CN103979982A - Zirconia metering nozzle preparing method adding zirconium sol in two steps - Google Patents
Zirconia metering nozzle preparing method adding zirconium sol in two steps Download PDFInfo
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Abstract
The invention provides a zirconia metering nozzle preparing method adding zirconium sol in two steps. The method includes steps of material mixing, compression moulding, drying, sintering, and vacuum soaking. The mixed materials comprise 20-50% by weight of partially-stable zirconia, 10-30% by weight of monoclinic zirconia, 30-40% by weight of monoclinic silicon-removed zirconium, 1-3% by weight of a stabilizing agent, and 3-5% by weight of a binding agent that including zirconia sol. In the subsequent vacuum soaking step, a sintered product is added into the zirconia sol and subjected to vacuumizing and soaking. According to the method, nanometer zirconia is introduced by a manner of adding the zirconium sol in two steps. The nanometer zirconia decomposed by utilization of the zirconium sol has functions of resisting high temperature, stress-induced transformation toughening and microcrack toughening, thus enhancing the washing resistance, corrosion resistance and thermal shock resistance of the zirconia metering nozzle, prolonging the service lifetime of the metering nozzle, and increasing the working efficiency of a continuous casting machine.
Description
Technical field
The present invention relates to cast the device preparing technical field of controlling molten steel flow for tundish continuously in ferrous metallurgical industry, especially, relate to a kind of two steps and add the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol preparation method.
Background technology
Metering nozzle is mounted in the functional device that continuous casting is made of a kind of high-temperature structural ceramics of tundish bottom, work to control molten steel flow, must possess good anti-thermal shock stability and corrosion-resistant property, to guarantee that molten steel can pass through in the uniform and stable inflow crystallizer of metering nozzle, thereby guarantee 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, not only can make continuous casting number of times increase, and is directly connected to the raising of production efficiency.
What use both at home and abroad at present, is mainly zirconium oxide metering nozzle.Because zirconium white martensitic transformation can occur and with larger volume change, therefore, pure zirconia can not be used as goods at 1100～1250 ℃.Zirconium oxide metering nozzle generally all uses calcium oxide PSZ to make, also have and use magnesia partial stabilized zirconia, but due to zirconium oxide metering nozzle in use the stablizer in zirconium white react and precipitation with compositions such as Fe, Mn in molten steel and the inclusion in molten steel, cause zirconium white because of stablizer precipitation spinodal decomposition, become monoclinic phase small-particle and flow away with molten steel; 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 resist washing away of 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 mouth of a river hole enlargement, cracking, greatly affected the work-ing life of zirconia metering nozzle, increase industrial cost, reduced production efficiency, thereby produced the metering nozzle that abrasion resistance, resistance to fouling and heat-shock resistance are strong and have very real meaning.
About using aspect bonding agent preparing zirconia metering nozzle, in publication number is the communique of CN102557690A, CN102584301A, has introduced and utilized ZrO
2-Al
2o
3gel is as bonding agent; Publication number be in CN102249704A communique applying nano monoclinic zirconia as bonding agent; At publication number, be to utilize dextrin solution as bonding agent in CN1844047 communique.At present, not yet have and using a kind of mixture in zirconia sol, resol, water and dextrin, starch, polyvinyl alcohol, pulp powder and as bonding agent, prepare the relevant report of the zirconia metering nozzle of abrasion resistance, resistance to fouling and thermal shock resistance excellence.
In addition, the thermal shock resistance of existing metering nozzle is poor is the major reason that metering nozzle bursts.Heat-shock resistance is a key property weighing metering nozzle material at high temperature result of use.So improvement of production process, the thermal shock resistance that improves goods is the key that prevents metering nozzle cracking.
Summary of the invention
The object of the invention is to provide a kind of two steps to add the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol 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 batch mixing, compression moulding and dryly burn 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 dryly burn till step and obtain burnt product;
C, burnt product is put into zirconium colloidal sol vacuumize and soak 1～5h, then through Overheating Treatment, can make two steps and add the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol.
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 dry burn till step and be: dry 24h under 105 ± 5 ℃ of conditions, at 1700-1800 ℃ of temperature, burn till after 5 hours, obtain burnt product.
Preferably, described heat treatment step is to heat-treat 8-12 hour at 450-600 ℃ of temperature.
The present invention has following beneficial effect:
The present invention adds the mode of zirconium colloidal sol to introduce nano zirconium dioxide by two steps in the preparation process of zirconia metering nozzle: first preparing in the bonding agent of zirconia metering nozzle and adding zirconia sol, follow-uply burnt product is put into zirconia sol vacuumizing immersion; Not only original position generates active higher nanometer zirconium dioxide particle, and nano zirconium dioxide crystal grain is evenly distributed in the skeleton gap of zirconia metering nozzle, utilize nano zirconium dioxide to there is the toughness reinforcing and tiny crack toughening effect of high temperature resistant and stress-induced phase transformation, greatly improve abrasion resistance, resistance to fouling and the thermal shock resistance of zirconia metering nozzle, extend the work-ing life of metering nozzle, improve the working efficiency of continuous caster.
