CN103130507A - Preparation method of antioxidant carbon block with heat and alkaline etching resistance - Google Patents
Preparation method of antioxidant carbon block with heat and alkaline etching resistance Download PDFInfo
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- CN103130507A CN103130507A CN2012104515582A CN201210451558A CN103130507A CN 103130507 A CN103130507 A CN 103130507A CN 2012104515582 A CN2012104515582 A CN 2012104515582A CN 201210451558 A CN201210451558 A CN 201210451558A CN 103130507 A CN103130507 A CN 103130507A
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Abstract
A preparation of an antioxidant carbon block with heat and alkaline etching resistance belongs to the heat and alkaline etching resistance material field. The preparation of the antioxidant carbon block with heat and alkaline etching resistance is characterized in that the antioxidant carbon block comprises the following raw materials, by mass, 60% to 80% of graphite micro powders, 5% to 20% of silicon powders, 5% to 30% of alumina sol, and 0% to 15% of silicon carbide micro powders, and the antioxidant carbon block is prepared by mixing materials, spray drying, forming, presintering and sintering. Heat and alkaline etching resistant and antioxidant experimental tests show that: carbon block materials of the antioxidant carbon block have alkaline etching resistant service life of 120 to 240 hours and antioxidant service life of 70 to 120 hours under high temperature of 1750 DEG C. Besides, the preparation of the antioxidant carbon block with heat and alkaline etching resistance is simple in process, capable of achieving production of a crucible large in size or furnace liner materials, convenient to apply to industries, and capable of being repeatedly used and lowering production cost.
Description
Technical field
The present invention relates to a kind of charcoal block of material, particularly relate to a kind of high temperature resistant alkaline etching, oxidation resistant charcoal block of material with long service life, be mainly used in crucible or furnace lining block material in melting, slag making, directional freeze and the ingot casting production technique that metallurgy method prepares solar-grade polysilicon.
Background technology
Along with energy dilemma is day by day serious, Sustainable Development and environment amenable novel energy have become the focus that the whole world is concerned about, and sun power has become the emphasis of various countries' new forms of energy development as cleaning, efficient, reproducible novel energy.At present, in all eurypalynous solar cells, polysilicon solar cell is the leading product that move towards application.And that the metallurgy method purifying solar energy level polysilicon has technique is simple, with low cost, and the characteristics that environmental pollution is low have become the main direction of solar-grade polysilicon development.
In metallurgy method purifying solar energy level polysilicon production process, as mine heat furnace smelting, the intermediate frequency furnace slag refining of industrial silicon, directional freeze and ingot casting production technique etc. all will use a large amount of crucibles or furnace lining material.Due to erosion and the high temperature oxidation of following the high-temperature fusion alkaline residue to crucible or furnace lining in the production of polysilicon technological process, generally the life-span of crucible or furnace lining longer, production cost is lower.At present, the crucible material that uses in directional freeze and ingot casting process is quartz-ceramics, and the mine heat furnace smelting of industrial silicon adopts charcoal element furnace lining, and intermediate frequency slag refining etc. adopt graphite material.
The quartz ceramic crucible main component is SiO
2, SiO in use
2Silicon easy and molten state reacts, and causes sticking crucible phenomenon, can cause that even crucible breaks; Often adopt when directional freeze and ingot casting to quartz crucible or ceramic crucible inwall and apply the high-purity Si of one deck
3N
4Coating directly contacts with crucible with the silicon that intercepts molten state.Publication number is to disclose a kind of surface in the patent application of CN101892517 A to be covered with SiO
2The Si of coated
3N
4The slurry of powder with bonding force and the resistance of oxidation of enhancing coating and crucible, but is difficult to reach the coating homogenizing, and is unfavorable for large-scale production in the brushing process.Patent application publication number is that CN102503545 A, CN101508590 A and CN102225837 A adopt the method for spraying to realize Si
3N
4The large-area applications of coating has reduced cost, but the coating of spraying is often excessively thin, the liquid of anti-silicon wash away ability.If spray blocked up, with crucible base in conjunction with bad, easy early fallout.The coating technology of quartz ceramic crucible can only solve silicon liquid and SiO
2The pyroreaction problem, and can not solve reusing of crucible.Cause the crucible cracking because quartz crucible in process of cooling, undergoes phase transition when 1250 ℃ of left and right, can't reuse; And the life-time service temperature can not satisfy the crucible of slag refining or the use temperature of furnace lining material and require (more than 1700 ℃) lower than 1500 ℃.Obviously, ceramic quartz crucible can not be used for the scale operation of metallurgy method directional freeze and slag refining.
