CN103130507B - 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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- CN103130507B CN103130507B CN201210451558.2A CN201210451558A CN103130507B CN 103130507 B CN103130507 B CN 103130507B CN 201210451558 A CN201210451558 A CN 201210451558A CN 103130507 B CN103130507 B CN 103130507B
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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, the oxidation resistant charcoal block of material with long service life, be mainly used in metallurgy method and prepare crucible or the furnace lining block material in the melting of solar-grade polysilicon, slag making, directional freeze and ingot casting production technique.
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 clean, efficient, reproducible novel energy.At present, in all eurypalynous solar cells, polysilicon solar cell is the leading product that move towards application.And that metallurgy method purifying solar energy level polysilicon has technique is simple, with low cost, the feature that environmental pollution is low, has become the main direction of solar-grade polysilicon development.
In metallurgy method purifying solar energy level polysilicon production process, as the mine heat furnace smelting of industrial silicon, intermediate frequency furnace slag refining, 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 high-temperature fusion alkaline residue to crucible or furnace lining in production of polysilicon technological process, under normal circumstances the life-span of crucible or furnace lining longer, production cost is lower.At present, the crucible material using 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.
Quartz ceramic crucible main component is SiO
2, in use SiO
2silicon easy and molten state reacts, and causes sticky crucible phenomenon, even can cause that crucible breaks; In the time of directional freeze and ingot casting, often adopt 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 in the patent application of CN101892517 A, to disclose a kind of surface to be covered with SiO
2the Si of coated
3n
4the slurry of powder, to strengthen bonding force and the resistance of oxidation of coating and crucible, but is difficult to reach coating homogenizing, and is unfavorable for large-scale production in 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 resistance to silicon wash away ability.If spray blocked up, bad with the combination of crucible base, easily early fallout.The coating technology of quartz ceramic crucible can only solve silicon liquid and SiO
2pyroreaction problem, and can not solve reusing of crucible.Cause crucible cracking because quartz crucible, in process of cooling, undergoes phase transition in the time of 1250 DEG C of left and right, cannot reuse; And life-time service temperature, lower than 1500 DEG C, can not meet the crucible of slag refining or the use temperature of furnace lining material and require (more than 1700 DEG C).Obviously, ceramic quartz crucible can not be used for the scale operation of metallurgy method directional freeze and slag refining.
Carbon Materials is to meet the main candidate material that polysilicon pyrotic smelting is purified, and has been widely used in the purification production except boron of mine heat furnace smelting and slag refining at present.In slagging process, the basicity of slag agent, on having direct impact except effect of boron, adds CaO, Na conventionally 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 relatively graphite has good oxidation-resistance, but under high temperature, melting alkali lye has strong corrosive nature to crucible or furnace lining, and fluorochemical in slag former is as NaF, CaF
2can strengthen slag agent and the infiltration of silicon liquid to charcoal element crucible with LiF, when serious, there will be the phenomenon of leaking silicon, affect its work-ing life.
At present, the Study of Antioxidation of Carbon Materials mainly concentrates on the surface oxidation-resistant of material, as patent application publication number CN102503518 A, CN102432345 A and CN102515850 A pass through respectively entrapping method, the compound coating that chemical Vapor deposition process and hot pressing sintering method are prepared 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 bottom debanding charcoal element matrix and the outer coating of SiC as compound coating, although this compound coating and matrix have good keying action, also has good high-temperature oxidation resistance simultaneously, but the single SiC layer in compound coating has more defect, as crackle and hole, be difficult to play long-time and the good combination of matrix; 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 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 high temperature siliconizing as silicided source, obtain SiC oxidation resistant coating.Although the application of coating has solved carbon material high-temperature oxidation resistance, has reduced cost, is convenient to production operation, the work-ing life of coating is short, cannot 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, and realization is reused, thereby reduce the manufacturing cost of 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 is evenly coated formation oxidation barrier layer after mixing mutually each other with anti-oxidant, or the fine and close further oxidation of oxide film prevention of oxidation formation.High-purity silicon powder is effective antioxidant composition, under high temperature, forms silicon-dioxide with oxygen effect, and softening silicon dioxide film is evenly 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 good oxidation-resistance; Under high temperature, oxygen is combined with silicon and is formed 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 DEG C, can improve the resistance to elevated temperatures of matrix.The high temperature alkali resistant that the present invention solves charcoal block of material from matrix loses, resistance to high temperature oxidation problem, will provide a kind of metallurgy method that is applicable to prepare crucible or the furnace lining material of polysilicon at melting, directional freeze, ingot casting and slag refining purifying technique.
Object 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 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 part silica flour can also react with carbon and generate SiC, 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 feature such as intensity is high, good heat conductivity, strong shock resistance that additive SiC also has, therefore SiC has improved the caustic corrosion resistance of charcoal piece, the ability of washing away of the liquid of resistance to molten silicon greatly.
