CN112647007B - Titanium-magnesium aluminate spinel-brown corundum composite sliding plate and production method thereof - Google Patents
Titanium-magnesium aluminate spinel-brown corundum composite sliding plate and production method thereof Download PDFInfo
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- CN112647007B CN112647007B CN202010853940.0A CN202010853940A CN112647007B CN 112647007 B CN112647007 B CN 112647007B CN 202010853940 A CN202010853940 A CN 202010853940A CN 112647007 B CN112647007 B CN 112647007B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/14—Closures
- B22D41/22—Closures sliding-gate type, i.e. having a fixed plate and a movable plate in sliding contact with each other for selective registry of their openings
- B22D41/28—Plates therefor
- B22D41/30—Manufacturing or repairing thereof
- B22D41/32—Manufacturing or repairing thereof characterised by the materials used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
Abstract
The invention relates to a titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate and a production method thereof, and the titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate comprises the following raw materials in percentage by weight: 35-65% of brown fused alumina, 4-8% of activated alumina micropowder, 10-38% of magnesium aluminate spinel, 5-15% of metal titanium, 5-10% of metal aluminum, and 3-5% of phenolic resin as a bonding agent. During production, the raw materials are weighed according to the proportion, evenly mixed, kneaded to obtain pug, then molded by machine pressing, dried for 24-48 h at 180-250 ℃, hooped, ground and coated to obtain the product of the invention. The method does not need high-temperature sintering or asphalt impregnation, is energy-saving and environment-friendly, has low production cost, and the prepared product has good oxidation resistance, thermal shock stability and erosion resistance, wherein the apparent porosity is 3-8%, and the bulk density is 3.05-3.20 g/cm 3 And the normal-temperature compressive strength is 120-200 MPa, and the high-temperature bending strength (1450 ℃ for 0.5h) is 25-60 MPa.
Description
Technical Field
The invention relates to a Ti-magnesia-alumina spinel-brown fused alumina composite sliding plate and a production method thereof, belonging to the technical field of refractory materials.
Background
The mainstream products of the sliding plate brick at present are aluminum carbon and aluminum zirconium carbon sliding plates, and the preparation process comprises two preparation processes of non-firing and high-temperature firing, wherein the non-firing sliding plate brick is mainly used for medium and small steel ladles and smelting common steel grades, and the high-temperature firing sliding plate brick has better performance due to pre-reaction, is suitable for large steel ladles, converters and the like and is also a preferred choice for variety steel smelting and the like, but the production process needs high-temperature firing and asphalt dipping procedures, and the production cost and the energy consumption are higher. The traditional sliding plate brick is made of carbon-containing refractory materials, the sliding plate brick has the problem of carbon oxidation in the using process, the carbon oxidation causes the loose structure of the sliding plate, so that oxides such as iron, manganese, calcium and the like permeate into a sliding plate matrix and react with alumina in the sliding plate to generate low-melting substances, the damage of the structure of the sliding plate brick is caused, and the carbon oxidation is accelerated. Causing the service life and the safety factor of the slide plate brick to be reduced. Meanwhile, the carbon-containing refractory material can cause the recarburization effect of molten steel due to the loss of the refractory material in the using process, and the carbon-containing refractory material has influence on the quality of the molten steel, particularly has more obvious influence on clean steel. Therefore, the method adopts a production and preparation process with no pollution and low energy consumption to develop the low-carbon/carbon-free sliding plate brick suitable for various types of steel, so as to improve the adaptability of the sliding plate brick to the steel grade, solve the carburization influence of the sliding plate brick on molten steel, and solve the technical problem to be solved urgently.
The Hongzaghuo, etc. in the research of non-oxide composite refractory material, the theory of metal-plastic phase composite refractory material and the process for realizing said material, i.e. transition-plastic phase process, are proposed. A certain amount of metal is added into the rigid inorganic oxide, and the metal changes the rigid forming of the original material into plastic forming in the material forming process, so that the blank making density is improved, and the porosity is reduced; in the sintering process, the metal phase is liquefied or softened, the pores are filled, and the metal phase reacts with the material and the ambient atmosphere to generate a non-oxide reinforcing phase, so that the high-temperature strength and the thermal shock stability of the material are improved. Therefore, the invention further researches a production method of the composite sliding plate without high-temperature sintering and asphalt impregnation by combining the transition plastic phase process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate and a production method thereof, wherein the method does not need high-temperature firing or asphalt impregnation, is energy-saving and environment-friendly, and has lower production cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
a titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate comprises the following raw materials in percentage by weight: 35-65% of brown fused alumina, 4-8% of activated alumina micropowder, 10-38% of magnesium aluminate spinel, 5-15% of metal titanium, 5-10% of metal aluminum, and 3-5% of phenolic resin as a bonding agent.
