CN111732416A - Ultralow-carbon magnesia carbon brick with excellent oxidation resistance and stripping resistance for ladle lining and preparation method thereof - Google Patents
Ultralow-carbon magnesia carbon brick with excellent oxidation resistance and stripping resistance for ladle lining and preparation method thereof Download PDFInfo
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- CN111732416A CN111732416A CN202010883042.XA CN202010883042A CN111732416A CN 111732416 A CN111732416 A CN 111732416A CN 202010883042 A CN202010883042 A CN 202010883042A CN 111732416 A CN111732416 A CN 111732416A
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 238
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 154
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 120
- 239000011449 brick Substances 0.000 title claims abstract description 65
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 51
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910007948 ZrB2 Inorganic materials 0.000 claims abstract description 39
- 239000005011 phenolic resin Substances 0.000 claims abstract description 39
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000010426 asphalt Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000004901 spalling Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000001095 magnesium carbonate Substances 0.000 claims description 16
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 16
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 16
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 17
- 239000010959 steel Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 3
- 239000010935 stainless steel Substances 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 36
- 230000035939 shock Effects 0.000 description 19
- 238000003763 carbonization Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011819 refractory material Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000002893 slag Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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Abstract
The invention provides an ultra-low carbon magnesia carbon brick for a ladle lining with excellent oxidation resistance and stripping resistance and a preparation method thereof, wherein the preparation raw materials comprise the following components in parts by mass: 70-120 parts of fused magnesia, 0.5-8 parts of graphite, 0.8-8 parts of liquid phenolic resin, 0.1-5 parts of carbon-containing resin powder and ZrB20.5-8 parts of-SiC complex phase material and 0.1-5 parts of high-temperature asphalt. The ultra-low carbon magnesia carbon brick for the steel ladle lining has good oxidation resistance and stripping resistance, can meet the smelting requirements of clean steel, ultra-low carbon steel and stainless steel, and has very excellent use effect.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to an ultra-low carbon magnesia carbon brick for a ladle lining with excellent oxidation resistance and stripping resistance and a preparation method thereof.
Background
The ladle, i.e. the ladle, is a container for holding molten steel in the steel industry, is made of steel, is internally provided with refractory bricks, and the molten steel flows out from a port at the bottom of the ladle for casting. The ladle is used for receiving molten steel and pouring in front of an open hearth furnace, an electric furnace or a converter in a steel plant and a foundry. The ladle is an important thermal device in a steel plant, the structure of the ladle consists of a metal shell, a lining refractory material, a ladle nozzle and the like, the selection of the lining material of the ladle is very important, and the service life of the ladle not only relates to the consumption of the refractory material and the steel-making cost, but also directly influences the yield and the quality of steel.
The magnesia carbon refractory material is a carbon composite refractory material with excellent characteristics of graphite and magnesia, has excellent erosion resistance and thermal shock resistance, and is widely used as a furnace lining material on a converter, an electric furnace and a refined steel ladle. In the using process, slag is easy to permeate into the refractory material, so that the slag corrosion resistance of the refractory material is obviously reduced, and meanwhile, the slag permeates and reacts with oxide refractory components in the refractory material, so that the surface layer of the refractory material is easy to sinter, and the thermal shock stability is reduced.
With the development of clean steel technology, the refractory material is required to have low carbon content, good erosion resistance, good stability and good molten steel or slag dissolution and permeability resistance in the using process, so that the pollution to molten steel is reduced as much as possible, and the carburetion and inclusion are reduced. However, the surface of the refractory material with low carbon content is easy to oxidize and decarbonize in the using process, and once decarbonization is carried out, sintering is easily generated among the components of the refractory material due to the infiltration of slag, so that the thermal shock stability of the refractory material is obviously reduced.
Disclosure of Invention
The invention aims to provide the ultralow-carbon magnesia carbon brick for the ladle lining and the preparation method thereof, wherein the ultralow-carbon magnesia carbon brick has excellent oxidation resistance and stripping resistance, can meet the requirements of smelting clean steel, ultralow-carbon steel and stainless steel, and has excellent use effects.