Carbon Materials is to satisfy the main candidate material that the polysilicon pyrotic smelting is purified, and has been widely used in mine heat furnace smelting and slag refining at present except the purification production of boron.In slagging process, the basicity of slag agent adds CaO, Na usually on except effect of boron, direct impact being arranged in production technique
2The basic oxide such as O and BaO are to improve the basicity of slag liquid.Although graphite has the effect of good high temperature resistance alkaline etching, oxidation-resistance property is very poor, and has relatively high cost.The cost of carbon material is relatively low, and graphite has oxidation-resistance preferably relatively, but under high temperature, melting alkali lye has strong corrosive nature to crucible or furnace lining, and the fluorochemical in slag former such as NaF, CaF
2Can strengthen slag agent and silicon liquid to the infiltration of charcoal element crucible with LiF, the phenomenon that silicon can occur leaking when serious affects its work-ing life.
At present, the Study of Antioxidation of Carbon Materials mainly concentrates on the surface oxidation-resistant of material, pass through respectively entrapping method as patent application publication number CN102503518 A, CN102432345 A and CN102515850 A, the compound coating that chemical Vapor deposition process and hot pressing sintering method prepare a kind of high-temperature oxidation resistant is coated on the surface of carbon material, and this compound coating is the refractory oxide ceramic coating of one deck densification.Because thermal expansivity and the carbon of SiC are close, therefore, all adopt SiC as bottom debanding charcoal element matrix and the outer coating of compound coating, although this compound coating and matrix have good keying action, also has simultaneously good high-temperature oxidation resistance, but the single SiC layer in compound coating has more defective, as crackle and hole, is difficult to play and is combined preferably with matrix for a long time; In addition, outer field oxide ceramic coating has higher thermal expansivity, easily produces penetrating crack, when comparatively serious, obscission can occur.Patent application publication number CN1762904 A and CN1762905 A adopt the slurry spread coating to prepare oxidation resistant coating; Publication number CN102167623 A adopts original position to generate SiC whisker layer connection matrix and coating, strengthens the keying action of coating and matrix; And publication number CN1235941 A, under vacuum condition, adopt SiO steam to carry out the high temperature siliconizing as silicided source, obtain the SiC oxidation resistant coating.Although the application of coating has solved the carbon material high-temperature oxidation resistance, has reduced cost, is convenient to production operation, the work-ing life of coating is short, can't reuse.
Summary of the invention
The crucible of the use in the large-scale production process of metallurgy method directional freeze and slag refining or furnace lining carbon material require to have the anti-melting alkali lye of good high temperature erosion property, high-temperature oxidation resistance, realize reusing, thus the manufacturing cost of reduction polysilicon.Therefore, solve the anti-oxidant problem of carbon material from matrix, be only effective fundamental way.Solution is exactly the Composition Design that carries out material, introduces oxidation resistant component phase in matrix, then passes through special mixing and molding and firing processes technique, to obtain required material.Carbon dust forms the oxidation barrier layer with anti-oxidant the coating each other after evenly mixing mutually, or oxidation forms fine and close oxide film and stops further oxidation.High-purity silicon powder is effective antioxidant composition, forms silicon-dioxide with the oxygen effect under high temperature, and softening silicon dioxide film evenly is coated on the surface of charcoal particle, has effectively stoped the oxidation of charcoal.Carborundum powder has good antioxidant property equally, and carbon and element silicon form extremely strong covalent linkage on the one hand, itself have oxidation-resistance preferably; Under high temperature, oxygen is combined with silicon and is formed the compact silicon dioxide film on the other hand, can effectively stop the diffusion of oxygen.Aluminum oxide is dystectic oxide compound, and its fusing point is 2050 ℃, can improve the resistance to elevated temperatures of matrix.The present invention solves the erosion of high temperature alkali resistant, the resistance to high temperature oxidation problem of charcoal block of material from matrix, will provide a kind of metallurgy method that is applicable to prepare polysilicon at crucible or the furnace lining material of melting, directional freeze, ingot casting and slag refining purifying technique.
