aluminium powder. Naturally coolingAfter, the aluminium powder of oven dry is put into ball mill, open vacuum system, be evacuated down to 0.1Pa,Close vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 20Pa, holdContinue when passing into nitrogen and carry out ball milling, nitrogen flow rate is 80mL/min, Ball-milling Time 8Hour. The aluminum powder particle size scope obtaining after ball milling is 1～5 μ m.
Select and comprise that carborundum accounts for that 85wt%, silicon account for 7wt%, ferriferous oxide accounts for 7wt%'sWaste material in crystalline silicon cutting technique, wherein, the particle diameter of carborundum is 10 μ m, siliconParticle diameter is 0.5 μ m. The ratio that is 4:1 according to the mass ratio of aluminium powder and ferriferous oxide powder (alsoWith this ratio-dependent and take the waste material in crystalline silicon cutting technique), take aluminium powder. PressThe ratio that is 2.5:1 according to the mass ratio of aluminium powder and carbon dust, takes the carbon that particle diameter is 500nmPowder. After carbon dust is fully mixed with aluminium powder, allocate in the waste material in crystalline silicon cutting technique,All powders are mixed, obtain comprising silica flour, ferriferous oxide powder, aluminium powder, carbon dustMixture with silicon carbide powder. In mixture, add bonding agent, obtain preparing low one-tenthThe raw material of this composite refractory, fully mix and blend, mixing time is no less than 30min.By above-mentioned raw materials adopt high tonnage tablet press machine or other conventional methods compressing, then enterRow is dried, 150 DEG C of bake out temperatures, and drying time 12 hours, obtains green compact, wherein,Bonding agent comprises dextrin, polyethylene glycol and ethanol, dextrin account for green compact quality 0.9%,Polyethylene glycol account for green compact quality 1.2%, ethanol account for green compact quality 1.7%.
(2) green compact of oven dry are put into nitriding furnace, open vacuum system, continue to take out trueHeating system to 1000 DEG C empty time, temperature is evacuated down to 0.08Pa after arriving 1000 DEG C,Close vacuum system. Then pass into high pure nitrogen that purity is greater than 99wt% to 20Pa, beatThe air valve that begins to rehearse continues to pass into nitrogen more than 10 minutes, closes liquid passage inlet and outlet,1000 DEG C are incubated 3 hours. After waiting for that thermit reaction fully occurs, by temperature from 1000DEG C rise to 1150 DEG C, opening gas circuit import and outlet, pass into nitrogen more than 10 minutes, gasBe depressed into 20Pa, be incubated 1 hour, when insulation, continue to pass into nitrogen. Wait aluminium powder turnsAfter changing into aluminium nitride, temperature is risen to 1500 DEG C from 1150 DEG C, be incubated 6 hoursMeanwhile, keep nitrogen to continue to pass into. Naturally cool to after room temperature, obtain multiple cheaplyClose refractory material, this cheaply composite refractory comprise carborundum phase, ferro-silicon nitridePhase and aluminium nitride phase, and described carborundum phase, described ferro-silicon nitride phase and described aluminium nitrideInterosculate mutually.
Be understandable that, above embodiment is only used to illustrate principle of the present inventionAnd the illustrative embodiments adopting, but the present invention is not limited thereto. For abilityThose of ordinary skill in territory, in the situation that does not depart from spirit of the present invention and essenceUnder, can make various modification and improvement, these modification and improvement are also considered as of the present inventionProtection domain.
Claims (10)
1. a preparation method for composite refractory cheaply, is characterized in that, bagDraw together following steps:
(1) raw material that comprises the waste material in carbon, aluminium and crystalline silicon cutting technique is pressed intoGreen compact, wherein, the waste material in described crystalline silicon cutting technique comprises carborundum, silicon, ironOxide, described aluminium is by carrying in the industrial waste ROLLING OIL in aluminium foil thermal rolling production processGet gained;
(2) by nitridation sintered described green compact, obtain composite refractory, this composite fireMaterial comprises carborundum phase, ferro-silicon nitride phase and aluminium nitride phase, and described carborundum phase,Described ferro-silicon nitride phase is interosculated mutually with described aluminium nitride.