In order to solve the problems, the invention provides an ultra-low carbon magnesia carbon brick for a ladle lining, which has excellent oxidation resistance and stripping resistance, and the preparation raw materials of the brick comprise the following components in parts by mass:
70-120 parts of fused magnesia, 0.5-8 parts of graphite, 0.8-8 parts of liquid phenolic resin, 0.1-5 parts of carbon-containing resin powder and ZrB20.5-8 parts of-SiC complex phase material and 0.1-5 parts of high-temperature asphalt.
Wherein ZrB2the-SiC complex phase material is formed by ZrB2The multiphase structure composed of the phase and the SiC phase serves as an antioxidant in the raw material. Wherein ZrB2Has higher thermal conductivity and elastic modulus, thus has relatively better thermal shock stability, but single-phase ZrB2Has relatively poor oxidation resistance, and the oxidation resistance is closely related to the use temperature. When the temperature is lower than 1100 ℃, the surface of boride is oxidized to generate B2O3The melting layer improves the oxidation resistance of the material; and above 1100 deg.C, liquid B2O3The evaporation is faster and the barrier effect is greatly reduced, resulting in a significant decrease in oxidation resistance. The ZrB can be obviously improved by introducing the SiC phase2The oxidation resistance of the material is mainly due to the fact that a layer of adhered borosilicate glass phase is formed on the surface of the material after SiC is introduced, and the material is effectiveInhibits further diffusion of oxygen within the material.
The liquid phenolic resin and the carbon-containing resin powder are used as binding agents, and if the single phenolic resin is used as the binding agent and carbonized at high temperature, the phenolic resin exists in the material in a glassy carbon form, so that the toughness is not enough, and the thermal shock stability of the material is reduced; and after the single carbon-containing resin powder is used as a bonding agent and carbonized at high temperature, the liquid phase has high viscosity and is in a non-flowing state and a mosaic structure, so that isotropic homogeneous carbon is formed, and compared with anisotropic carbon, the isotropic carbon shrinks by 90 percent and 5 percent, so that high-strength compact carbon is formed. When the carbon-containing resin powder and the phenolic resin are used as the binding agent to be mixed and carbonized, an embedded structure is formed on the interface of a carbonized tissue, and the binding strength of the material is improved.
Wherein, the high-temperature asphalt has the functions of improving the bonding strength of the material and having high carbon residue rate after carbonization. The high-temperature pitch and phenolic resin can form a composite binder, and a mixed structure of homogeneous carbon and graphitized carbon is formed after heat treatment. The carbonization process of the phenolic resin is solid-phase carbonization, and the intermediate does not undergo a liquid phase, so that amorphous pyrolytic carbon is directly formed; the carbonization process of the asphalt is liquid-phase carbonization, and a flowing liquid phase formed in the carbonization process interacts with the solid-phase carbonization of the phenolic resin, so that the binding phase is of a porous mosaic structure, and the strength is improved.
Preferably, the preparation raw materials comprise the following components in parts by weight:
88-95 parts of fused magnesia, 1-4 parts of graphite, 1.5-4 parts of liquid phenolic resin, 0.5-2 parts of carbon-containing resin powder and ZrB21-5 parts of-SiC complex phase material and 0.5-2 parts of high-temperature asphalt.
Further preferably, the preparation raw materials comprise, by mass:
92 parts of fused magnesia, 2 parts of graphite, 3 parts of liquid phenolic resin, 2 parts of carbon-containing resin powder and ZrB23 parts of-SiC complex phase material and 1 part of high-temperature asphalt.
Preferably, said ZrB2In the-SiC multiphase material, the volume fraction of SiC is 15% -25%, ZrB2The volume fraction of (A) is 75-85%.
Preferably, the fused magnesite comprises, by mass:
20-35 parts of fused magnesite with the grade of 5-3mm, 25-35 parts of fused magnesite with the grade of 3-1mm, 10-25 parts of fused magnesite with the grade of 1-0.074mm and 15-25 parts of fused magnesite with the grade of 0.074 mm;
the content of magnesium oxide in the fused magnesia is more than 97.2 percent.
Preferably, the graphite is one or a combination of several of graphite with the specification of-190, -193, -194, -197 and-198;
the carbon content in the graphite is > 96%.
Preferably, the liquid phenolic resin has a viscosity of not less than 1200 mPa · s at 25 ℃ or lower.
