CN103979982B - Two steps add the zirconia metering nozzle preparation method of zirconium colloidal sol - Google Patents
Two steps add the zirconia metering nozzle preparation method of zirconium colloidal sol Download PDFInfo
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- CN103979982B CN103979982B CN201410200855.9A CN201410200855A CN103979982B CN 103979982 B CN103979982 B CN 103979982B CN 201410200855 A CN201410200855 A CN 201410200855A CN 103979982 B CN103979982 B CN 103979982B
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Abstract
The invention provides the zirconia metering nozzle preparation method that a kind of two steps add zirconium colloidal sol, comprise that batch mixing, compression moulding and drying are burnt till, vacuum soaking step; Batch mixing comprise weight percent be 20 ~ 50% PSZ, 10 ~ 30% monoclinic zirconias, 30 ~ 40% monocline desilicated zirconias and the stablizer of 1-3%, the bonding agent of 3-5%, bonding agent contains zirconia sol, and follow-up vacuum is soaked in operation and burnt product is put into zirconia sol vacuumized immersion.The mode that the present invention adds zirconium colloidal sol by two steps introduces nano zirconium dioxide, the nano zirconium dioxide utilizing zirconium colloidal sol to decomposite has high temperature resistant and stress-induced phase transformation is toughness reinforcing and microcrack evolution equation effect, improve the abrasion resistance of zirconia metering nozzle, resistance to fouling and thermal shock resistance, extend the work-ing life of metering nozzle, improve the working efficiency of continuous caster.
Description
Technical field
The present invention relates in ferrous metallurgical industry and cast the device preparing technical field that tundish controls molten steel flow continuously, especially, relate to a kind of two steps and add zirconium colloidal sol toughen and intensify zirconia metering nozzle preparation method.
Background technology
The functional device that a kind of high-temperature structural ceramics that metering nozzle is mounted in continuous casting tundish bottom makes, play a part to control molten steel flow, excellent heat-resistant knocking stability and corrosion-resistant property must be possessed, to ensure that molten steel can pass through in the uniform and stable inflow crystallizer of metering nozzle, thus ensure normally carrying out of continuous casting.The reliable use properties of metering nozzle is for provider's billet continuous casting machine high-quality molten steel and successfully pouring operation is all extremely important, continuous casting number of times not only can be made to increase, and be directly connected to the raising of production efficiency.
At present, the mainly zirconium oxide metering nozzle used both at home and abroad.Because zirconium white martensitic transformation can occur and with larger volume change, therefore, pure zirconia can not be used as goods at 1100 ~ 1250 DEG C.Zirconium oxide metering nozzle generally all uses calcium oxide PSZ to make, also to have and use magnesia partial stabilized zirconia, but because the inclusion in the compositions such as the stablizer in zirconium oxide metering nozzle in use zirconium white and Fe, the Mn in molten steel and molten steel reacts and precipitation, cause zirconium white because of stablizer precipitation spinodal decomposition, becoming monoclinic phase small-particle with molten steel flows away; In addition when above-mentioned reaction occurs, the weave construction of metering nozzle inside can be destroyed, when the bonding strength of material is not enough to washing away of opposing molten steel, the particle and the fine powder that are positioned at working face are washed away by molten steel, cause the situations such as the mouth of a river is expanding, cracking, greatly have impact on the work-ing life of zirconia metering nozzle, increase industrial cost, reduce production efficiency, thus producing the strong metering nozzle of abrasion resistance, resistance to fouling and heat-shock resistance has very real meaning.
About preparing in zirconia metering nozzle use bonding agent, be describe in the publication of CN 102557690A, CN 102584301A to utilize ZrO at publication number
2-Al
2o
3gel is as bonding agent; Publication number be in CN 102249704A publication applying nano monoclinic zirconia as bonding agent; Be utilize dextrin solution as bonding agent in CN 1844047 publication at publication number.At present, a kind of mixture in zirconia sol, resol, water and dextrin, starch, polyvinyl alcohol, pulp powder is not yet had to prepare the relevant report of the zirconia metering nozzle of abrasion resistance, resistance to fouling and thermal shock resistance excellence as bonding agent.
