CN116693276A - TiN-MgAlON-Al 2 O 3 Composite refractory material, preparation method and application - Google Patents

TiN-MgAlON-Al 2 O 3 Composite refractory material, preparation method and application Download PDF

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CN116693276A
CN116693276A CN202310557514.6A CN202310557514A CN116693276A CN 116693276 A CN116693276 A CN 116693276A CN 202310557514 A CN202310557514 A CN 202310557514A CN 116693276 A CN116693276 A CN 116693276A
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tin
mgalon
refractory material
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composite refractory
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CN116693276B (en
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马晨红
李勇
仝尚好
刘雷
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University of Science and Technology Beijing USTB
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Abstract

The invention relates to a TiN-MgAlON-Al 2 O 3 Composite refractory material, preparation method and application. The method comprises the following steps: mixing and stirring corundum, titanium aluminum alloy powder, magnesia and a binding agent according to a certain proportion to prepare pug; pressing the pug into a composite green body and drying; the composite green body is subjected to nitriding sintering to prepare TiN-MgAlON-Al 2 O 3 Composite refractory material. The invention takes titanium aluminum alloy powder, alumina powder, magnesia powder and magnesia particles as raw materials to prepare the chromium-free and carbon-free TiN-MgAlON-Al 2 O 3 A composite material. The invention adopts high-melting-point TiAl alloy as a raw material to be used as a precursor for synthesizing intermediate phases of TiN and AlNThe high-efficiency synthesis and uniform distribution of TiN and MgAlON are realized through a high-efficiency gas-solid reaction mechanism, and the composition and microstructure of the material are optimized. The invention improves the service life of the RH refining furnace when the prepared refractory material is used as the inner lining of the RH refining furnace, and simultaneously meets the smelting requirements of high-quality steel such as ultra-low carbon steel, clean steel and the like.