Another aspect of the present invention provides a method for preparing the ultra-low carbon magnesia carbon brick for a ladle lining, which has excellent oxidation resistance and spalling resistance, comprising the steps of:
the preparation raw materials are mixed, then formed and subjected to heat treatment to obtain the ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and spalling resistance.
Preferably, the method specifically comprises the following steps:
s1, mixing the fused magnesite with the size fraction of 5-3mm, the fused magnesite with the size fraction of 3-1mm and the fused magnesite with the size fraction of 1-0.074 mm;
s2, adding liquid phenolic resin into the mixture obtained in the step S1, and mixing;
s3, adding graphite into the mixture obtained in the step S2, and mixing;
s4, mixing the fused magnesia with the grain size of 0.074mm, carbon-containing resin powder and ZrB2Mixing and co-grinding the-SiC complex phase material and high-temperature asphalt to obtain fine powder;
s5, adding the fine powder obtained in the step S4 into the mixture obtained in the step S3, and mixing;
s6, placing the mixture obtained in the step S5 into a mould for forming;
and S7, performing heat treatment on the product molded in the step S6 to obtain the ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and spalling resistance.
Preferably, in step S6, the mixture is molded by using a brick press, which is a 630T or 1000T electric screw brick press.
Preferably, in step S7, a heat treatment kiln is used to perform heat treatment on the molded product, wherein the temperature inside the heat treatment kiln is 160-240 ℃ and the treatment time is 12-32 h. .
Compared with the prior art, the invention has the following beneficial effects:
1. the ultralow-carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance is prepared by adding ZrB into the raw materials2-SiC complex phase material as antioxidant material, wherein ZrB2Has higher thermal conductivity and elastic modulus, thus has relatively better thermal shock stability, but single-phase ZrB2Has relatively poor oxidation resistance, and the oxidation resistance is closely related to the use temperature. When the temperature is lower than 1100 ℃, the surface of boride is oxidized to generate B2O3The melting layer improves the oxidation resistance of the material; and above 1100 deg.C, liquid B2O3The evaporation is faster and the barrier effect is greatly reduced, resulting in a significant decrease in oxidation resistance. The ZrB can be obviously improved by introducing the SiC phase2The oxidation resistance of the material is mainly because a layer of adhered borosilicate glass phase is formed on the surface of the material after the SiC is introduced, so that the further diffusion of oxygen in the material is effectively inhibited;
2. according to the ultralow-carbon magnesia carbon brick for the ladle lining, which is excellent in oxidation resistance and stripping resistance, liquid phenolic resin and carbon-containing resin powder in the raw materials are used as binding agents, and if the phenolic resin is used as the binding agent alone and carbonized at high temperature, the phenolic resin exists in the material in a glassy carbon form, so that the toughness is not enough, and the thermal shock stability of the material is reduced; and after the single carbon-containing resin powder is used as a bonding agent and carbonized at high temperature, the liquid phase has high viscosity and is in a non-flowing state and a mosaic structure, so that isotropic homogeneous carbon is formed, and compared with anisotropic carbon, the isotropic carbon shrinks by 90 percent and 5 percent, so that high-strength compact carbon is formed. When the carbon-containing resin powder and the phenolic resin are used as the binding agent to be mixed and carbonized, an embedded structure is formed on the interface of a carbonized tissue, and the binding strength of the material is improved.
3. The ultralow-carbon magnesia carbon brick for the ladle lining, which has excellent oxidation resistance and stripping resistance, has the advantages that the high-temperature asphalt has the effect of improving the bonding strength of the material, and the carbon residue rate after carbonization is high. The high-temperature pitch and phenolic resin can form a composite binder, and a mixed structure of homogeneous carbon and graphitized carbon is formed after heat treatment. The carbonization process of the phenolic resin is solid-phase carbonization, and the intermediate does not undergo a liquid phase, so that amorphous pyrolytic carbon is directly formed; the carbonization process of the asphalt is liquid-phase carbonization, and a flowing liquid phase formed in the carbonization process interacts with the solid-phase carbonization of the phenolic resin, so that the binding phase is of a porous mosaic structure, and the strength is improved.