In heat-processed, there is crystal formation and be finally converted into stable α-Al in alumina sol
2o
3thereby, the high-temperature oxidation resistance of raising charcoal piece.Wherein, alumina sol is selected AlCl
3for presoma, precursor aluminum oxide refers to a kind of raw material in earlier stage that obtains 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
3under alkaline condition, be hydrolyzed:
AlCl
3+3NH
3·H
2O→Al(OH)
3↓+3NH
4Cl
Al(OH)
3→AlOOH+H
2O
AlOOH is dehydration polycondensation raw catenulate (AlOOH) under acidic conditions
2(m+n) H
2o
In heat-processed:
(AlOOH)
2·(m+n)H
2O
AlOOH(boehmite)
γ-Al
2O
3 δ- Al
2O
3 θ-Al
2O
3 α-Al
2O
3
Alkaline etching that one of the present invention is high temperature resistant, 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 to heating in water bath to 80 DEG C, 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, and churning time 2h ~ 24h obtains having the colloidal sol of 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) dry: to adopt centrifugal spraying mode to be dried, obtain thering is 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, said cold isostatic compaction is placed into the rubber diaphragm tool of filling powder in airtight container, apply respectively 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 baking are slowly heated up and are heated to 500-900 DEG C, and insulation 2-10h, obtains biscuit;
(6) sintering: biscuit is heated to 1400-1600 DEG C, and insulation 2-10h, is cooled to room temperature, and sintering process is to pass under hydrogen condition simultaneously and carry out at carbon dust covering protection;
(7) the charcoal piece after sintering is carried out to 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 is all controlled at 50 DEG C ~ 90 DEG C; Hydrolysis time 1h ~ 24h; 50 ~ 80 DEG C 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 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 in 75 μ m left and right.While adopting planetary ball mill to mix, rotating speed: 500r/min; Time: 0.5-2h.While adopting mechanical kneading, power: 15KW; Time: 1-2h.
In step (3), when centrifugal spraying mode is dried, slurry solid content (massfraction) 30-70%; Fog-spray nozzle rotating speed: 10000---12500r/min; Hot-wind inlet temperature: 200-220 DEG C; Hot-blast outlet temperature: 100-120 DEG C; Peristaltic pump speed: 100---150rpm; Negative pressure :-350Pa in tower.
In step (4), while adopting vibratory compaction, exciting force: 6500-6900N; Time of vibration: 2-10min; Vibrational frequency: 20-35HZ; Peak swing: 2-3mm.While 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
3; Apparent porosity: 5-12%; Ultimate compression strength: 30-50MPa; Bending strength: 5-20MPa.
2. high temperature alkali resistant erosion experiment
(1) sample of above-mentioned charcoal piece intercepting certain size is placed in to high-strength graphite crucible, the slag agent that then landfill has mixed; 1750 DEG C 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 basic slag agent is the one in calcium system or sodium system, and calcium is that 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; Have the vestige of obvious erosion, erosion rate of weight loss is 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 of above-mentioned charcoal piece intercepting certain size is placed in to corundum crucible, 1750 DEG C 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 while 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 taking 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 are improved, and utilize centrifugal spray drying and isostatic cool pressing technology, successfully realize pressureless sintering, obtained 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 DEG C, 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.
Taking high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Take 5Kg in the ratio of high purity graphite micro mist 80%, silica flour 5%, alumina sol 10% and silicon carbide micro-powder 5%, according to the processing parameter of batch mixing, dry, forming of green body, presintering, sintering circuit, obtain 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 high temperature anti-slag erosion experiment, slag agent: CaO, 60%; SiO
2, 30%; CaF
2, 10%.1750 DEG C 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 high-temperature oxidation resistant experiment, 1750 DEG C 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 DEG C, 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.
Taking high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Take 5Kg in the ratio of high purity graphite micro mist 70%, silica flour 10%, alumina sol 10% and silicon carbide micro-powder 10%, according to aforesaid processing parameter, carry out successively batch mixing, dry, moulding, presintering, sintering and obtain 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 high temperature anti-slag erosion experiment, slag agent: CaO, 40%; SiO
2, 50%; CaF
2, 10%.1750 DEG C 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 high-temperature oxidation resistant experiment, 1750 DEG C 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 DEG C, 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.
Taking high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Take 5Kg in the ratio of high purity graphite micro mist 60%, silica flour 10%, alumina sol 20% and silicon carbide micro-powder 10%, according to aforesaid processing parameter, carry out successively batch mixing, dry, moulding, presintering, sintering and obtain 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 high temperature anti-slag erosion experiment, slag agent: NaCO
3, 60%; SiO
2, 30%; NaF, 10%.1750 DEG C 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 high-temperature oxidation resistant experiment, 1750 DEG C 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 DEG C, 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.
Taking high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Take 5Kg in the ratio of high purity graphite micro mist 80%, silica flour 5%, alumina sol 10% and silicon carbide micro-powder 5%, according to aforesaid processing parameter, carry out successively batch mixing, dry, moulding, presintering, sintering and obtain 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 high temperature anti-slag erosion experiment, slag agent: NaCO
3, 40%; SiO
2, 50%; NaF, 10%.1750 DEG C 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 high-temperature oxidation resistant experiment, 1750 DEG C 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 DEG C, 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.