Purpose of the present invention can not fundamentally solve oxidation resistant problem for carbon material surface oxidation-resistant in prior art exactly, provide a kind of metallurgy method that is applicable to prepare polysilicon at the crucible of melting, directional freeze, ingot casting and slag refining purifying technique or the oxidation-resistance material of furnace lining, this material has high temperature resistant alkaline etching, resistance to high temperature oxidation and nonexpondable advantage; Foreign matter content is low simultaneously, can be on the mass formation impact of polysilicon.
High temperature resistant alkaline etching of the present invention, oxidation-resistance charcoal block of material, this charcoal piece material of main part composition (mass percent) is graphite microparticles 60-80%, silica flour 5-20%; Alumina sol 5-30% and silicon carbide micro-powder 0-15%.
Under hot conditions, silica flour preferential oxidation in the charcoal piece, the SiO of generation glassy phase
2, and then the oxide film of formation one deck densification is coated on the surface of carbon, the oxidation of inhibition carbon; And the part silica flour can also generate SiC with carbon reaction, and SiC itself has good antioxidant property, and under high temperature, oxygen is combined formation compact silicon dioxide film with silicon, can effectively stop the diffusion of oxygen.Corrosion-resistant, high temperature resistant, the characteristics such as intensity is high, good heat conductivity, strong shock resistance that additive SiC also has, so SiC has improved the caustic corrosion resistance of charcoal piece, the ability of washing away of the liquid of anti-the molten silicon greatly.
Crystal formation occurs and is finally converted into stable α-Al in heat-processed in alumina sol
2O
3Thereby, the high-temperature oxidation resistance of raising charcoal piece.Wherein, alumina sol is selected AlCl
3Be presoma, the precursor aluminum oxide refers to obtain the raw material in a kind of early stage of alumina powder, and major ingredient is aluminium hydroxide, and at high temperature calcining can obtain highly active aluminum oxide, is suitable for sintering aid.
Under the condition of heating in water bath, successively obtain by hydrolysis, acidolysis.
AlCl
3Be hydrolyzed under alkaline condition:
AlCl
3+3NH
3·H
2O→Al(OH)
3↓+3NH
4Cl
Al(OH)
3→AlOOH+H
2O
Catenulate (AlOOH) given birth in AlOOH dehydration polycondensation under acidic conditions
2(m+n) H
2O
In heat-processed:
A kind of high temperature resistant alkaline etching of the present invention, oxidation resistant charcoal block of material, its preparation process comprises the following steps:
1. the preparation of charcoal block of material
(1) preparation of alumina sol: liquor alumini chloridi is adopted heating in water bath to 80 ℃, then drip ammoniacal liquor to it, drip endpoint pH and be controlled at 7.0 ~ 9.5, generate until no longer include white precipitate; Then continue to drip peptizing agent and carry out acidolysis, drip endpoint pH and be controlled at 3.0 ~ 6.0; Hydrolysis and acidolysis process keep stirring, churning time 2h ~ 24h, the colloidal sol that obtains having certain viscosity;
(2) batch mixing: in charcoal piece material of main part ratio, graphite microparticles, silica flour and silicon carbide micro-powder are mixed, then add alumina sol, adopt the mode of planetary ball mill or mechanical kneading to mix, the slurry that obtains being evenly distributed;
(3) drying: adopt the centrifugal spraying mode to carry out drying, obtain having the powder that particle size distribution range is narrow, balling ratio is high, mobility of particle is good;
