CN1300061C - Preparation method of silica alumina gel bonding agent for corundum-mullite composite ceramic - Google Patents
Preparation method of silica alumina gel bonding agent for corundum-mullite composite ceramic Download PDFInfo
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- CN1300061C CN1300061C CNB2005100493565A CN200510049356A CN1300061C CN 1300061 C CN1300061 C CN 1300061C CN B2005100493565 A CNB2005100493565 A CN B2005100493565A CN 200510049356 A CN200510049356 A CN 200510049356A CN 1300061 C CN1300061 C CN 1300061C
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Abstract
The present invention discloses a preparation method of a silicon aluminum gel binding agent used for corundum-mullite compound ceramics. Silicon sol and aluminum sol are mainly used as raw materials, and silicon aluminum gel is prepared by controlling the pH value of the aluminum sol and by a sol-gel process. In the process of preparing the gel, the content of silicon and aluminum can be controlled by dewatering, and gel time can be controlled by introducing ammonia water or acetylacetone. An aluminum fluoride mineralizing agent is introduced in the silicon aluminum for controlling the crystal forms of mullite phases generated in the firing process of the silicon aluminum gel. The silicon aluminum gel can be used as a binding agent in the preparation process of ceramics and refractory materials, and can also be used for preparing superfine mullite powder. In the process of use, the mineralizing agent is introduced for controlling the crystal forms of the generated mullite components to promote the enhancement of the performance of the ceramics or the refractory materials.
Description
Technical field
The present invention relates to pottery and burn till and use wedding agent, especially relate to a kind of preparation method of silica alumina gel bonding agent for corundum-mullite composite ceramic.
Background technology
Wedding agent time by its existence in pottery and fire resistive material product can be divided into temporary transient wedding agent and permanent bond agent: the former decomposes because of intensification in goods sintering or use, volatilization and leave goods, its nubbin are no longer to goods or seldom product properties is exerted an influence; The latter then for good and all stays in the goods in sintering and use, and must the performance of goods be exerted an influence.This permanent bond agent often is divided into two classes that change and do not change again in sintering or use.In general, most wedding agents can make the high-temperature behavior of goods descend, for pyroceramic and refractory materials, between this particle or the best combination between particle and fine powder mutually beyond doubt its principal phase itself or fire performance with principal crystalline phase is close and product properties produced second phase that well influences, at pyroceramic and refractory materials is in the goods of dominant mechanism with the solid state sintering, micro mist adds as sintering aids, also serves as this effect in conjunction with phase simultaneously in the goods sintering process.But, the micro mist that adds in general pyroceramic and refractory materials technology mostly is micron order, active and not really high, thinner super-fine powder then costs an arm and a leg, make general pyroceramic be difficult to accept, what degree of scatter was the highest, activity is maximum obviously is the solution that is distributed to ion, molecule, but in general pyroceramic and refractory materials technology, be added to as combination, its amount again very little.
Be widely used in making intermediate product---co-precipitation (or hydrolysis) gel of the sol-gel method of super-fine powder in recent years, because its dispersity is higher than general micro mist, and it is mixed very even, active higher, and has the good binding performance, utilize it as fine particle and the matrix intersection of being distributed in of wedding agent energy, and its multicomponent mixture of the as easy as rolling off a log adjustment of co-precipitation gel, can press goods easily and performance demands be added multi-component in conjunction with phase at its key position, it also can use the formed arogel mixture of precipitation pack in the sol-gel method as wedding agent equally.This low temperature active sintering for pyroceramic and refractory materials has been opened up new approach.