Taking high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Take 5Kg in the ratio of high purity graphite micro mist 70%, silica flour 10%, alumina sol 10% and silicon carbide micro-powder 10%, according to aforesaid processing parameter, carry out successively batch mixing, dry, moulding, presintering, sintering and obtain 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 high temperature anti-slag erosion experiment, slag agent: NaHCO
3, 60%; SiO
2, 30%; NaF, 10%.1750 DEG C 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 high-temperature oxidation resistant experiment, 1750 DEG C 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 DEG C, 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.
Taking high purity graphite micro mist, silica flour, alumina sol, silicon carbide micro-powder as raw material; Take 5Kg in the ratio of high purity graphite micro mist 60%, silica flour 10%, alumina sol 20% and silicon carbide micro-powder 10%, according to aforesaid processing parameter, carry out successively batch mixing, dry, moulding, presintering, sintering and obtain 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 high temperature anti-slag erosion experiment, slag agent: NaHCO
3, 40%; SiO
2, 50%; NaF, 10%.1750 DEG C 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 high-temperature oxidation resistant experiment, 1750 DEG C of experimental temperatures, insulation 40h.The performance test results is as shown in example in table 36.
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 note: 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 note: 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 (6)
1. a preparation method for high temperature resistant alkaline etching, anti-oxidation carbon piece, is characterized in that this charcoal piece material of main part composition quality per-cent is graphite microparticles 60-80%, silica flour 5-20%; Alumina sol 5-30% and silicon carbide micro-powder 0-15%; The preparation method of this charcoal piece comprises the steps:
(1) preparation of alumina sol: liquor alumini chloridi is adopted to heating in water bath to 80 DEG C, then drip ammoniacal liquor to it and be hydrolyzed, 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 be ceaselessly stirring all, and churning time 2h ~ 24h obtains having the colloidal sol of 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) dry: to adopt centrifugal spraying mode to be dried;
(4) forming of green body: adopt vibratory compaction or cold isostatic compaction;
(5) presintering: the green compact after baking are slowly heated up and are heated to 500-900 DEG C, and insulation 2-10h, obtains biscuit;
(6) sintering: biscuit is heated to 1400-1600 DEG C, insulation 2-10h, cool to room temperature, sintering process is to pass under hydrogen condition simultaneously and carry out at carbon dust covering protection.
2. the preparation method of a kind of high temperature resistant alkaline etching according to claim 1, anti-oxidation carbon piece, is characterized by step (2): graphite microparticles is selected high purity graphite, and Si powder selects metallurgical grade silicon purity at 98%-99% silicon raw material; Silicon carbide purity is more than 99%; Graphite microparticles, Si powder, silicon carbide micro-powder granularity are 75 μ m.
3. the preparation method of a kind of high temperature resistant alkaline etching according to claim 1, anti-oxidation carbon piece, is characterized in that in step (2): while adopting planetary ball mill to mix, and mechanical separator speed: 500r/min; Time: 0.5-2h; While adopting mechanical kneading, power: 15KW; Time: 1-2h.
4. the preparation method of a kind of high temperature resistant alkaline etching according to claim 1, anti-oxidation carbon piece, is characterized in that in step (3): while adopting centrifugal spraying mode to be dried, and slurry solid content massfraction 30-70%; Fog-spray nozzle rotating speed: 10000-12500r/min; Hot-wind inlet temperature: 200-220 DEG C; Hot-blast outlet temperature: 100-120 DEG C; Peristaltic pump speed: 100---150rpm; Negative pressure :-350Pa in tower.
5. the preparation method of a kind of high temperature resistant alkaline etching according to claim 1, anti-oxidation carbon piece, is characterized in that: in step (4), and while adopting vibratory compaction, exciting force: 6500-6900N; Time of vibration: 2-10min; Vibrational frequency: 20-35HZ; Peak swing: 2-3mm, while adopting isostatic cool pressing, operating pressure: 300-400MPa; Dwell time: 2-10min.
6. the preparation method of a kind of high temperature resistant alkaline etching according to claim 1, anti-oxidation carbon piece, is characterized in that: in step (6): the charcoal piece density after sintering: 1.6-2.0g/cm
3; Apparent porosity: 5-12%; Ultimate compression strength: 30-50MPa; Bending strength: 5-20MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210451558.2A CN103130507B (en) | 2012-11-13 | 2012-11-13 | Preparation method of antioxidant carbon block with heat and alkaline etching resistance |
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| CN104591771B (en) * | 2015-01-03 | 2016-08-24 | 南通扬子碳素股份有限公司 | The surface modifying method of 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 |
| CN109279894B (en) * | 2018-10-18 | 2021-08-10 | 邯郸市永年区科冠铸造材料厂 | Graphite drop tank and preparation method thereof |
| CN115448722B (en) * | 2022-11-10 | 2023-05-05 | 长沙中瓷新材料科技有限公司 | Preparation method of large-structure graphite sagger |
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