In addition, the thermal shock resistance difference of existing metering nozzle is the major reason that metering nozzle bursts.Heat-shock resistance is the key property weighing metering nozzle material at high temperature result of use.Therefore improvement of production process, the thermal shock resistance improving goods is the key preventing metering nozzle from ftractureing.
Summary of the invention
The object of the invention is to provide a kind of two steps to add zirconium colloidal sol toughen and intensify zirconia metering nozzle preparation method, to solve the technical problem that existing metering nozzle thermal shock resistance is poor and work-ing life is shorter.
For achieving the above object, a kind of two steps add the zirconia metering nozzle preparation method of zirconium colloidal sol, comprise that batch mixing, compression moulding and drying are burnt till, vacuum soaking step:
A, batch mixing: PSZ, monoclinic zirconia, monocline desilicated zirconia, bonding agent and stablizer batch mixing are even, and the mass ratio of each component is respectively:
B, compression moulding and drying are burnt till step and are obtained burnt product;
C, burnt product is put into zirconium colloidal sol vacuumize immersion 1 ~ 5h, then two steps can be obtained through Overheating Treatment and add zirconium colloidal sol toughen and intensify zirconia metering nozzle.
Preferably, the weight percent of described bonding agent component and each component is:
Preferably, described zirconium colloidal sol is zirconia sol.
Preferably, the solid phase weight ratio of zirconia sol is 2 ~ 12%.
Preferably, described stablizer is at least one in yttrium oxide, water-ground limestone, light calcium carbonate, magnesiumcarbonate.
Preferably, described resol is the even additive of acceleration of sintering, and it is the heat-reactive phenolic resin of fixed carbon content >=45%.
Preferably, described compression moulding and drying are burnt till step and are: dry 24h under 105 ± 5 DEG C of conditions, after burning till 5 hours, obtains burnt product at 1700-1800 DEG C of temperature.
Preferably, described heat treatment step is heat-treat 8-12 hour at 450-600 DEG C of temperature.
The present invention has following beneficial effect:
The mode that the present invention adds zirconium colloidal sol by two steps in the preparation process of zirconia metering nozzle introduces nano zirconium dioxide: first in the bonding agent preparing zirconia metering nozzle, add zirconia sol, follow-uply burnt product is put into zirconia sol vacuumizes immersion; The not only active higher nanometer zirconium dioxide particle of in-situ preparation, and nano zirconium dioxide crystal grain is comparatively evenly distributed in the skeleton gap of zirconia metering nozzle, nano zirconium dioxide is utilized to have the toughness reinforcing and microcrack evolution equation effect of high temperature resistant and stress-induced phase transformation, greatly improve the abrasion resistance of zirconia metering nozzle, resistance to fouling and thermal shock resistance, extend the work-ing life of metering nozzle, improve the working efficiency of continuous caster.
Zirconia sol used in the present invention is with normal temperature binding agent and the effect generating active nano zirconium dioxide particle.The nanometer zirconium dioxide particle size formed after zirconia sol decomposes is little, surface energy is high, be easy to be combined with other atom, produce very strong interfacial interaction, there is again rigidity and high thermal resistance simultaneously, add high-temperature-phase in matrix, thus improve thermal shock resistance and the creep-resistant property of zirconia metering nozzle.Nanometer zirconium dioxide particle is mainly distributed in the matrix scaffold gap of zirconia metering nozzle, creates strengthening effect.Nano zirconium dioxide second-phase is introduced in matrix, micro-flaw is produced because they are different from matrix expansion coefficient, these micro-flaws not only can improve the fracture surface energy of material, and the Young's modulus of material can be reduced, therefore nanometer zirconium dioxide particle effectively can improve the microtexture of goods, improves the thermal shock resistance of metering nozzle; The zirconia sol added can reduce the temperature of monoclinic zirconia monoclinic phase to tetragonal phase converting, thus improves the thermal shock resistance of metering nozzle.
Zirconia sol, except improving the heat-shock resistance of zirconia metering nozzle, can also reduce the void content of material, improve the viscosity of glassy phase, thus the creep-resistant property of metering nozzle is greatly improved.