The wedding agent that corundum-mullite and mullite product are commonly used has clay at present, the mullite fine powder, aluminum oxide fine powder and silicon powder, have only clay to have good plasticity in these wedding agents, certain bonding strength can be provided, silicon powder then needs the aquation of long period can produce certain intensity afterwards, mullite fine powder and aluminum oxide fine powder then belong to poor material can't provide corresponding strength at all, clay and silicon powder are easily brought the impurity of more amount in the process of introducing, aluminum oxide powder and mullite fine powder bonded pottery then need other organic bond, and the firing temperature height.We have then developed silica-alumina gel as these ceramic wedding agents under the condition of present corundum-mullite pottery and mullite ceramic wedding agent present situation, certain green compact bonding strength can not only be provided, can also reduce the introducing of impurity, improve the over-all properties of pottery.
The commercial silica-alumina gel of preparation seldom at present, have only independent aluminium glue or silica gel to buy, silica-alumina gel commonly used then is the method preparation by sol-gel, utilize the hydrolysis and the polyreaction of alkoxide to make uniform sol, form gel at last, preparation silica-alumina gel cost is very high, can't use at refractory materials or conventional ceramic field at all, is difficult to realize large-scale industrial production and application.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of silica alumina gel bonding agent for corundum-mullite composite ceramic.Utilize aluminium glue and silica gel to be fit to the silica-alumina gel of present refractory materials and pottery use for feedstock production.
The technical solution used in the present invention is that this method comprises following each step:
1) with commercially available alumina content be the aluminium glue of 10～20wt% to be added to acidifying pH value be to dilute in 2.5～3.0 the deionized water, stirring and being mixed with alumina content is that the aluminium colloidal sol of 5～10wt% is standby;
2) be to add deionized water in the silicon sol of 18wt% to dilute at silica content, stirring and being mixed with silica content is that the silicon sol of 5～10wt% is standby;
3) with the aluminium colloidal sol for preparing stirring and refluxing half an hour in 60～95 ℃ of reactors, be cooled to 10～50 ℃, add quantitative silicon sol, stir while adding in mullite chemistry formula ratio, control pH value≤3 simultaneously, churning time is 1～3 hour preparation silicon-aluminum sol;
4) by dehydration preparation mullite concentration be 5～10% silica-alumina gel.
Mullite concentration by dehydration preparation is in 5～10% the silica-alumina gel, to add the gelation time that ammoniacal liquor or organic bases 3-aminopropanol can be accelerated silicon-aluminum sol, adds the gelation time that methyl ethyl diketone can delay silicon-aluminum sol.
Being used for deionized water acidifying material is acetate, nitric acid, hydrochloric acid or oxalic acid.
2～10% of adding silicon-aluminum sol weight aluminum trifluoride mineralizer stirs the silica-alumina gel that obtains containing mineralizer in the silicon-aluminum sol for preparing.
The useful effect that the present invention has is: provide a kind of and can effectively improve ceramic performance, can under lower temperature condition, realize the agglomerating silicon alumina gel binder again, mainly be as raw material with silicon sol and aluminium colloidal sol, pH value by the control aluminium glue prepares silica-alumina gel by sol-gel process.In the process of preparation gel,, introduce ammoniacal liquor or methyl ethyl diketone may command gelation time, the crystal formation of the mullite thing phase that introducing aluminum trifluoride mineralizer controllable silicon alumina gel generates in silica-alumina gel in sintering process by dehydration may command sial content.Aluminium silicon gel can be as wedding agent in the process that pottery and refractory materials prepare, also can be used for the preparation of ultra-fine mullite powder, in use introduce the crystal shape that the mineralizer may command generates the mullite component, promote the raising of pottery or capabilities of refractory materials.
Description of drawings
Fig. 1 is a TEM photo after 100 ℃ of oven dry of dry gel powder;
Fig. 2 is a TEM photo after 1100 ℃ of thermal treatments of dry gel powder;
Fig. 3 is rubber powder end TEM photo after 1250 ℃ of thermal treatment;
Fig. 4 is fluorinated aluminium dry gel powder TEM photo after 1250 ℃ of thermal treatment.
