CN115650742B - Preparation method of metal-containing Al in-situ composite carbon-containing refractory material - Google Patents
Preparation method of metal-containing Al in-situ composite carbon-containing refractory material Download PDFInfo
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Abstract
The invention belongs to the technical field of refractory material preparation, and mainly provides a preparation method of a metal-containing Al in-situ composite carbon-containing refractory material. The preparation method of the Al-containing composite carbon-containing refractory material uses composite powder of zirconia@Al with a core-shell structure as a precursor, adds the precursor containing 3-12wt% of zirconia@Al with the core-shell structure into the carbon-containing refractory material, and avoids Al by high-temperature heat treatment under the protection of nitrogen atmosphere 4 C 3 In addition, an aluminum-containing compound is synthesized in situ in the carbon-containing refractory material to form a ceramic bonding phase mainly containing the aluminum-containing compound, so that the bonding strength of the material is improved. The invention utilizes the oxide to completely coat Al to avoid the generation of aluminum carbide; by utilizing the low-temperature reaction characteristic of metallic aluminum, the metallic aluminum is combined with nitrogen and oxygen in the atmosphere at a lower temperature to generate aluminum-containing chemical compounds, and a ceramic bonding phase is added on the basis of carbon bonding; the material prepared by the method not only can improve the characteristic of low strength of the material after oxidation, but also can improve the high-temperature performance of the material and improve the molten steel scouring resistance of the material.
Description
Technical Field
The invention belongs to the technical field of refractory material preparation, and mainly provides a preparation method of a metal-containing Al in-situ composite carbon-containing refractory material.
Background
The carbon-containing refractory is a carbon-bonded refractory which is produced by using oxides and graphite as main raw materials and using an organic substance such as a phenolic resin as a binder. Because the oxide in the carbon-containing refractory material has the characteristics of high melting point, higher molten steel erosion resistance and the like; graphite has the characteristics of low thermal expansion, higher slag erosion resistance and the like, so that the material has excellent thermal shock resistance, erosion resistance and the like, and is widely used in continuous casting steel processes with harsh use conditions, such as long water gaps, immersed water gaps, integral stopper rods, sliding plates and the like, which are all carbon-containing refractory materials. However, carbonaceous refractory materials have a fatal disadvantage in that they are easily oxidized or dissolved in molten steel at high temperatures, forming a loose oxide layer on the surface of the material. When molten steel flows over the surface of the material, oxides on the surface are removed by the molten steel strip, graphite is exposed, and the two processes alternately occur, so that finally the carbon-containing refractory material is corroded. With the increase of alloy amount in steel, the molten steel scouring resistance of the material can not meet the actual production requirement; the steel erosion resistance of the material can be improved to some extent by reducing the carbon content, but this is achieved at the expense of the thermal shock resistance of the material. The carbon content cannot be reduced without limitation, and must be in a reasonable range, so that not only can the erosion resistance of the material be ensured, but also the material can be ensured to have higher thermal shock resistance. Another technical idea is to form a ceramic bonding phase in the material to improve the high temperature strength and further improve the scouring resistance. The metal Al is introduced into the carbon-containing refractory material to form a high-melting-point ceramic bonding phase, but aluminum carbide is formed after the metal Al is subjected to high-temperature heat treatment, and is a substance which is easy to hydrate and easy to cause expansion and cracking of the material; to solve this problem ZL200910066116.4 was prepared by reacting 3si+Al 4 C 3 +2N 2 The preparation method of the precursor is difficult to avoid contact of Al and carbon, and easily generates easily-hydratable aluminum carbide; both ZL201410434393.7 and ZL201911164211.8 propose the use of Al-containing composite powders coated with titanium oxide, but in either caseThe high-energy ball milling preparation or the gel casting preparation is simple in coating, the uniformity of a titanium oxide protective layer formed around Al is poor, in addition, the structure is easy to damage due to high-speed mixing, the easily hydrated aluminum carbide is difficult to avoid to be generated, and the production quality accident is easy to be caused.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of an Al-containing composite carbon-containing refractory material.
The invention adopts the technical proposal for accomplishing the purpose:
a preparation method of an Al-containing composite carbon-containing refractory material utilizes composite powder of zirconia@Al with a core-shell structure as a precursor, adds 3-12wt% of the precursor of zirconia@Al with the core-shell structure into the carbon-containing refractory material, and avoids Al by high-temperature heat treatment under the protection of nitrogen atmosphere 4 C 3 In addition, an aluminum-containing compound is synthesized in situ in the carbon-containing refractory material to form a ceramic bonding phase mainly containing the aluminum-containing compound, so that the bonding strength of the material is improved.