4. The ultralow-carbon magnesia carbon brick for the ladle lining, which has excellent oxidation resistance and stripping resistance, has good oxidation resistance and stripping resistance under the condition of low carbon content, can meet the requirements of smelting of clean steel, ultralow-carbon steel and stainless steel, and has very excellent use effect, and under the preferable raw material formula, the volume density of the ultralow-carbon magnesia carbon brick is more than or equal to 3.12g/cm3The apparent porosity (× 24h at 200 ℃) is less than or equal to 3.8 percent, the normal-temperature compressive strength (× 24h at 200 ℃) is more than or equal to 82MPa, the high-temperature rupture strength (× 0.5h at 1400 ℃) is more than or equal to 18.2MPa, and the retention rate of the thermal shock residual strength is more than or equal to 15.4 percent.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the content of magnesia in fused magnesia is more than 97.2%; the carbon content in the graphite is more than 96 percent; the liquid phenolic resin has a viscosity of not less than 1200 mPas at 25 ℃.
Example 1
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 18 parts of fused magnesia with the grain size of 0.074mm, 1904 parts of graphite, 3 parts of liquid phenolic resin, 2 parts of carbon-containing resin powder, ZrB25 parts of-SiC complex phase material and 2 parts of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 75% by volume; the volume fraction of SiC was 25%.
The preparation method of the ultralow-carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following steps of:
s1, dry-mixing 5-3mm, 3-1mm and 1-0.074mm fused magnesite in parts by weight for about 1 minute;
s2, uniformly and slowly adding weighed liquid phenolic resin into the mixture obtained in the step S1, and mixing for about 2 minutes;
s3, adding graphite into the mixture obtained in the step S2 for about 3 minutes, and mixing;
s4, mixing the fused magnesia with the grain size of 0.074mm, carbon-containing resin powder and ZrB2Mixing and co-grinding the-SiC complex phase material and high-temperature asphalt to obtain fine powder;
s5, adding the fine powder obtained in the step S4 into the mixture obtained in the step S3, mixing for 15-20 minutes, and discharging after the inspection is qualified;
s6, putting the mixture obtained in the step S5 into a mould, and molding on a 630T or 1000T electric spiral brick press according to the variety and the shape of the brick;
and S7, pushing the green brick molded in the step S6 into a heat treatment kiln for heat treatment, wherein the temperature inside the heat treatment kiln is 180 ℃, and the treatment time is 24 hours, so that the ultralow-carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and spalling resistance is obtained.
Example 2
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 20 parts of fused magnesia with the grain size of 0.074mm, 1933 parts of graphite, 3 parts of liquid phenolic resin, 1 part of carbon-containing resin powder, ZrB24 parts of-SiC complex phase material and 2 parts of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 85% by volume; the volume fraction of SiC was 15%.
The preparation method of the ultra-low carbon magnesia carbon brick for a ladle liner having excellent oxidation resistance and spalling resistance of the present example was the same as that of example 1.
Example 3
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 22 parts of fused magnesia with the grain size of 0.074mm, graphite-1942 parts, 3 parts of liquid phenolic resin, 2 parts of carbon-containing resin powder, ZrB23 parts of-SiC complex phase material and 1 part of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 80% by volume; the volume fraction of SiC was 20%.
The preparation method of the ultra-low carbon magnesia carbon brick for a ladle liner having excellent oxidation resistance and spalling resistance of the present example was the same as that of example 1.
Example 4
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 24 parts of fused magnesia with the grain size of 0.074mm, 1901 parts of graphite, 3 parts of liquid phenolic resin, 1 part of carbon-containing resin powder, ZrB23 parts of-SiC complex phase material and 1 part of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 78%; the volume fraction of SiC was 22%.
The preparation method of the ultra-low carbon magnesia carbon brick for a ladle liner having excellent oxidation resistance and spalling resistance of the present example was the same as that of example 1.
Example 5
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
20 parts of fused magnesia with the grain size of 5-3mm, 35 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 25 parts of fused magnesia with the grain size of 0.074mm, 1904 parts of graphite, 1.5 parts of liquid phenolic resin, 2 parts of carbon-containing resin powder, ZrB21 part of-SiC complex phase material and 0.5 part of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 82% by volume; the volume fraction of SiC was 18%.