Embodiment
(alumina content 10～20wt%) is added to fill in acetate acidifying deionized water (the pH value the is 2.5) container and dilutes with aluminium glue, it is that 5% aluminium colloidal sol is standby that stirring is mixed with alumina content, also add simultaneously deionized water and dilutes in silicon sol (silica content is 18wt%), it is that 5% silicon sol is standby that stirring is mixed with silica content.With aluminium colloidal sol stirring and refluxing half an hour in 80 ℃ of reactors, be cooled to 40 ℃, adding a certain amount of silica content by the mullite proportioning is 5% silicon sol, stir while adding, will control pH value≤3 simultaneously, churning time is 2 hours, the preparation silicon-aluminum sol, by the silica-alumina gel of dehydration preparation different concns, add the gelation time that ammoniacal liquor or organic bases 3-aminopropanol can be accelerated silicon-aluminum sol then, add the gelation time that methyl ethyl diketone can delay silicon-aluminum sol.
Table 1 is the gelling situation of aluminium silicon sol under different pH condition, finds that the colloidal sol of pH value≤3.0 can keep translucent nothing precipitation in for a long time, and the colloidal sol of pH=3.2～8.0 all presents muddiness or deposited phenomenon.Wherein pH=3.2, turbidity was less when 3.5 liang of samples began, along with the prolongation turbidity of time increases gradually, and other samples seem quite muddy at the very start, sedimentation gradually then.
The gelling situation of table 1 aluminium silicon sol system under different pH values
| Sample number into spectrum | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 |
| The pH value | 2.5 | 3.0 | 3.2 | 3.5 | 4.0 | 5.0 | 6.0 | 7.0 |
| The gelling situation | Keep translucent | Keep translucent | Begin to keep translucent, muddy gradually, precipitation is arranged | Keep translucent at the beginning, muddy gradually, precipitation is arranged | Promptly muddy at the beginning, precipitation is arranged | Promptly muddy at the beginning, precipitation is arranged | Promptly muddy at the beginning, flocks is arranged | Promptly muddy at the beginning, flocks is arranged |
The gelation time of table 2 aluminium silicon sol under differing temps and pH value condition, along with the raising gel time of temperature and pH value shortens gradually, wherein the effect of temperature is particularly evident, and the gelation time under the room temperature condition is about 10 days, and only needs 2 hours at 80 ℃.Add ammoniacal liquor among the aluminium silicon sol, the rapid gelling of colloidal sol loses flowability and obtains the gel that alkalizes; Add the gelation time that methyl ethyl diketone can prolong the aluminium silicon sol and give in aluminium colloidal sol, introduce the 10ml methyl ethyl diketone in 200ml aluminium colloidal sol, under 80 ℃ condition, gelation time is 3.5 hours, has prolonged 1.5 hours.
The gelation time of table 2 aluminium silicon sol under differing temps and pH value condition
| Gelling temp (℃) | Room temperature (20) | 40 | 60 | 80 |
| A1 (pH=2.5) gelation time | 12 days | 30 hours | 8 hours | 2 hours |
| A2 (pH=3.0) gelation time | 10 days | 28 hours | 7 hours | 2 hours |
Fig. 1, Fig. 2, Fig. 3 are to the transmission electron microscope collection of illustrative plates of Gelatin powder after heat treatments at different, are the porous coacervates through the Gelatin powder after 100 ℃ of oven dry; Through 1100 ℃ of thermal treatments after 2 hours mainly by 30-40nm etc. axle shape particle constitute; And through 1250 ℃ of thermal treatments after 2 hours, mullite powder is a plate-like grain, zoon.Fig. 4 for silica-alumina gel add aluminum trifluoride through 1250 ℃ of thermal treatments after the powder TEM photo of gained, as seen from the figure, powder has formed the whisker shape structure that is crisscross, from Fig. 4 B as can be known the length of whisker be 28 μ m, wide is 700nm, and length-to-diameter ratio is greater than 30, and its crystalline structure is the mullite phase as can be seen from Figure 4, the introducing of aluminum fluoride helps silica-alumina gel and at high temperature generates mullite crystal whisker, shows good thermal shock resistance in the mullite bonded corundum ceramic.