The preparation of the precursor comprises the following steps: the precursor is composite powder of zirconia@Al with a core-shell structure, al=is pre-oxidized for 30min at 400-500 ℃, a compact alumina layer is formed on the surface of Al, and surface modified Al powder is realized; then taking 1 part of Al powder, 10 parts of deionized water and 0.05 part of polyvinyl alcohol, and forming an Al suspension A through ultrasonic dispersion; 1 part of ZrOCl 2 ·8H 2 O,10 parts of deionized water and 2 parts of citric acid, and forming a solution B through strong stirring; slowly adding 1 part of A into 1-5 parts of B, stirring strongly, adjusting the pH value of the solution to 9.5 by using 0.1mol/l ammonia water, transferring to a reaction kettle, and carrying out hydrothermal reaction for 24 hours at 150 ℃; and taking out the reaction product, spray-drying, and then carrying out heat treatment for 1h at 450 ℃ to obtain the composite powder of the zirconia@Al with the core-shell structure.
The method is characterized in that: the carbon-containing refractory material is an alumina-graphite composite material, a zirconia-graphite composite material, a magnesia-graphite composite material and a magnesia-alumina spinel-graphite composite material.
According to the preparation method of the Al-containing composite carbon-containing refractory material, the oxide is used for completely coating the Al to avoid the generation of aluminum carbide; by utilizing the low-temperature reaction characteristic of metallic aluminum, the metallic aluminum is combined with nitrogen and oxygen in the atmosphere at a lower temperature to generate aluminum-containing chemical compounds, and a ceramic bonding phase is added on the basis of carbon bonding; the material prepared by the method not only can improve the characteristic of low strength of the material after oxidation, but also can improve the high-temperature performance of the material and improve the molten steel scouring resistance of the material.
Detailed Description
The invention will be described in detail with reference to specific examples:
example 1:
pre-oxidizing Al at 400 ℃ for 30min to form a compact alumina layer on the surface of Al, so as to realize surface modification; then taking 1 part of the powder, 10 parts of deionized water and 0.05 part of polyvinyl alcohol, and forming an Al suspension A through ultrasonic dispersion; 1 part of ZrOCl2.8H2O, 10 parts of deionized water and 2 parts of citric acid, and forming a solution B through strong stirring; slowly adding 1 part of A into 1 part of B, stirring strongly, adjusting the pH value of the solution to 9.5 by using 0.1mol/l ammonia water, transferring to a reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 24 hours; and taking out the reaction product, spray-drying, and then carrying out heat treatment for 1h at 450 ℃ to obtain the composite powder of the zirconia@Al with the core-shell structure.
Taking aluminum oxide and graphite as main raw materials, wherein the aluminum oxide content is 87wt%, the graphite content is 10wt%, 3wt% of composite powder of zirconia@Al with a core-shell structure is added, liquid phenolic resin is taken as a binding agent, the materials are mixed by a high-speed mixer and subjected to isostatic compaction under 120MPa, and finally, the materials are subjected to heat treatment in an atmosphere protection treatment furnace, wherein AlN and Al are contained in the aluminum oxide-graphite composite material after the heat treatment 2 OC is generated, and the high-temperature strength of the material is 11.2Mpa.
Example 2:
pre-oxidizing Al at 500 ℃ for 30min to form a compact alumina layer on the surface of Al, so as to realize surface modification; then taking 1 part of the powder, 10 parts of deionized water and 0.05 part of polyvinyl alcohol, and forming an Al suspension A through ultrasonic dispersion; 1 part of ZrOCl2.8H2O, 10 parts of deionized water and 2 parts of citric acid, and forming a solution B through strong stirring; slowly adding 1 part of A into 5 parts of B, stirring strongly, adjusting the pH value of the solution to 9.5 by using 0.1mol/l ammonia water, transferring to a reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 24 hours; and taking out the reaction product, spray-drying, and then carrying out heat treatment for 1h at 450 ℃ to obtain the composite powder of the zirconia@Al with the core-shell structure.
The preparation method comprises the steps of taking magnesia-alumina spinel and graphite as main raw materials, wherein the magnesia-alumina spinel contains 78wt% and the graphite contains 10wt%, adding composite powder of zirconia@Al with a core-shell structure and 12wt%, taking liquid phenolic resin as a binding agent, mixing by a high-speed mixer, carrying out isostatic compaction under 120MPa, and finally carrying out heat treatment in an atmosphere protection treatment furnace, wherein AlN and Al are contained in the magnesia-alumina spinel-graphite composite material after heat treatment 2 O 3 And Al 2 OC is generated, and the high-temperature strength of the material is 17.9Mpa.