(4) forming of green body: adopt vibratory compaction or cold isostatic compaction, the rubber diaphragm tool that said cold isostatic compaction will be filled powder is placed in airtight container, apply each to equal pressure by oil pump, under the effect of high pressure, make the moulding process of fine and close base substrate;
(5) presintering: the green compact after toasting slowly heat up and are heated to 500-900 ℃, and insulation 2-10h obtains biscuit;
(6) sintering: biscuit is heated to 1400-1600 ℃, and insulation 2-10h is cooled to room temperature, and sintering process is to pass into simultaneously under the hydrogen condition at the carbon dust covering protection to carry out;
(7) the charcoal piece after sintering is carried out the measurement of density, apparent porosity, ultimate compression strength and bending strength;
In step (1), presoma aluminum chloride content 5% ~ 30%, water-content 90% ~ 65%, ammoniacal liquor content 1% ~ 5%.Peptizing agent (nitric acid, hydrochloric acid, glacial acetic acid) content 1% ~ 5%; Hydrolysis temperature all is controlled at 50 ℃ ~ 90 ℃; Hydrolysis time 1h ~ 24h; 50 ~ 80 ℃ of gelatinization temperatures, gelation time 2h ~ 24h.Wherein, aluminum chloride, ammoniacal liquor, nitric acid, hydrochloric acid and glacial acetic acid all adopt analytical pure; The median size of aluminum chloride is 75 μ m; The massfraction 2% ~ 10% of ammoniacal liquor; The massfraction 25% ~ 50% of acetic acid, the massfraction 10% ~ 30% of hydrochloric acid, the massfraction of nitric acid is 20% ~ 60%.
In step (2), graphite microparticles is selected high purity graphite, and the Si powder can select metallurgical grade silicon purity at 98%-99% silicon raw material; Silicon carbide purity is also more than 99%; Graphite microparticles, Si powder, silicon carbide micro-powder granularity are about 75 μ m.When adopting planetary ball mill to mix, rotating speed: 500r/min; Time: 0.5-2h.When adopting mechanical kneading, power: 15KW; Time: 1-2h.
In step (3), when the centrifugal spraying mode is carried out drying, slurry solid content (massfraction) 30-70%; Fog-spray nozzle rotating speed: 10000---12500r/min; Hot-wind inlet temperature: 200-220 ℃; Hot-blast outlet temperature: 100-120 ℃; Peristaltic pump speed: 100---150rpm; Negative pressure :-350Pa in tower.
In step (4), when adopting vibratory compaction, exciting force: 6500-6900N; Time of vibration: 2-10min; Vibrational frequency: 20-35HZ; Peak swing: 2-3mm.When adopting isostatic cool pressing, operating pressure: 300-400MPa; Dwell time: 2-10min.
In step (7), the charcoal piece density after sintering: 1.6-2.0g/cm
3Apparent porosity: 5-12%; Ultimate compression strength: 30-50MPa; Bending strength: 5-20MPa.
2. high temperature alkali resistant erosion experiment
(1) sample with above-mentioned charcoal piece intercepting certain size is placed in the high-strength graphite crucible, the then slag agent that mixed of landfill; 1750 ℃ of experimental temperatures, insulation 1--50h.
(2) after experiment finishes, knock out the residual slag agent of sample surfaces part, pattern and erosion rate of weight loss before and after comparative sample; The mensuration of ultimate compression strength and bending strength; And the calculating in reduction and work-ing life.
In step (1), what select is that the basic slag agent is a kind of in calcium system or sodium system, and calcium is that the slag agent is: CaO-SiO
2-CaF
2, wherein the shared mass percent of each component is: CaO, 40-60%; SiO
2, 50-30%; CaF
2, 10%.Sodium is that slag system is: Na
2CO
3/ NaHCO
3-SiO
2-NaF, wherein the shared mass percent of each component is: Na
2CO
3/ NaHCO
3, 40-60%; SiO
2, 50-30%; NaF, 10%.Above slag agent is analytical pure, each slag agent consumption 200g.Specimen size: 50mm * 30mm * 20mm; High-strength graphite crucible size: external diameter, 120mm; Internal diameter: 100mm; Height, 100mm.Experimentation is to carry out in medium-frequency induction furnace, and under vacuum or protective atmosphere condition.