Claims (4)
1, a kind of preparation method of silica alumina gel bonding agent for corundum-mullite composite ceramic is characterized in that this method comprises following each step:
1) with commercially available alumina content be the aluminium glue of 10～20wt% to be added to acidifying pH value be to dilute in 2.5～3.0 the deionized water, stirring and being mixed with alumina content is that the aluminium colloidal sol of 5～10wt% is standby;
2) be to add deionized water in the silicon sol of 18wt% to dilute at silica content, stirring and being mixed with silica content is that the silicon sol of 5～10wt% is standby;
3) with the aluminium colloidal sol for preparing stirring and refluxing half an hour in 60～95 ℃ of reactors, be cooled to 10～50 ℃, add quantitative silicon sol, stir while adding in mullite chemistry formula ratio, control pH value≤3 simultaneously, churning time is 1～3 hour preparation silicon-aluminum sol;
4) by dehydration preparation mullite concentration be 5～10% silica-alumina gel.
2, the preparation method of a kind of silica alumina gel bonding agent for corundum-mullite composite ceramic according to claim 1, it is characterized in that: the mullite concentration by dehydration preparation is in 5～10% the silica-alumina gel, add ammoniacal liquor or organic bases 3-aminopropanol and can accelerate the gelation time of silicon-aluminum sol, add the gelation time that methyl ethyl diketone can delay silicon-aluminum sol.
3, the preparation method of a kind of silica alumina gel bonding agent for corundum-mullite composite ceramic according to claim 1 is characterized in that: being used for deionized water acidifying material is acetate, nitric acid, hydrochloric acid or oxalic acid.
4, the preparation method of a kind of silica alumina gel bonding agent for corundum-mullite composite ceramic according to claim 1 is characterized in that: 2～10% of adding silicon-aluminum sol weight aluminum trifluoride mineralizer stirs the silica-alumina gel that obtains containing mineralizer in the silicon-aluminum sol for preparing.
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| CNB2005100493565A CN1300061C (en) | 2005-03-14 | 2005-03-14 | Preparation method of silica alumina gel bonding agent for corundum-mullite composite ceramic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101224986B (en) * | 2007-01-15 | 2011-08-10 | 中冶武汉冶金建筑研究院有限公司 | Normal-temperature high-strength fire mud for dry quenching furnace |
| CN101857448B (en) * | 2010-06-03 | 2012-10-03 | 安吉科灵磁性材料有限公司 | Titanium dioxide sol reinforced corundum-mullite product and production method thereof |
| CN102167601A (en) * | 2010-12-20 | 2011-08-31 | 中钢集团洛阳耐火材料研究院有限公司 | Corundum-mullite burn-bearing board having high fineness |
| CN108383132B (en) * | 2018-03-19 | 2021-07-16 | 华南理工大学 | Low-temperature preparation method of superfine mullite powder |
| CN108530101A (en) * | 2018-07-06 | 2018-09-14 | 佛山陵朝新材料有限公司 | A kind of preparation method of high stomata dispersibility high-alumina insulated brick material |
| CN109180174B (en) * | 2018-09-26 | 2019-09-27 | 西安航空学院 | The method of the colloidal sol mixing-fine grinding-pressurization raising mullite strength of materials |
| CN110498688A (en) * | 2019-09-16 | 2019-11-26 | 江苏瑞复达新材料有限公司 | A kind of structural ceramics enhancing high silicon oxygen Aluminum sol powder and preparation method thereof |
| CN112521133A (en) * | 2020-12-18 | 2021-03-19 | 洛阳索莱特材料科技有限公司 | Preparation method of ultrahigh-temperature corundum-mullite ceramic product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5250476A (en) * | 1991-04-30 | 1993-10-05 | Haldor Topsoe A/S | Ceramic binder and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5250476A (en) * | 1991-04-30 | 1993-10-05 | Haldor Topsoe A/S | Ceramic binder and use thereof |
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