Example 3:
pre-oxidizing Al at 500 ℃ for 30min to form a compact alumina layer on the surface of Al, so as to realize surface modification; then taking 1 part of the powder, 10 parts of deionized water and 0.05 part of polyvinyl alcohol, and forming an Al suspension A through ultrasonic dispersion; 1 part of ZrOCl 2 8H2O,10 parts of deionized water, 2 parts of citric acid, and forming a solution B by strong stirring; slowly adding 1 part of A into 2 parts of B, stirring strongly, adjusting the pH value of the solution to 9.5 by using 0.1mol/l ammonia water, transferring to a reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 24 hours; and taking out the reaction product, spray-drying, and then carrying out heat treatment for 1h at 450 ℃ to obtain the composite powder of the zirconia@Al with the core-shell structure.
The method comprises the steps of taking fused magnesia and graphite as main raw materials, wherein the magnesia content is 82wt%, the graphite content is 10wt%, 8wt% of composite powder of zirconia@Al with a core-shell structure is added, liquid phenolic resin is taken as a bonding agent, mixing by a high-speed mixer and isostatic pressing under 120MPa are carried out, finally, heat treatment is carried out in an atmosphere protection treatment furnace, and AlN and Al are contained in the magnesia-graphite composite material after the heat treatment 2 O 3 And Al 2 OC is generated, and the high-temperature strength of the material is 14.6Mpa.
Example 4:
pre-oxidizing Al at 500 ℃ for 30min to form a compact alumina layer on the surface of Al, so as to realize surface modification; then taking 1 part of the powder, 10 parts of deionized water and 0.05 part of polyvinyl alcohol, and forming an Al suspension A through ultrasonic dispersion; 1 part of ZrOCl 2 8H2O,10 parts of deionized water, 2 parts of citric acid, and forming a solution B by strong stirring; slowly adding 1 part of A into 2 parts of B, stirring strongly, adjusting the pH value of the solution to 9.5 by using 0.1mol/l ammonia water, transferring to a reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 24 hours; and taking out the reaction product, spray-drying, and then carrying out heat treatment for 1h at 450 ℃ to obtain the composite powder of the zirconia@Al with the core-shell structure.
The method comprises the steps of taking fused zirconia and graphite as main raw materials, wherein the zirconia content is 82wt%, the graphite content is 10wt%, 8wt% of composite powder of zirconia@Al with a core-shell structure is added, liquid phenolic resin is taken as a binding agent, mixing by a high-speed mixer and isostatic pressing under 120MPa are carried out, finally, heat treatment is carried out in an atmosphere protection treatment furnace, and AlN and Al are contained in the zirconia-graphite composite material after the heat treatment 2 O 3 And Al 2 OC is generated, and the high-temperature strength of the material is 14.8Mpa.
Claims (2)
1. A preparation method of an Al-containing composite carbon-containing refractory material utilizes composite powder of zirconia@Al with a core-shell structure as a precursor, adds 3-12wt% of the precursor of zirconia@Al with the core-shell structure into the carbon-containing refractory material, and avoids Al by high-temperature heat treatment under the protection of nitrogen atmosphere 4 C 3 In addition, an aluminum-containing compound is synthesized in situ in the carbon-containing refractory material to form a ceramic bonding phase mainly containing the aluminum-containing compound, so that the bonding strength of the material is improved; the preparation of the precursor comprises the following steps: the precursor is composite powder of zirconia@Al with a core-shell structure, firstly, al is pre-oxidized for 30min at 400-500 ℃, a compact alumina layer is formed on the surface of the Al, and surface modified Al powder is realized; then taking 1 part of surface modified Al powder, 10 parts of deionized water and 0.05 part of polyvinyl alcohol, and forming an Al suspension A through ultrasonic dispersion; 1 part of ZrOCl 2 ·8H 2 O,10 parts of deionized water and 2 parts of citric acid, and forming a solution B through strong stirring; slowly adding 1 part of A into 1-5 parts of B, stirring strongly, adjusting the pH value of the solution to 9.5 by using 0.1mol/l ammonia water, transferring to a reaction kettle, and carrying out hydrothermal reaction for 24 hours at 150 ℃; and taking out the reaction product, spray-drying, and then carrying out heat treatment for 1h at 450 ℃ to obtain the composite powder of the zirconia@Al with the core-shell structure.
2. The method for preparing the Al-containing composite carbon-containing refractory material according to claim 1, wherein: the carbon-containing refractory material is an alumina-graphite composite material, a zirconia-graphite composite material, a magnesia-graphite composite material and a magnesia-alumina spinel-graphite composite material.
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