In step (2), after high temperature alkali resistant erosion experiment, charcoal piece provided by the invention has obvious dry slag phenomenon; Profile is complete, and corner angle are clearly demarcated, the obvious attenuate of thickness; The vestige that obvious erosion is arranged, erosion rate of weight loss are 0-30%; Ultimate compression strength: 0-30MPa; Bending strength: 0-15MPa; Reduction: 0.04-0.08mm/h; Work-ing life: 120-240h.
3. high-temperature oxidation resistance experiment
(1) sample with above-mentioned charcoal piece intercepting certain size is placed in corundum crucible, 1750 ℃ of experimental temperatures, insulation 1-50h.Specimen size: 50mm * 30mm * 20mm; Corundum crucible size: external diameter, 120mm; Internal diameter: 100mm; Height, 100mm.
(2) after experiment finishes, pattern and oxidative mass loss before and after comparative sample; The mensuration of ultimate compression strength and bending strength; And the calculating in reduction and work-ing life.
In step (1), experimentation is to carry out in medium-frequency induction furnace, and is exposed in air.
In step (2), there is obvious oxidation on the charcoal piece surface after oxidation-resistance experiment finishes, the obvious attenuation of thickness, and the phenomenon that has powder to come off when touching; Mass loss: 0-50%; Residual ultimate compression strength: 0-30MPa; Residual bending strength: 0-10MPa; Reduction: 0.08-0.15mm/h; Work-ing life: 70-120h.
The advantage of high temperature resistant alkaline etching provided by the invention, anti-oxidation carbon piece is:
(1) the present invention is take the material composition design theory as guidance, by adding silica flour, silicon carbide micro-powder, alumina sol, high temperature resistant, caustic corrosion resistance, the antioxidant property of carbon material matrix have been improved, and utilize centrifugal spray drying and isostatic cool pressing technology, successful realization pressureless sintering, obtain high densification, high-intensity charcoal piece.
(2) charcoal piece of the present invention can be applied to crucible or the furnace lining block material in melting, slag making, directional freeze and the ingot casting production technique of polysilicon, can be widely used in metallurgical industry and association area thereof.
(3) preparation technology of the present invention is simple, can realize the production of large size crucible or furnace lining, is convenient to industrial applications, and Reusability repeatedly, has reduced production cost.
Embodiment
Embodiment 1
Get aluminum chloride 150g, the massfraction of ammoniacal liquor 100ml(ammoniacal liquor is 5%), distilled water 750g.Aluminum chloride is added in distilled water, and heating in water bath to 80 ℃ drips ammoniacal liquor and stirs, and the massfraction that drips glacial acetic acid 50ml(glacial acetic acid after being hydrolyzed 2h is 40%), continue insulated and stirred 6h, obtain solid content and be 15% alumina sol.
Take high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Ratio in high purity graphite micro mist 80%, silica flour 5%, alumina sol 10% and silicon carbide micro-powder 5% takes 5Kg, according to the processing parameter of batch mixing, drying, forming of green body, presintering, sintering circuit, obtains required charcoal piece.The performance test results is as shown in example in table 11.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high temperature anti-slag erosion experiment, slag agent: CaO, 60%; SiO
2, 30%; CaF
2, 10%.1750 ℃ of experimental temperatures, insulation 20-h.The performance test results is as shown in example in table 21.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high-temperature oxidation resistant experiment, 1750 ℃ of experimental temperatures, insulation 10h.The performance test results is as shown in example in table 31.
Embodiment 2
Get aluminum chloride 200g, the massfraction of ammoniacal liquor 150ml(ammoniacal liquor is 5%), distilled water 650g.Aluminum chloride is added in distilled water, and heating in water bath to 75 ℃ drips ammoniacal liquor and stirs, and the massfraction that drips hydrochloric acid 75ml(hydrochloric acid after being hydrolyzed 2h is 25%), continue insulated and stirred 10h, obtain solid content and be 20% alumina sol.