The particle size range of the brown corundum is as follows: the granularity is more than 1mm and less than or equal to 3mm, the granularity is more than 0.2mm and less than or equal to 1mm, and the granularity is more than or equal to 3mm and less than or equal to 1 mm.
The particle size range of the magnesium aluminate spinel is as follows: the granularity is more than 0.2mm and less than or equal to 1mm, the granularity is more than 0.044mm and less than or equal to 0.2mm and the granularity is more than or equal to 5 mm and less than or equal to 0.044 mm.
The weight ratio of different particle sizes is: particle size 1: particle size 2: particle size 3: particle size 4: particle size 5: the granularity is 6-15-20: 15-25: 0 to 20: 0 to 10: 0 to 25: 3 to 14.
The granularity of the metal aluminum is less than or equal to 0.044 mm.
The granularity of the metal titanium is as follows: d 50 The model of the active alumina micro powder is RG4000 with the particle size of 100 nm.
The production method of the titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate comprises the following steps:
(1) weighing various raw materials according to a ratio, putting metal titanium, activated alumina micro powder, metal aluminum, brown corundum with the particle size of less than or equal to 0.2mm and magnesium aluminate spinel into a mixer, and mixing for 15-30 minutes to obtain mixed powder for later use;
(2) adding brown aluminium oxide and magnesium aluminate spinel with the granularity of more than 0.2mm into a wet mill, uniformly mixing, and then adding phenolic resin;
(3) after the brown corundum and the magnesium aluminate spinel with the granularity larger than 0.2mm are wetted by the phenolic resin, adding the mixed powder, mixing for 20-40 min to obtain a mud material for forming, ageing the mud material for 4-8 h under the conditions of constant temperature and constant humidity, and pressing and forming to obtain a slide plate brick blank;
(4) naturally drying the green bricks for 12-24 hours, and then putting the green bricks into a dryer for drying;
(5) after drying, the product of the invention is prepared by hooping, grinding and coating.
The conditions of constant temperature and constant humidity are as follows: the temperature is 25-35 ℃, and the relative humidity is 40-50%.
The drying temperature in the dryer is 180-250 ℃, and the drying time is 24-48 h.
The drying process comprises a heating and heat preservation stage, wherein heat preservation is carried out for 3-5 h at 100 ℃ before drying, and heat preservation is carried out for 8-10 h after the heating reaches the target drying temperature.
The invention has the beneficial effects that:
the invention takes the transition plasticity theory as the basis, and enables the metal titanium to play the role of a transition plasticity phase in the using process of the sliding plate, namely, part of the metal titanium is converted into non-oxide reinforced phases Ti (C, N) in situ in the temperature rising process of the sliding plate, and the rest of the metal titanium is taken as the transition plasticity phase, so that the non-fired and non-impregnated titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate which has excellent performance and does not need a high-temperature firing and asphalt impregnation process is prepared, and the composite sliding plate is energy-saving and environment-friendly and has lower production cost.
The invention overcomes the adverse effect of carbon content reduction of the carbon-containing refractory material on the erosion resistance and the thermal shock stability of the carbon-containing refractory material, reduces the production cost, improves the production efficiency, shortens the production period, and simultaneously ensures that the sliding plate brick has the characteristics of excellent strength, oxidation resistance, thermal shock stability, erosion resistance, long service life, high safety factor and the like. The specific analysis is as follows:
(1) the brown corundum is adopted as the aggregate, and has the characteristics of high purity, good crystallization, strong fluidity, low linear expansion coefficient, high wear resistance and corrosion resistance, so that the material has the advantages of corrosion resistance and thermal shock resistance.
(2) The invention adopts strict grain size distribution, especially limits the grain sizes of brown corundum and magnesium aluminate spinel, on one hand, ensures reasonable proportion of granular materials and fine powder with different grain sizes, on the other hand, ensures reasonable proportion of the granular materials with different grain sizes, and the reasonable grain size distribution can ensure the volume density and apparent porosity of the product.