In addition, the present invention introduces appropriate carbon by adding heat-reactive phenolic resin in bonding agent in goods inside, heat-reactive phenolic resin fixed carbon content >=45%, can strengthen compared with the thermal conductivity of thick product in sintering process, controlled by suitable atmosphere and temperature, a small amount of carbon residue of goods inside can be made to burn at a suitable temperature, thus make burning till of goods more full and uniform, and then improve heat-shock resistance and the scour resistance of metering nozzle.
Therefore, adopt the zirconia metering nozzle that the inventive method is obtained, its main physical and chemical index is: zirconium white weight ratio >=95%, volume density is 5.0 ~ 5.5g/cm3, cold crushing strength >=200MPa, thermal shock resistance (1100 DEG C, water-cooled) >=8 times, work-ing life can reach more than 25 hours.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.The present invention is further detailed explanation below.
Embodiment
Below embodiments of the invention are described in detail, but the multitude of different ways that the present invention can limit according to claim and cover is implemented.
Embodiment 1
A kind of two steps add the preparation method of zirconium colloidal sol toughen and intensify zirconia metering nozzle, by the electric smelting calcium oxide PSZ particle that weight percent is 25%, the electric smelting calcium oxide PSZ fine powder of 20%, the monocline desilicated zirconia micro mist of 35%, the monoclinic zirconia micro mist constitutive material of 20%, add account for raw material gross weight 1% yttrium oxide as stablizer, and then add the zirconia sol accounting for material gross weight 3%, the bonding agent of dextrin and water composition, in bonding agent, the ratio of each component is: 66% zirconia sol, 30% water, 4% dextrin, the solid phase weight content of zirconia sol is 6%.
Its preparation process is as follows:
1) whole raw material is put into mixer and be dry mixed 4 minutes, then add bonding agent wet mixing based on zirconia sol 5 minutes;
2) by gained mixture ageing mixture mechanical pressing after 10 hours, forming pressure is 520MPa, and dry 24h under 105 ± 5 DEG C of conditions, burns till 3 hours at 1750 DEG C of temperature;
3) burnt product is put into zirconium colloidal sol and vacuumize immersion 3h, dry, finally at 500 DEG C of temperature, heat-treat 8 hours, obtain two steps and add zirconium colloidal sol toughen and intensify zirconia metering nozzle.
Zirconia metering nozzle prepared by the present embodiment, main physical and chemical index is: zirconium white weight ratio=96%, and volume density is 5.3g/cm
3, cold crushing strength=210MPa, thermal shock resistance (1100 DEG C, water-cooled)=8 times, work-ing life can reach 26 hours.
The physical and chemical index of current existing metering nozzle is: zirconium white weight ratio>=90%, and volume density is 3.8 ~ 5.2g/cm
3, cold crushing strength is 80-180MPa, and thermal shock resistance (1100 DEG C, water-cooled) is for 5-6 time, and work-ing life is 22 hours.
It should be noted that: the particle diameter of electric smelting calcium oxide PSZ particle is more than or equal to 75 μm, the particle diameter of electric smelting calcium oxide PSZ fine powder is at 23 μm-75 μm, the particle diameter of monocline desilicated zirconia micro mist is at 13 μm-23 μm, the particle diameter of monoclinic zirconia micro mist is at 13 μm-23 μm, and the weight percent of above-mentioned four can be:
After the size limited proportion of each component is got off, then can the contact area of each component of precise hard_drawn tuhes and speed of reaction, make reaction more even.
The component particle diameter proportion of composing of each embodiment also can be described above below, repeats no more.
Embodiment 2
A kind of two steps add the preparation method of zirconium colloidal sol toughen and intensify zirconia metering nozzle, be the electric smelting calcium oxide PSZ particle of 35%, electric smelting calcium oxide PSZ fine powder, the monocline desilicated zirconia micro mist of 30%, the monoclinic zirconia micro mist constitutive material of 10% of 25% by weight percent, add account for raw material gross weight 2% water-ground limestone and light calcium carbonate as stablizer, in stablizer, the ratio of each component is: 65% water-ground limestone, 35% light calcium carbonate; And then add account for material gross weight 4% zirconia sol, resol, water, starch composition bonding agent, in bonding agent, the ratio of each component is: 50% zirconia sol, 2% resol, 40% water, 8% starch, and the solid phase weight content of zirconia sol is 12%.