Zirconia sol used in the present invention is with the effect of normal temperature binding agent and generation active nano zirconium dioxide particle.The nanometer zirconium dioxide particle size forming after zirconia sol decomposes is little, surface can be high, be easy to be combined with other atom, produce very strong interfacial interaction, there is again rigidity and high thermal resistance simultaneously, increase high-temperature-phase in matrix, thereby improved 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, has produced strengthening effect.In matrix, introduce nano zirconium dioxide second-phase, because they are different from the matrix coefficient of expansion, produce micro-flaw, these micro-flaws not only can improve the fracture surface energy of material, and can reduce the Young's modulus of material, therefore nanometer zirconium dioxide particle can effectively improve the microtexture of goods, improves the thermal shock resistance of metering nozzle; The zirconia sol adding can reduce monoclinic zirconia monoclinic phase to the temperature of tetragonal phase converting, thereby 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, the viscosity of raising glassy phase, thereby the creep-resistant property of metering nozzle is greatly improved.
In addition, the present invention introduces appropriate carbon by add heat-reactive phenolic resin in bonding agent in goods inside, heat-reactive phenolic resin fixed carbon content >=45%, can strengthen the thermal conductivity in sintering process compared with thick product, by suitable atmosphere and temperature, control, can make a small amount of carbon residue of goods inside burn at suitable temperature, thereby make burning till of goods more full and uniform, and then improve heat-shock resistance and the scour resistance of metering nozzle.
Therefore, the zirconia metering nozzle that adopts the inventive method to make, its main physical and chemical index is: zirconium white weight ratio>=95%, volume density is 5.0～5.5g/cm
3, cold crushing strength>=200MPa, thermal shock resistance (1100 ℃, water-cooled)>=8 times, can reach more than 25 hours work-ing life.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below the present invention is further detailed explanation.
Embodiment
Below embodiments of the invention are elaborated, but the multitude of different ways that the present invention can limit and cover according to claim is implemented.
Embodiment 1
A kind of two steps add the preparation method of the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol, the electric smelting calcium oxide PSZ particle that is 25% by weight percent, 20% electric smelting calcium oxide PSZ fine powder, 35% monocline desilicated zirconia micro mist, 20% monoclinic zirconia micro mist constitutive material, add the yttrium oxide that accounts for raw material gross weight 1% as stablizer, and then add the zirconia sol that accounts for material gross weight 3%, the bonding agent that dextrin and water form, 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 materials are put into mixer and be dry mixed 4 minutes, then add and take zirconia sol as main bonding agent wet mixing 5 minutes;
2) by gained mixture ageing mixture mechanical pressing after 10 hours, forming pressure is 520MPa, and under 105 ± 5 ℃ of conditions, dry 24h burns till 3 hours at 1750 ℃ of temperature;
3) burnt product is put into zirconium colloidal sol and vacuumized immersion 3h, dry, finally at 500 ℃ of temperature, heat-treat 8 hours, obtain two steps and add the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol.
Zirconia metering nozzle prepared by the present embodiment, main physical and chemical index is: zirconium white weight ratio=96%, volume density is 5.3g/cm
3, cold crushing strength=210MPa, thermal shock resistance (1100 ℃, water-cooled)=8 times, can reach 26 hours work-ing life.
The physical and chemical index of current existing metering nozzle is: zirconium white weight ratio>=90%, volume density is 3.8～5.2g/cm
3, cold crushing strength is 80-180MPa, and thermal shock resistance (1100 ℃, water-cooled) is 5-6 time, and be about 22 hours work-ing life.
It should be noted that: the particle diameter of electric smelting calcium oxide PSZ particle is more than or equal to 75 μ m, the particle diameter of electric smelting calcium oxide PSZ fine powder is at 23 μ m-75 μ m, the particle diameter of monocline desilicated zirconia micro mist is at 13 μ m-23 μ m, the particle diameter of monoclinic zirconia micro mist is at 13 μ m-23 μ m, and above-mentioned four weight percent can be:
After the size limited proportion of each component is got off, can accurate contact area and the speed of reaction of controlling each component, make reaction more even.
The component particle diameter proportion of composing of each embodiment also can as mentioned above, repeat no more below.
Embodiment 2
A kind of two steps add the preparation method of the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol, the electric smelting calcium oxide PSZ particle that is 35% by weight percent, 25% electric smelting calcium oxide PSZ fine powder, 30% monocline desilicated zirconia micro mist, 10% monoclinic zirconia micro mist constitutive material, add and account for the water-ground limestone of raw material gross weight 2% 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 and account for the bonding agent that the zirconia sol, resol, water, starch of material gross weight 4% form, in bonding agent, the ratio of each component is: 50% zirconia sol, 2% resol, 40% water, 8% starch, 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 goods that thickness is larger.