(3) The invention introduces magnesia-alumina spinel to make the material alkaline, and utilizes the characteristic that MgO in the spinel does not react with molten steel and steel slag to form low-melting matters to make the material have excellent erosion resistance, and simultaneously avoids the defect of poor volume stability of MgO introduced by magnesia.
(4) The composite metal aluminum and metal titanium micro powder are used as metal raw materials, on one hand, the composite metal aluminum and metal titanium micro powder are used as antioxidants, compared with the single metal aluminum, the composite metal aluminum and metal titanium micro powder have excellent oxidation resistance, on the other hand, the metal titanium can generate non-oxide reinforced phases Ti (C, N) in situ in the high-temperature use process, and the erosion resistance and the high-temperature strength of the material are improved.
(5) The product obtained by the invention is a metal and nonmetal combined sliding plate, wherein the free titanium can reduce the porosity of the material and play a role of a plastic phase, and the toughness and the thermal shock stability of the material are improved.
(6) The titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate has excellent physical performance indexes, wherein the apparent porosity is 3-8%, and the volume density is 3.05-3.20 g/cm 3 And the normal-temperature compressive strength is 120-200 MPa, and the high-temperature bending strength (1450 ℃ for 0.5h) is 25-60 MPa.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
The titanium-magnesia-alumina spinel-brown fused alumina composite sliding plate has the following requirements on the granularity of raw materials:
the particle size of brown corundum includes: the granularity is more than 1mm and less than or equal to 3mm, the granularity is more than 0.2mm and less than or equal to 1mm, and the granularity is more than or equal to 3mm and less than or equal to 1 mm; the particle size of the magnesium aluminate spinel includes: the granularity is more than 0.2mm and less than or equal to 1mm, the granularity is more than 0.044mm and less than or equal to 0.2mm and the granularity is more than or equal to 5 mm and less than or equal to 0.044 mm; the granularity of the metal aluminum is less than or equal to 0.044 mm; the particle size of the metallic titanium is as follows: d 50 ＝100nm，
The weight ratio of different particle sizes is: particle size 1: particle size 2: particle size 3: particle size 4: particle size 5: the granularity is 6-15-20: 15-25: 0 to 20: 0-10: 0 to 25: 3 to 14.
Example 1
A titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate comprises the following raw materials in percentage by weight: 50% of brown fused alumina, 32% of magnesium aluminate spinel, 8% of activated alumina micropowder, 5% of metal titanium, 5% of metal aluminum and 3% of thermosetting phenolic resin.
The weight ratio of different particle sizes is: particle size 1: particle size 2: particle size 3: particle size 5: particle size 6 ═ 15: 25: 10: 18: 14;
wherein the type of the activated alumina micro powder is RG 4000; the type of the binding agent phenolic resin is PF 5323;
the production method of the composite sliding plate comprises the following steps:
(1) weighing various raw materials according to a ratio, putting metal titanium, activated alumina micro powder, metal aluminum, brown corundum with the particle size of less than or equal to 0.2mm and magnesium aluminate spinel into a mixer, and mixing for 15-30 minutes to obtain mixed powder for later use;
(2) adding brown aluminium oxide and magnesium aluminate spinel with the granularity of more than 0.2mm into a wet mill, uniformly mixing, and then adding phenolic resin;
(3) after the brown corundum and the magnesium aluminate spinel with the granularity larger than 0.2mm are wetted by the phenolic resin, adding mixed powder for mixing for 20-40 min to obtain a mud material for forming, ageing the mud material for 4-8 h under the conditions of constant temperature and constant humidity (the temperature is 25-35 ℃, and the relative humidity is 40-50%), and then pressing and forming to obtain a slide brick blank;
(4) naturally drying the green bricks for 12-24 hours, and then putting the green bricks into a dryer for drying, wherein the drying temperature in the dryer is 180-250 ℃, and the drying time is 24-48 hours; the drying process comprises a heating and heat preservation stage, wherein heat preservation is performed for 3-5 hours at 100 ℃ during drying, and then heat preservation is performed for 8-10 hours after the temperature is raised to reach the target drying temperature.
(5) After drying, the product of the invention is prepared by hooping, grinding and coating.