Take high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Ratio in high purity graphite micro mist 70%, silica flour 10%, alumina sol 10% and silicon carbide micro-powder 10% takes 5Kg, according to aforesaid processing parameter, carries out successively batch mixing, drying, moulding, presintering, sintering and obtains required charcoal piece.The performance test results is as shown in example in table 12.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high temperature anti-slag erosion experiment, slag agent: CaO, 40%; SiO
2, 50%; CaF
2, 10%.1750 ℃ of experimental temperatures, insulation 40-h.The performance test results is as shown in example in table 22.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high-temperature oxidation resistant experiment, 1750 ℃ of experimental temperatures, insulation 15h.The performance test results is as shown in example in table 32.
Embodiment 3
Get aluminum chloride 250g, the massfraction of ammoniacal liquor 200ml(ammoniacal liquor is 5%), distilled water 550g.Aluminum chloride is added in distilled water, and heating in water bath to 85 ℃ drips ammoniacal liquor and stirs, and the massfraction that drips nitric acid 100ml(nitric acid after being hydrolyzed 2h is 20%), continue insulated and stirred 20h, obtain solid content and be 25% alumina sol.
Take high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Ratio in high purity graphite micro mist 60%, silica flour 10%, alumina sol 20% and silicon carbide micro-powder 10% takes 5Kg, according to aforesaid processing parameter, carries out successively batch mixing, drying, moulding, presintering, sintering and obtains required charcoal piece.The performance test results is as shown in example in table 13.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high temperature anti-slag erosion experiment, slag agent: NaCO
3, 60%; SiO
2, 30%; NaF, 10%.1750 ℃ of experimental temperatures, insulation 20h.The performance test results is as shown in example in table 23.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high-temperature oxidation resistant experiment, 1750 ℃ of experimental temperatures, insulation 20h.The performance test results is as shown in example in table 33.
Embodiment 4
Get aluminum chloride 150g, the massfraction of ammoniacal liquor 100ml(ammoniacal liquor is 5%), distilled water 750g.Aluminum chloride is added in distilled water, and heating in water bath to 80 ℃ drips ammoniacal liquor and stirs, and the massfraction that drips glacial acetic acid 50ml(glacial acetic acid after being hydrolyzed 2h is 40%), continue insulated and stirred 6h, obtain solid content and be 15% alumina sol.
Take high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Ratio in high purity graphite micro mist 80%, silica flour 5%, alumina sol 10% and silicon carbide micro-powder 5% takes 5Kg, according to aforesaid processing parameter, carries out successively batch mixing, drying, moulding, presintering, sintering and obtains required charcoal piece.The performance test results is as shown in example in table 14.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high temperature anti-slag erosion experiment, slag agent: NaCO
3, 40%; SiO
2, 50%; NaF, 10%.1750 ℃ of experimental temperatures, insulation 40-h.The performance test results is as shown in example in table 24.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high-temperature oxidation resistant experiment, 1750 ℃ of experimental temperatures, insulation 20-h.The performance test results is as shown in example in table 34.
Embodiment 5
Get aluminum chloride 200g, the massfraction of ammoniacal liquor 150ml(ammoniacal liquor is 5%), distilled water 650g.Aluminum chloride is added in distilled water, and heating in water bath to 75 ℃ drips ammoniacal liquor and stirs, and the massfraction that drips hydrochloric acid 75ml(hydrochloric acid after being hydrolyzed 2h is 25%), continue insulated and stirred 10h, obtain solid content and be 20% alumina sol.