Resol is the even additive of acceleration of sintering, and it is the heat-reactive phenolic resin of fixed carbon content >=45%, is mainly used in burning till the larger goods of thickness.
Its preparation process is as follows:
1) whole raw material is put into mixer and be dry mixed 3 minutes, then add bonding agent wet mixing based on zirconia sol 4 minutes;
2) by gained mixture ageing mixture mechanical pressing after 12 hours, forming pressure is 560Mpa, and dry 24h under 105 ± 5 DEG C of conditions, burns till 5 hours at 1780 DEG C of temperature;
3) burnt product is put into zirconium colloidal sol and vacuumize immersion 5h, dry, finally at 500 DEG C of temperature, heat-treat 10 hours, obtain two steps and add zirconium colloidal sol toughen and intensify zirconia metering nozzle.
Zirconia metering nozzle prepared by the present embodiment, main physical and chemical index is: zirconium white weight ratio=96%, and volume density is 5.4g/cm
3, cold crushing strength=220MPa, thermal shock resistance (1100 DEG C, water-cooled)=9 times, work-ing life can reach 27 hours.
Embodiment 3
A kind of two steps add the preparation method of zirconium colloidal sol toughen and intensify zirconia metering nozzle, be the electric smelting calcium oxide PSZ particle of 45%, electric smelting calcium oxide PSZ fine powder, the monocline desilicated zirconia micro mist of 35%, the monoclinic zirconia micro mist constitutive material of 10% of 10% by weight percent, add account for raw material gross weight 3% yttrium oxide, water-ground limestone and light calcium carbonate as stablizer, in stablizer, the ratio of each component is: 5% yttrium oxide, 45% water-ground limestone, 50% light calcium carbonate; And then add account for material gross weight 5% zirconia sol, water, pulp powder composition bonding agent, in bonding agent, the ratio of each component is: 80% zirconia sol, 17% water, 3% pulp powder, and the solid phase weight content of zirconia sol is 2%.
Its preparation process is as follows:
1) whole raw material is put into mixer and be dry mixed 5 minutes, then add bonding agent wet mixing based on zirconia sol 4 minutes;
2) by gained mixture ageing mixture mechanical pressing after 14 hours, forming pressure is 600MPa, and dry 24h under 105 ± 5 DEG C of conditions, burns till 5 hours at 1750 DEG C of temperature;
3) burnt product is put into zirconium colloidal sol and vacuumize immersion 4h, dry, finally at 500 DEG C of temperature, heat-treat 12 hours, obtain two steps and add zirconium colloidal sol toughen and intensify zirconia metering nozzle.
Zirconia metering nozzle prepared by the present embodiment, main physical and chemical index is: zirconium white weight ratio=95%, and volume density is 5.2g/cm
3, cold crushing strength=210MPa, thermal shock resistance (1100 DEG C, water-cooled)=8 times, work-ing life can reach 26 hours.
Following examples adopt the preparation method that embodiment one to three is identical, shown in the concrete table composed as follows of each component.
In above-described embodiment the component of stablizer and weight percent as shown in the table.
| Yttrium oxide | Water-ground limestone | Light calcium carbonate | Magnesiumcarbonate | |
| Embodiment four | — | — | — | 100 |
| Embodiment five | 10 | — | — | 90 |
| Embodiment six | — | 100 | — | — |
| Embodiment seven | 5 | 70 | 25 | — |
| Embodiment eight | — | — | 100 | — |
| Embodiment nine | — | 35 | 65 | — |
| Embodiment ten | 5 | 60 | 35 | — |
In above-described embodiment the component of bonding agent and weight percent as shown in the table.
In above-described embodiment, the solid phase weight content of zirconia sol is as shown in the table.
In raw material, the size of each grain diameter of components, grating are directly connected to burning till of metering nozzle and degree of compactness, and the particle diameter of particle, fine powder, micro mist as above each embodiment carries out proportioning, can guarantee that the metering nozzle made has rational compactness extent and excellent performance.