The performance indexes of the obtained product are as follows: apparent porosity of 3.2% and volume density of 3.10g/cm 3 The normal temperature compressive strength is 120MPa, and the high temperature rupture strength (1450 ℃ C. multiplied by 0.5h) is 25.4 MPa.
Example 2
A titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate comprises the following raw materials in percentage by weight: 65% of brown fused alumina, 10% of magnesium aluminate spinel, 7% of activated alumina micropowder, 8% of metallic titanium, 10% of metallic aluminum and 4% of thermosetting phenolic resin.
The weight ratio of different particle sizes is: particle size 1: particle size 2: particle size 3: particle size 6-20: 25: 20: 10.
the production method of the composite sliding plate is the same as that of the embodiment 1, and the performance indexes of the obtained product are as follows: apparent porosity of 4.1% and volume density of 3.20g/cm 3 The normal temperature compressive strength is 168MPa, and the high temperature rupture strength (1450 ℃ C. multiplied by 0.5h) is 52.8 MPa.
Example 3
A titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate comprises the following raw materials in percentage by weight: 53 percent of brown fused alumina, 23 percent of magnesia alumina spinel, 4 percent of activated alumina micropowder, 12 percent of metallic titanium, 8 percent of metallic aluminum and 4 percent of thermosetting phenolic resin.
The weight ratio of different particle sizes is: particle size 1: particle size 2: particle size 3: particle size 4: particle size 5, particle size 6 ═ 18: 20: 15: 5: 10: 8.
the production method of the composite sliding plate is the same as that of the embodiment 1, and the performance indexes of the obtained product are as follows: the apparent porosity is 5.9 percent, and the volume density is 3.16g/cm 3 The normal temperature compressive strength is 142MPa, and the high temperature rupture strength (1450 ℃ carbon burying multiplied by 0.5h) is 43.5 MPa.
Example 4
A titanium-magnesium aluminate spinel-brown corundum composite sliding plate comprises the following raw materials in percentage by weight: 35% of brown fused alumina, 38% of magnesium aluminate spinel, 7% of activated alumina micropowder, 15% of metallic titanium, 5% of metallic aluminum and 5% of thermosetting phenolic resin.
The weight ratio of different particle sizes is: particle size 1: particle size 2: particle size 4: particle size 5, particle size 6 ═ 20: 15: 10: 25: 3.
the production method of the composite sliding plate is the same as that of the embodiment 1, and the performance indexes of the obtained product are as follows: the apparent porosity is 7.8 percent, and the volume density is 3.05g/cm 3 The normal temperature compressive strength is 198MPa, and the high temperature rupture strength (1450 ℃ C. multiplied by 0.5h) is 59.7 MPa.
EXAMPLE 5 product Performance analysis of the invention
The titanium-magnesium aluminate spinel-brown corundum composite sliding plate is compared with HBMLT-80 in the industry standard YB/T5049-2019, the specific method refers to the industry standard, and the results are shown in the following table.
As can be seen from the above table: compared with the industrial standard, the product of the invention has the advantages that each performance index reaches and is superior to the industrial standard, and the product has obvious performance advantages.
Claims (7)
1. The titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate is characterized by comprising the following raw materials in percentage by weight: 35-65% of brown fused alumina, 4-8% of activated alumina micropowder, 10-38% of magnesium aluminate spinel, 5-15% of metal titanium, 5-10% of metal aluminum, and 3-5% of phenolic resin as a bonding agent in the total amount of the raw materials;
the particle size range of the brown corundum is as follows: the granularity is more than 1mm and less than or equal to 3mm, the granularity is more than 0.2mm and less than or equal to 1mm, and the granularity is more than or equal to 3mm and less than or equal to 1 mm;
the particle size range of the magnesia-alumina spinel is as follows: the granularity is more than 0.2mm and less than or equal to 1mm, more than 0.044mm and less than or equal to 0.5 mm, and the granularity is more than or equal to 6 and less than or equal to 0.044 mm;
the weight ratio of different particle sizes is: particle size 1: particle size 2: particle size 3: particle size 4: particle size 5: particle size 6 is 15-20: 15-25: 0 to 20: 0 to 10: 0 to 25: 3-14;
the apparent porosity of the titanium-magnesia-alumina spinel-brown fused alumina composite sliding plate is 3-8%, and the volume density of the sliding plate is 3.05-3.20 g/cm 3 The normal-temperature compressive strength is 120-200 MPa, and the high-temperature flexural strength is 25-60 MPa.