The preparation method of the ultra-low carbon magnesia carbon brick for a ladle liner having excellent oxidation resistance and spalling resistance of the present example was the same as that of example 1.
Example 6
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
30 parts of fused magnesia with the grain size of 5-3mm, 25 parts of fused magnesia with the grain size of 3-1mm, 20 parts of fused magnesia with the grain size of 1-0.074mm, 15 parts of fused magnesia with the grain size of 0.074mm, 1901 parts of graphite, 4 parts of liquid phenolic resin, 0.5 part of carbon-containing resin powder, ZrB22 parts of-SiC complex phase material and 2 parts of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 80% by volume; the volume fraction of SiC was 20%.
The preparation method of the ultra-low carbon magnesia carbon brick for a ladle liner having excellent oxidation resistance and spalling resistance of the present example was the same as that of example 1.
Example 7
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
20 parts of fused magnesia with the grain size of 5-3mm, 25 parts of fused magnesia with the grain size of 3-1mm, 10 parts of fused magnesia with the grain size of 1-0.074mm, 15 parts of fused magnesia with the grain size of 0.074mm, 1900.5 parts of graphite, 0.8 part of liquid phenolic resin, 5 parts of carbon-containing resin powder, ZrB20.5 part of-SiC complex phase material and 5 parts of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 78%; the volume fraction of SiC was 22%.
The preparation method of the ultra-low carbon magnesia carbon brick for a ladle liner having excellent oxidation resistance and spalling resistance of the present example was the same as that of example 1.
Example 8
The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance, which is described in the embodiment, comprises the following preparation raw materials in parts by mass:
35 parts of fused magnesia with the grain size of 5-3mm, 35 parts of fused magnesia with the grain size of 3-1mm, 25 parts of fused magnesia with the grain size of 1-0.074mm, 25 parts of fused magnesia with the grain size of 0.074mm, 1908 parts of graphite, 8 parts of liquid phenolic resin, 0.1 part of carbon-containing resin powder, ZrB28 parts of-SiC complex phase material and 0.1 part of high-temperature asphalt; wherein ZrB2ZrB in-SiC complex phase material2Is 78%; the volume fraction of SiC was 22%.
The preparation method of the ultra-low carbon magnesia carbon brick for a ladle liner having excellent oxidation resistance and spalling resistance of the present example was the same as that of example 1.
Comparative example 1
The low-carbon magnesia carbon brick of the comparative example is prepared from the following raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 18 parts of fused magnesia with the grain size of 0.074mm, 1904 parts of graphite, 3 parts of liquid phenolic resin, 2 parts of carbon-containing resin powder and 2 parts of high-temperature asphalt, and the preparation method is the same as that of the example 1.
Comparative example 2
The low-carbon magnesia carbon brick of the comparative example is prepared from the following raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 18 parts of fused magnesia with the grain size of 0.074mm, 1904 parts of graphite, 3 parts of liquid phenolic resin, 2 parts of carbon-containing resin powder, ZrB25 parts of high-temperature asphalt and 2 parts of high-temperature asphalt; the preparation method is the same as that of example 1.
Comparative example 3
The low-carbon magnesia carbon brick of the comparative example is prepared from the following raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 18 parts of fused magnesia with the grain size of 0.074mm, 1904 parts of graphite, 3 parts of liquid phenolic resin, 2 parts of carbon-containing resin powder, ZrB25 parts of a mixture of SiC and 2 parts of high-temperature asphalt; the preparation method is the same as that of example 1. Wherein ZrB2ZrB in mixture with SiC2Is 75% by volume and the volume fraction of SiC is 25%.
Comparative example 4
The low-carbon magnesia carbon brick of the comparative example is prepared from the following raw materials in parts by mass:
25 parts of fused magnesia with the grain size of 5-3mm, 30 parts of fused magnesia with the grain size of 3-1mm, 15 parts of fused magnesia with the grain size of 1-0.074mm, 18 parts of fused magnesia with the grain size of 0.074mm, 1904 parts of graphite, 3 parts of liquid phenolic resin, ZrB25 parts of-SiC complex phase material and 2 parts of high-temperature asphalt; the preparation method is the same as that of example 1.