Its preparation process is as follows:
1) whole raw materials are put into mixer and be dry mixed 3 minutes, then add and take zirconia sol as main bonding agent wet mixing 4 minutes;
2) by gained mixture ageing mixture mechanical pressing after 12 hours, forming pressure is 560Mpa, and under 105 ± 5 ℃ of conditions, dry 24h burns till 5 hours at 1780 ℃ of temperature;
3) burnt product is put into zirconium colloidal sol and vacuumized immersion 5h, dry, finally at 500 ℃ of temperature, heat-treat 10 hours, obtain two steps and add the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol.
Zirconia metering nozzle prepared by the present embodiment, main physical and chemical index is: zirconium white weight ratio=96%, volume density is 5.4g/cm
3, cold crushing strength=220MPa, thermal shock resistance (1100 ℃, water-cooled)=9 times, can reach 27 hours work-ing life.
Embodiment 3
A kind of two steps add the preparation method of the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol, the electric smelting calcium oxide PSZ particle that is 45% by weight percent, 10% electric smelting calcium oxide PSZ fine powder, 35% monocline desilicated zirconia micro mist, 10% monoclinic zirconia micro mist constitutive material, add the yttrium oxide, water-ground limestone and the light calcium carbonate that account for raw material gross weight 3% as stablizer, in stablizer, the ratio of each component is: 5% yttrium oxide, 45% water-ground limestone, 50% light calcium carbonate; And then add and account for the bonding agent that the zirconia sol, water, pulp powder of material gross weight 5% form, in bonding agent, the ratio of each component is: 80% zirconia sol, 17% water, 3% pulp powder, the solid phase weight content of zirconia sol is 2%.
Its preparation process is as follows:
1) whole raw materials are put into mixer and be dry mixed 5 minutes, then add and take zirconia sol as main bonding agent wet mixing 4 minutes;
2) by gained mixture ageing mixture mechanical pressing after 14 hours, forming pressure is 600MPa, and under 105 ± 5 ℃ of conditions, dry 24h burns till 5 hours at 1750 ℃ of temperature;
3) burnt product is put into zirconium colloidal sol and vacuumized immersion 4h, dry, finally at 500 ℃ of temperature, heat-treat 12 hours, obtain two steps and add the toughness reinforcing enhancing zirconia metering nozzle of zirconium colloidal sol.
Zirconia metering nozzle prepared by the present embodiment, main physical and chemical index is: zirconium white weight ratio=95%, volume density is 5.2g/cm
3, cold crushing strength=210MPa, thermal shock resistance (1100 ℃, water-cooled)=8 times, can reach 26 hours work-ing life.
Following examples adopt the identical preparation method of embodiment mono-to three, shown in the concrete table composed as follows of each component.
In above-described embodiment, the component of stablizer and weight percent are as shown in the table.
| ? | Yttrium oxide | Water-ground limestone | Light calcium carbonate | Magnesiumcarbonate |
| Embodiment tetra- | — | — | — | 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 are 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 of making has rational compactness extent and excellent performance.
The zirconia metering nozzle that above embodiment tetra-to embodiment ten prepares, its main physical and chemical index is: zirconium white weight ratio>=95%, volume density is 5.0～5.5g/cm
3, cold crushing strength>=200MPa, thermal shock resistance (1100 ℃, 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 modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. two steps add a zirconia metering nozzle preparation method for zirconium colloidal sol, it is characterized in that, comprise batch mixing, compression moulding and dryly burn 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 dryly burn till step and obtain burnt product;
C, burnt product is put into zirconium colloidal sol vacuumize and soak 1～5h, then through Overheating Treatment, can make two steps and add the toughness reinforcing enhancing zirconia metering nozzle of 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 weight percent of described bonding agent component and each component is:
。
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 zirconium colloidal sol is zirconia sol.
4. a kind of two steps according to claim 3 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%.
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, described stablizer is at least one in yttrium oxide, water-ground limestone, light calcium carbonate, magnesiumcarbonate.
6. a kind of two steps according to claim 2 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%.
7. 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 compression moulding and dry burn till step and be: dry 24h under 105 ± 5 ℃ of conditions, at 1700-1800 ℃ of temperature, burn till after 5 hours, obtain burnt product.
8. 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 to heat-treat 8-12 hour at 450-600 ℃ of temperature.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106007743A (en) * | 2016-05-13 | 2016-10-12 | 西安建筑科技大学 | Method for preparing 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106007743A (en) * | 2016-05-13 | 2016-10-12 | 西安建筑科技大学 | Method for preparing zirconium oxide metering 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 |
| CN116768620B (en) * | 2023-06-05 | 2024-06-07 | 长江师范学院 | Steel slag erosion resistant sizing nozzle and preparation method and application thereof |
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