2. The titanium-magnesium aluminate spinel-brown fused alumina composite skateboard of claim 1, wherein the particle size of the metallic aluminum is less than or equal to 0.044 mm.
3. The titanium-magnesium aluminate spinel-brown fused alumina composite skateboard according to claim 1, wherein the particle size of the metallic titanium is as follows: d 50 The model of the active alumina micro powder is RG4000 with the particle size of 100 nm.
4. A method for producing a titanium-magnesium aluminate spinel-brown fused alumina composite skateboard according to any one of claims 1 to 3, comprising the steps of:
(1) weighing various raw materials according to a ratio, putting metal titanium, activated alumina micro powder, metal aluminum, brown corundum with the particle size of less than or equal to 0.2mm and magnesium aluminate spinel into a mixer, and mixing for 15-30 minutes to obtain mixed powder for later use;
(2) adding brown aluminium oxide and magnesium aluminate spinel with the granularity of more than 0.2mm into a wet mill, uniformly mixing, and then adding phenolic resin;
(3) after the brown corundum and the magnesium aluminate spinel with the granularity larger than 0.2mm are wetted by the phenolic resin, adding the mixed powder, mixing for 20-40 min to obtain a mud material for forming, ageing the mud material for 4-8 h under the conditions of constant temperature and constant humidity, and pressing and forming to obtain a slide plate brick blank;
(4) naturally drying the green bricks for 12-24 hours, and then drying in a dryer;
(5) drying, hooping, grinding, and coating.
5. The production method of the titanium-magnesium aluminate spinel-brown fused alumina composite skateboard according to claim 4, wherein the conditions of constant temperature and constant humidity are as follows: the temperature is 25-35 ℃, and the relative humidity is 40-50%.
6. The production method of the titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate according to claim 4, wherein the drying temperature in a dryer is 180-250 ℃, and the drying time is 24-48 h.
7. The production method of the titanium-magnesium aluminate spinel-brown fused alumina composite sliding plate according to claim 6, wherein the drying process comprises a heating and heat preservation stage, the drying process is performed for 3-5 hours at the temperature of 100 ℃, and the heating process is performed for 8-10 hours after reaching the target drying temperature.
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| CN103145433A (en) * | 2013-03-25 | 2013-06-12 | 北京科技大学 | Unfired ferrosilicon nitride-spinel-corundum composite refractory material and preparation method thereof |
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| CN1166585C (en) * | 2001-11-05 | 2004-09-15 | 武汉科技大学 | Production process of magnesia-alumina spinel titanium nitride composite material |
| CN102627463B (en) * | 2012-04-09 | 2014-03-12 | 江苏诺明高温材料股份有限公司 | Aluminum-spinel-corundum composite refractory material and preparation method as well as application thereof |
| CN110436902A (en) * | 2019-07-29 | 2019-11-12 | 北京科技大学 | RH refining furnace SiC-AlN solid solution combination Brown Alundum refractory material and preparation method thereof |
| CN110511003A (en) * | 2019-09-03 | 2019-11-29 | 北京科技大学 | A kind of Ti (C, N) solid solution combining corundum based refractory materials and preparation method thereof |
| CN110550940A (en) * | 2019-09-03 | 2019-12-10 | 北京科技大学 | Ti (C, N) solid solution combined corundum-spinel refractory material and preparation method thereof |
| CN110540412A (en) * | 2019-09-03 | 2019-12-06 | 北京科技大学 | Al2O3-C sliding plate containing metal titanium and preparation method thereof |
| CN111410519B (en) * | 2020-04-24 | 2022-10-04 | 河南熔金高温材料股份有限公司 | Aluminum titanate-added Al 2 O 3 -C sliding brick and production method thereof |
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| CN103145433A (en) * | 2013-03-25 | 2013-06-12 | 北京科技大学 | Unfired ferrosilicon nitride-spinel-corundum composite refractory material and preparation method thereof |
| CN108911767A (en) * | 2018-07-27 | 2018-11-30 | 通达耐火技术股份有限公司 | A kind of RH refining furnace key position corundum system unburned brick and preparation method thereof |
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