Take high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Ratio in high purity graphite micro mist 70%, silica flour 10%, alumina sol 10% and silicon carbide micro-powder 10% takes 5Kg, according to aforesaid processing parameter, carries out successively batch mixing, drying, moulding, presintering, sintering and obtains required charcoal piece.The performance test results is as shown in example in table 25.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high temperature anti-slag erosion experiment, slag agent: NaHCO
3, 60%; SiO
2, 30%; NaF, 10%.1750 ℃ of experimental temperatures, insulation 20h.The performance test results is as shown in example in table 35.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high-temperature oxidation resistant experiment, 1750 ℃ of experimental temperatures, insulation 30h.The performance test results is as shown in example in table 15.
Embodiment 6
Get aluminum chloride 250g, the massfraction of ammoniacal liquor 200ml(ammoniacal liquor is 5%), distilled water 550g.Aluminum chloride is added in distilled water, and heating in water bath to 85 ℃ drips ammoniacal liquor and stirs, and the massfraction that drips nitric acid 100ml(nitric acid after being hydrolyzed 2h is 20%), continue insulated and stirred 20h, obtain solid content and be 25% alumina sol.
Take high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Ratio in high purity graphite micro mist 60%, silica flour 10%, alumina sol 20% and silicon carbide micro-powder 10% takes 5Kg, according to aforesaid processing parameter, carries out successively batch mixing, drying, moulding, presintering, sintering and obtains required charcoal piece.The performance test results is as shown in example in table 16.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high temperature anti-slag erosion experiment, slag agent: NaHCO
3, 40%; SiO
2, 50%; NaF, 10%.1750 ℃ of experimental temperatures, insulation 40h.The performance test results is as shown in example in table 26.
The charcoal piece that intercepting is of a size of 50mm * 30mm * 20mm carries out the high-temperature oxidation resistant experiment, 1750 ℃ of experimental temperatures, insulation 40h.The performance test results is as shown in example in table 36.
The subordinate list explanation
Table 1 is the physicals after charcoal piece sintering of the present invention
Table 2 is the physicals after charcoal piece high temperature anti-slag erosion experiment of the present invention
Table 3 is the physicals after charcoal piece high-temperature oxidation resistant experiment of the present invention
Physicals after table 1 charcoal piece of the present invention sintering
Physicals after table 2 charcoal piece of the present invention high temperature anti-slag erosion experiment
(table is annotated: reduction is the thickness of attenuate in the unit time; When thickness reduces to a half, stop using; Work-ing life=0.5 * thickness/reduction)
Physicals after the experiment of table 3 charcoal piece of the present invention high-temperature oxidation resistant
(table is annotated: reduction is the thickness of attenuate in the unit time; When thickness reduces to a half, stop using; Work-ing life=0.5 * thickness/reduction)
Claims (8)
1. the preparation method of a high temperature resistant alkaline etching, anti-oxidation carbon piece, is characterized in that this charcoal piece material of main part composition (mass percent) is graphite microparticles 60-80%, silica flour 5-20%; Alumina sol 5-30% and silicon carbide micro-powder 0-15%.
2. the preparation method of a high temperature resistant alkaline etching, anti-oxidation carbon piece, is characterized in that this preparation method comprises the steps:
(1) preparation of alumina sol: liquor alumini chloridi is adopted heating in water bath to 80 ℃, then drip ammoniacal liquor to it, drip endpoint pH and be controlled at 7.0 ~ 9.5, white precipitate to be no longer included generates; Then continue to drip peptizing agent and carry out acidolysis, drip endpoint pH and be controlled at 3.0 ~ 6.0; Hydrolysis and acidolysis process all ceaselessly stir, churning time 2h ~ 24h, the colloidal sol that obtains having certain viscosity;
(2) batch mixing: in proportion graphite microparticles, silica flour and silicon carbide micro-powder are mixed, then add alumina sol, adopt the mode of planetary ball mill or mechanical kneading to mix, the slurry that obtains being evenly distributed;
(3) drying: adopt the centrifugal spraying mode to carry out drying;
(4) forming of green body: adopt vibratory compaction or cold isostatic compaction;
(5) presintering: the green compact after toasting slowly heat up and are heated to 500-900 ℃, and insulation 2-10h obtains biscuit;
(6) sintering: biscuit is heated to 1400-1600 ℃, insulation 2-10h, room temperature when being cooled to, sintering process are to pass into simultaneously under the hydrogen condition at the carbon dust covering protection to carry out.