2. the preparation side of composite refractory cheaply according to claim 1Method, is characterized in that, in described step (1), the particle diameter of described carbon is 0.2～0.5 μ m,The particle diameter of described aluminium is 1～5 μ m, and the particle diameter of described carborundum is 0.5～10 μ m, described inThe particle diameter of silicon is 0.5～10 μ m.
3. the preparation side of composite refractory cheaply according to claim 1Method, is characterized in that, giving up in the described crystalline silicon cutting technique in described step (1)The mass percentage content of the oxide of carborundum in material, silicon, iron is than being (70～85):(8～20)：(7～10)。
4. the preparation side of composite refractory cheaply according to claim 1Method, is characterized in that, the described aluminium in described step (1) and the mass ratio of described carbon are(2～2.5)：1。
5. the preparation side of composite refractory cheaply according to claim 1Method, is characterized in that, the described aluminium in described step (1) and the oxide of described ironMass ratio is (3.5～5): 1.
6. the preparation side of composite refractory cheaply according to claim 1Method, is characterized in that, described by the industrial waste ROLLING OIL in aluminium foil thermal rolling production processThe method of middle extraction aluminium is specially: by the industrial waste rolling in aluminium foil thermal rolling production processOil filters and obtains leaching thing, and this is leached to thing under inert atmosphere, at 570～620 DEG C,Calcine 2～3 hours, obtain the aluminium of surface without ROLLING OIL.
7. the preparation side of composite refractory cheaply according to claim 1Method, is characterized in that, the preparation process of the described raw material in described step (1) is specially:In the waste material in described crystalline silicon cutting technique, allocate described aluminium and described carbon into, then addBonding agent obtains described raw material.
8. the preparation side of composite refractory cheaply according to claim 7Method, is characterized in that, described bonding agent comprises dextrin, polyethylene glycol and ethanol, described inDextrin account for described green compact quality 0.5～1%, described polyethylene glycol accounts for the matter of described green compactAmount 1～2%, described ethanol account for described green compact quality 1.5～2%.
9. the preparation side of composite refractory cheaply according to claim 1Method, is characterized in that, the nitridation sintered concrete grammar in described step (2) comprise withLower step:
(21) described green compact are put into nitriding furnace;
(22) open vacuum system, heating system to 900 when continuing to vacuumize～1000DEG C, temperature is evacuated down to 0.1～0.01Pa after arriving 900～1000 DEG C, closes vacuum system;
(23) then pass into high pure nitrogen to 10～20Pa that purity is 99wt%;
(24) open drain tap and continue to pass into nitrogen 5～10 minutes, close liquid passage inletAnd outlet;
(25) 900～1000 DEG C of insulations 3～4 hours, carry out thermit reaction;
(26) after waiting for that thermit reaction fully occurs, temperature is risen to from 900～1000 DEG C1100～1200 DEG C, opening gas circuit import and outlet, pass into nitrogen 5～10 minutes, air pressureTo 10～20Pa, be incubated 1～2 hour, when insulation, continue to pass into nitrogen;
(27) after waiting for that aluminium powder changes into aluminium nitride, by temperature from 1100～1200 DEG CRise to 1450～1550 DEG C, when being incubated 4～6 hours, keep nitrogen to continue to pass into;
(28) naturally cool to after room temperature, obtain described composite refractory.
10. a composite refractory cheaply, is characterized in that, it is wanted by rightAsk the method preparation described in 1～9 any one.
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| CN103553647A (en) * | 2013-10-08 | 2014-02-05 | 常州工程职业技术学院 | Method for preparation of silicon nitride bonded silicon carbide refractory material by using silicon cutting waste mortar |
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