The zirconia metering nozzle that above embodiment four to embodiment ten prepares, its main physical and chemical index is: zirconium white weight ratio>=95%, and volume density is 5.0 ~ 5.5g/cm
3, cold crushing strength>=200MPa, thermal shock resistance (1100 DEG C, water-cooled)>=8 times, work-ing life is all more than 25 hours.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. two steps add a zirconia metering nozzle preparation method for zirconium colloidal sol, it is characterized in that, comprise that batch mixing, compression moulding and drying are burnt till, vacuum soaking step:
A, batch mixing: electric smelting calcium oxide PSZ, monoclinic zirconia, the even constitutive material of monocline desilicated zirconia batch mixing, the mass ratio that each component accounts for raw material gross weight is respectively:
Electric smelting calcium oxide PSZ 20-50%
Monoclinic zirconia 10-30%
Monocline desilicated zirconia 30-40%;
The quality of said components is 100% than sum;
The mass ratio that bonding agent, stablizer account for raw material gross weight is respectively:
Bonding agent 3-5%
Stablizer 1-3%,
The weight percent of described bonding agent component and each component is:
Zirconia sol 50 ~ 80%
Resol 0 ~ 3%
Water 18 ~ 40%
One 2 ~ 10% in dextrin, starch, polyvinyl alcohol, pulp powder;
B, compression moulding and drying are burnt till step and are obtained burnt product;
C, burnt product is put into zirconium colloidal sol vacuumize immersion 1 ~ 5h, then can obtain through Overheating Treatment the zirconia metering nozzle that two steps add zirconium colloidal sol.
2. a kind of two steps according to claim 1 add the zirconia metering nozzle preparation method of zirconium colloidal sol, it is characterized in that, the solid phase weight ratio of zirconia sol is 2 ~ 12%.
3. a kind of two steps according to claim 1 add the zirconia metering nozzle preparation method of zirconium colloidal sol, it is characterized in that, described stablizer is at least one in yttrium oxide, water-ground limestone, light calcium carbonate, magnesiumcarbonate.
4. a kind of two steps according to claim 1 add the zirconia metering nozzle preparation method of zirconium colloidal sol, it is characterized in that, described resol is the even additive of acceleration of sintering, and it is the heat-reactive phenolic resin of fixed carbon content >=45%.
5. a kind of two steps according to claim 1 add the zirconia metering nozzle preparation method of zirconium colloidal sol, it is characterized in that, step is burnt till in described compression moulding and drying: dry 24h under 105 ± 5 DEG C of conditions, after burning till 5 hours, obtains burnt product at 1700-1800 DEG C of temperature.
6. a kind of two steps according to claim 1 add the zirconia metering nozzle preparation method of zirconium colloidal sol, it is characterized in that, described heat treatment step is heat-treat 8-12 hour at 450-600 DEG C of temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105418096A (en) * | 2015-12-01 | 2016-03-23 | 浙江铁狮高温材料有限公司 | Self-adaptive zirconium oxide tundish nozzle |
| CN106007743B (en) * | 2016-05-13 | 2019-01-29 | 西安建筑科技大学 | A kind of preparation method of zirconium oxide metering nozzle |
| CN107488034A (en) * | 2017-08-25 | 2017-12-19 | 南通通州湾新材料科技有限公司 | A kind of feeding of high zirconium content and preparation method thereof |
| CN116768620A (en) * | 2023-06-05 | 2023-09-19 | 长江师范学院 | Steel slag erosion resistant sizing nozzle and preparation method and application thereof |
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| CN101503304A (en) * | 2009-03-26 | 2009-08-12 | 中钢集团洛阳耐火材料研究院有限公司 | Low temperature method for manufacturing high thermal shock superhigh temperature zircite product |
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| CN101503304A (en) * | 2009-03-26 | 2009-08-12 | 中钢集团洛阳耐火材料研究院有限公司 | Low temperature method for manufacturing high thermal shock superhigh temperature zircite product |
| CN102249704A (en) * | 2011-04-22 | 2011-11-23 | 浙江省长兴铁狮耐火材料有限公司 | Zirconia metering nozzle manufacturing method |
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