Determination of physical and chemical indexes of ultra-low carbon magnesia carbon brick for steel ladle lining
The volume density, the apparent porosity, the compressive strength, the breaking strength and the thermal shock stability of the ultra-low carbon magnesia carbon brick for the ladle lining obtained in each example and the comparative example are measured, wherein the method for measuring the retention rate of the thermal shock residual strength comprises the following steps: cutting sample blocks of the pressure-resistant standard brick with the size of 65mm multiplied by 65mm, and respectively detecting the pressure resistance before thermal shock and the residual pressure resistance after 1 time of air-cooling thermal shock, wherein the residual pressure resistance after 1 time of air-cooling thermal shock/the pressure resistance before thermal shock is 100% = the residual strength retention rate after shock. The measurement results are shown in Table 1.
ZrB was not added to the ultra-low carbon magnesia carbon brick for ladle lining of comparative example 12The compressive strength, the breaking strength, the thermal shock stability and the oxidation resistance of the-SiC complex phase material are poor; ZrB was added in comparative example 22Its oxidation resistance is still poor; ZrB was added in comparative example 32Physical mixing of a mixture with SiC alone is not effective in ZrB when slag is formed2The surface forms an adhesive borosilicate glass phase to inhibit further diffusion of oxygen, so that the compression strength, the breaking strength, the thermal shock stability and the oxidation resistance of the magnesia carbon brick of the comparative example are reduced to some extent, and ZrB can not be fully exerted2And the role of SiC; in comparative example 4, only the liquid phenolic resin is added, and the carbon-containing resin is not added, so that the compressive strength and the flexural strength are poorer than those of example 1; the ultralow-carbon magnesia carbon brick for the ladle lining, which has excellent oxidation resistance and stripping resistance, has good normal-temperature compressive strength, good high-temperature rupture strength and strong thermal shock stability. Wherein, the preferred formulations of examples 1-6 yield products having a bulk density of 3.12g/cm or greater3The apparent porosity (× 24h at 200 ℃) is less than or equal to 3.8%, the normal-temperature compressive strength (× 24h at 200 ℃) is more than or equal to 82MPa, the high-temperature breaking strength (× 0.5.5 h at 1400 ℃) is more than or equal to 18.2MPa, and the retention rate of the thermal shock residual strength is more than or equal to 15.4%.
TABLE 1
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and stripping resistance is characterized by comprising the following preparation raw materials in parts by weight:
70-120 parts of fused magnesia, 0.5-8 parts of graphite, 0.8-8 parts of liquid phenolic resin, 0.1-5 parts of carbon-containing resin powder and ZrB20.5-8 parts of-SiC complex phase material and 0.1-5 parts of high-temperature asphalt.
2. The ultra-low carbon magnesia carbon brick for the ladle lining, which has excellent oxidation resistance and stripping resistance, according to claim 1, is characterized in that the preparation raw materials comprise the following components in parts by mass:
88-95 parts of fused magnesia, 1-4 parts of graphite, 1.5-4 parts of liquid phenolic resin, 0.5-2 parts of carbon-containing resin powder and ZrB21-5 parts of-SiC complex phase material and 0.5-2 parts of high-temperature asphalt.
3. The ultra-low carbon magnesia carbon brick for ladle lining excellent in oxidation resistance and spalling resistance according to claim 1, wherein:
the ZrB2In the-SiC multiphase material, the volume fraction of SiC is 15% -25%, ZrB2The volume fraction of (A) is 75-85%.
4. The ultra-low carbon magnesia carbon brick for the ladle lining, which has excellent oxidation resistance and spalling resistance, according to claim 1, wherein the fused magnesia comprises the following components in parts by mass:
20-35 parts of fused magnesite with the grade of 5-3mm, 25-35 parts of fused magnesite with the grade of 3-1mm, 10-25 parts of fused magnesite with the grade of 1-0.074mm and 15-25 parts of fused magnesite with the grade of 0.074 mm;
the content of magnesium oxide in the fused magnesia is more than 97.2 percent.
5. The ultra-low carbon magnesia carbon brick for ladle lining excellent in oxidation resistance and spalling resistance according to claim 1, wherein:
the graphite is one or a combination of several of graphite with the specifications of-190, -193, -194, -197 and-198;
the carbon content in the graphite is > 96%.