3. the preparation method of according to claim 1 with 2 described a kind of high temperature resistant alkaline etchings, anti-oxidation carbon piece, it is characterized by in step (1): presoma aluminum chloride content 5% ~ 30%, water-content 90% ~ 65%, ammoniacal liquor content 1% ~ 5%, peptizing agent (composition is nitric acid, hydrochloric acid, glacial acetic acid) content 1% ~ 5%; Hydrolysis temperature is controlled at 50 ℃ ~ 90 ℃; Hydrolysis time 1h ~ 24h; 50 ~ 80 ℃ of gelatinization temperatures, gelation time 2h ~ 24h, wherein, aluminum chloride, ammoniacal liquor, nitric acid, hydrochloric acid and glacial acetic acid all adopt analytical pure; The median size of aluminum chloride is 75 μ m; The massfraction 2% ~ 10% of ammoniacal liquor; The massfraction 25% ~ 50% of acetic acid, the massfraction 10% ~ 30% of hydrochloric acid, the massfraction of nitric acid is 20% ~ 60%.
4. the preparation method of according to claim 1 with 2 described a kind of high temperature resistant alkaline etchings, anti-oxidation carbon piece, it is characterized in that in step (2): graphite microparticles is selected high purity graphite, and the Si powder can select metallurgical grade silicon purity at 98%-99% silicon raw material; Silicon carbide purity is also more than 99%; Graphite microparticles, Si powder, silicon carbide micro-powder granularity are about 75 μ m.
5. the preparation method of according to claim 1 with 2 described a kind of high temperature resistant alkaline etchings, anti-oxidation carbon piece is characterized in that in step (2): when adopting planetary ball mill to mix, and mechanical separator speed: 500r/min; Time: 0.5-2h; When adopting mechanical kneading, power: 15KW; Time: 1-2h.
6. the preparation method of according to claim 1 with 2 described a kind of high temperature resistant alkaline etchings, anti-oxidation carbon piece is characterized in that in step (3): when adopting the centrifugal spraying mode to carry out drying, and slurry solid content (massfraction) 30-70%; Fog-spray nozzle rotating speed: 10000---12500r/min; Hot-wind inlet temperature: 200-220 ℃; Hot-blast outlet temperature: 100-120 ℃; Peristaltic pump speed: 100---150rpm; Negative pressure :-350Pa in tower.
7. the preparation method of according to claim 1 with 2 described a kind of high temperature resistant alkaline etchings, anti-oxidation carbon piece is characterized in that: in step (4), and when adopting vibratory compaction, exciting force: 6500-6900N; Time of vibration: 2-10min; Vibrational frequency: 20-35HZ; Peak swing: 2-3mm, when adopting isostatic cool pressing, operating pressure: 300-400MPa; Dwell time: 2-10min.
8. the preparation method of according to claim 1 with 2 described a kind of high temperature resistant alkaline etchings, anti-oxidation carbon piece, is characterized in that: in step (7): the charcoal piece density after sintering: 1.6-2.0g/cm
3Apparent porosity: 5-12%; Ultimate compression strength: 30-50MPa; Bending strength: 5-20MPa.
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CN103553664A (en) * | 2013-10-23 | 2014-02-05 | 上海科盛陶瓷有限公司 | Manufacturing method of composite ceramic graphite crucible special for tin melting |
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CN104591771A (en) * | 2015-01-03 | 2015-05-06 | 南通扬子碳素股份有限公司 | Surface modification method for graphite electrode |
CN105036801A (en) * | 2015-07-17 | 2015-11-11 | 常州大学 | Carbon/carbon composite material surface high temperature oxidation resistant coating and preparation method thereof |
CN107917855A (en) * | 2017-11-29 | 2018-04-17 | 辽宁科技大学 | A kind of method and device for detecting iron-containing charge integral high temperature metallurgical performance |
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