6. The ultra-low carbon magnesia carbon brick for ladle lining excellent in oxidation resistance and spalling resistance according to claim 1, wherein:
the viscosity of the liquid phenolic resin is not lower than 1200 mPa & s at the temperature of below 25 ℃.
7. A method for preparing the ultra-low carbon magnesia carbon brick for ladle lining excellent in oxidation resistance and spalling resistance according to any one of claims 1 to 6, comprising the steps of:
the preparation raw materials are mixed, then formed and subjected to heat treatment to obtain the ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and spalling resistance.
8. The method for preparing the ultra-low carbon magnesia carbon brick for the ladle lining, which has excellent oxidation resistance and spalling resistance, according to claim 7, is characterized by comprising the following steps:
s1, mixing the fused magnesite with the size fraction of 5-3mm, the fused magnesite with the size fraction of 3-1mm and the fused magnesite with the size fraction of 1-0.074 mm;
s2, adding liquid phenolic resin into the mixture obtained in the step S1, and mixing;
s3, adding graphite into the mixture obtained in the step S2, and mixing;
s4, mixing the fused magnesia with the grain size of 0.074mm, carbon-containing resin powder and ZrB2Mixing and co-grinding the-SiC complex phase material and high-temperature asphalt to obtain fine powder;
s5, adding the fine powder obtained in the step S4 into the mixture obtained in the step S3, and mixing;
s6, placing the mixture obtained in the step S5 into a mould for forming;
and S7, performing heat treatment on the product molded in the step S6 to obtain the ultra-low carbon magnesia carbon brick for the ladle lining with excellent oxidation resistance and spalling resistance.
9. The method for preparing the ultra-low carbon magnesia carbon brick for the ladle liner with excellent oxidation resistance and spalling resistance according to claim 8, wherein the method comprises the following steps:
in step S6, a brick press is used to mold the mixture, where the brick press is a 630T or 1000T electric spiral brick press.
10. The method for preparing the ultra-low carbon magnesia carbon brick for the ladle liner with excellent oxidation resistance and spalling resistance according to claim 8, wherein the method comprises the following steps:
in the step S7, a heat treatment kiln is adopted to carry out heat treatment on the molded product, wherein the temperature in the heat treatment kiln is 160-240 ℃ during the heat treatment, and the treatment time is 12-32 h.
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| CN112500137A (en) * | 2021-02-05 | 2021-03-16 | 北京利尔高温材料股份有限公司 | Ladle anti-erosion magnesia refractory mortar and preparation method thereof |
| CN113461407A (en) * | 2021-09-02 | 2021-10-01 | 北京利尔高温材料股份有限公司 | Low-carbon magnesia carbon brick with oxidation resistance and preparation method thereof |
| CN113461407B (en) * | 2021-09-02 | 2022-01-07 | 北京利尔高温材料股份有限公司 | A kind of low-carbon magnesia-carbon brick with anti-oxidation performance and preparation method thereof |
| CN114180954A (en) * | 2022-02-15 | 2022-03-15 | 北京利尔高温材料股份有限公司 | Environment-friendly low-carbon aluminum-magnesium spinel brick and preparation method thereof |
| CN114180941A (en) * | 2022-02-15 | 2022-03-15 | 北京利尔高温材料股份有限公司 | Oxidation-resistant low-carbon magnesia carbon brick and preparation method thereof |
| CN114180954B (en) * | 2022-02-15 | 2022-05-17 | 北京利尔高温材料股份有限公司 | Environment-friendly low-carbon aluminum-magnesium spinel brick and preparation method thereof |
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Inventor after: Liu Li Inventor after: Zhao Xiantang Inventor after: He Feng Inventor after: Guo Yulong Inventor after: Zhang Han Inventor after: Zhao Jizeng Inventor after: Zhao Wei Inventor after: Yan Hao Inventor after: Ren Lin Inventor after: Liu Jingxuan Inventor before: Liu Li Inventor before: Guo Yulong Inventor before: Zhang Han Inventor before: Zhao Jizeng Inventor before: Zhao Wei Inventor before: Yan Hao Inventor before: Ren Lin Inventor before: Liu Jingxuan Inventor before: Zhao Xiantang |
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