Description

TiN-MgAlON-Al 2 O 3 Composite refractory material, preparation method and application
Technical Field
The invention belongs to the technical field of refractory materials, and in particular relates to a TiN-MgAlON-Al 2 O 3 Composite refractory material, preparation method and application.
Background
External refining is a key process in the production of steel, especially high-quality clean steel. Impurities and inclusions in molten steel can be removed by external refining while adjusting and homogenizing the chemical composition of the molten steel. The RH vacuum refining technology has the advantages of high efficiency, suitability for batch processing, low equipment investment, easy operation and the like, is one of the most important methods in external refining, and is widely applied to modern steelworks. The refractory material for the inner lining of the RH refining furnace has harsh service environment and needs to bear the vacuum effect of high temperature (up to 1700 ℃) for a long time, the scouring and erosion effect of molten steel, the cyclic thermal shock effect and the like, so the refractory material is required to have high refractoriness, high strength, wear resistance, erosion resistance, good thermal shock resistance, good vacuum stability and the like.
The service temperature of the refractory material for the RH refining furnace lining may be as high as 1700 ℃. At present, the refractory material for the lining of the RH refining furnace mainly comprises magnesia chrome bricks (more than or equal to 50 percent), and the refractory material of magnesia carbon bricks (5 percent) is partially used. The RH lower tank is a high corrosion area of the whole furnace lining, and mainly uses Cr with good slag permeation resistance 2 O 3 And the content reaches 24 to 26 percent, and the magnesia chrome bricks are combined again by electric melting. However, cr in the presence of an alkaline oxide in a high temperature oxidizing atmosphere 2 O 3 Cr in the material 3+ Will be converted into Cr 6+ ，Cr 6+ Is a toxic carcinogen and has great harm to human body and environment. The carbon material has higher heat conductivity and is not easy to be wetted by slag, and the magnesia carbon brick developed by introducing the carbonaceous raw material into the MgO material has good slag penetration resistance, corrosion resistance and spalling resistance, and the service life is improved by about 15 percent compared with that of the common magnesia chrome brick. However, under high temperature vacuum conditions, C in magnesia carbon bricks can cause MgO to undergo a reduction reaction, mg (g) and CO (g) are formed to escape, and the structure is loose. Meanwhile, carbon causes pollution to molten steel, so that the magnesia carbon brick is not suitable for smelting low-carbon steel and clean steel.
In the prior art, metal aluminum powder, aluminum oxide powder and magnesia particles are used as raw materials, the temperature is kept at 500-700 ℃ for 2-10h, and then the temperature is kept at 1400-1700 ℃ for 2-6h, so that the MgAlON combined corundum composite refractory material is prepared. However, mgO matrix and single metal aluminum are adopted as raw materials, the melting point is low, and the severe nitriding temperature is higher than 800 ℃. That is, the aluminum powder in the billet has melted before the severe nitriding temperature of the metallic aluminum is reached. The formation of molten aluminum in the system causes the reduction of the reactivity of aluminum on one hand, and on the other hand, the inward diffusion of nitrogen is greatly hindered, so that the synthesis difficulty and the uneven distribution of AlN mesophase are caused, the controllable synthesis and the even distribution of MgAlON are further hindered, and free metallic aluminum exists in the obtained material, so that the material performance is not ideal.
Disclosure of Invention
In order to overcome the problems existing in the prior art, the invention provides a TiN-MgAlON-Al 2 O 3 The composite refractory material, the preparation method and the application are used for solving the problems in the prior art.
TiN-MgAlON-Al 2 O 3 A method of preparing a composite refractory material, the method comprising the steps of:
s1, mixing and stirring corundum, titanium aluminum alloy powder, magnesia and a binding agent according to a certain proportion to prepare pug;
s2, pressing the pug into a composite green body, and drying the green body;
s3, nitriding and sintering the composite green body to obtain the TiN-MgAlON-Al 2 O 3 Composite refractory material.
The aspects and any possible implementation manner described above further provide an implementation manner, wherein the mass fraction ratio of corundum, titanium aluminum alloy powder and magnesia in S1 is as follows: 65 to 90 weight percent of corundum and 5 to 20 weight percent of titanium aluminum alloy powder; 5-15 wt% of magnesia; the mass fraction ratio of the binding agent is 2-5 wt%.
In aspects and any one of the possible implementations described above, there is further provided an implementation wherein the corundum includes corundum aggregate having a particle size of 3-1 mm, less than 1mm and activated alumina fines having a particle size of less than 5 μm.
In the aspect and any possible implementation manner, there is further provided an implementation manner, wherein in the mass fraction range of the corundum, the corundum aggregate with the particle size of 3-1 mm and less than 1mm is 75-90% by mass, and the alumina fine powder is 10-25% by mass.
In the aspect and any possible implementation manner as described above, there is further provided an implementation manner, where the drying in S2 includes: and drying the composite green body at the temperature of 120-200 ℃ for 10-50 hours.
In the aspect and any possible implementation manner as described above, there is further provided an implementation manner, where the nitriding sintering in S3 includes: and placing the dried composite green body in a sagger, placing the sagger in a nitriding furnace filled with nitrogen, heating to 1200-1800 ℃ at a speed of 3-20 ℃/min, and preserving heat for 1-8 h for nitriding and firing.
In the aspect and any possible implementation manner, there is further provided an implementation manner, wherein the mass percentage of Ti in the titanium-aluminum alloy is 2% -80%.
In aspects and any one of the possible implementations described above, there is further provided an implementation, the binder is a thermosetting phenolic resin binder.
The invention also provides a TiN-MgAlON-Al 2 O 3 Composite refractory material of TiN-MgAlON-Al 2 O 3 The composite refractory material is prepared by the preparation method.
The invention also provides a TiN-MgAlON-Al 2 O 3 Use of a composite refractory material as a lining in an RH refining furnace.
The beneficial effects of the invention are that
Compared with the prior art, the invention has the following beneficial effects:
the invention aims at the prior art that the magnesia chrome brick (MgO-Cr) 2 O 3 ) Medium Cr 3+ Is easily converted into Cr 6+ Harmful to human health and pollutes the environment,and carbon in magnesia carbon brick (MgO-C) is easy to dissolve in molten steel, and causes carburetion pollution and the like. The invention takes titanium aluminum alloy powder, alumina powder, magnesia powder and magnesia particles as raw materials to prepare the chromium-free and carbon-free TiN-MgAlON-Al 2 O 3 Composite material, and TiN and MgAlON synergistically enhanced Al is prepared by high-temperature nitridation 2 O 3 Composite refractory material. The invention adopts high-melting-point TiAl alloy as a raw material to be used as a precursor for synthesizing intermediate phases of TiN and AlN, realizes high-efficiency synthesis and uniform distribution of the TiN and MgAlON through a high-efficiency gas-solid reaction mechanism, and optimizes the composition and microstructure of the prepared material. MgAlON has excellent molten iron and slag erosion resistance and thermal shock resistance, tiN has excellent wear resistance, higher hardness and good high-temperature stability, and the synergistic effect of the two can greatly improve the service life of the RH refining furnace when the prepared refractory material is used as an inner lining of the RH refining furnace, and simultaneously meets the smelting requirements of high-quality steel such as ultra-low carbon steel, clean steel and the like:
(1) Under RH refining service environment, C in MgO-C material in the prior art is easy to dissolve in molten steel, and pollutes the molten steel; mgO-Cr 2 O 3 Cr in composite material 3+ Is easily converted into Cr 6+ Harm to human health and pollute the environment. TiN-MgAlON-Al in the invention 2 O 3 The composite refractory material is sintered by high-temperature nitridation to be Al which is synergistically enhanced by TiN and MgAlON 2 O 3 The composite material is a carbon-free and chromium-free refractory material, has excellent chemical stability, does not pollute molten steel and has no harm to the environment and human body;
(2) In the RH refining service process, single MgAlON-MgO/Al in the prior art 2 O 3 The composite refractory material has insufficient wear resistance and is easy to cause material defects and damage. The TiN has high melting point, high hardness, excellent wear resistance, excellent erosion resistance, excellent thermal shock resistance and excellent chemical stability, and the key service performance of the refractory material for the RH refining furnace can be cooperatively improved by utilizing the TiAl alloy to synthesize the TiN and the MgAlON in situ, so that the long-life development of the refractory material for the RH refining furnace can be realized.
Drawings
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is a schematic diagram of a Ti-Al binary phase according to the present invention.
Detailed Description
For a better understanding of the present invention, the present disclosure includes, but is not limited to, the following detailed description, and similar techniques and methods should be considered as falling within the scope of the present protection. In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
It should be understood that the described embodiments of the invention are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As shown in FIG. 1, the TiN-MgAlON-Al of the present invention 2 O 3 A method of preparing a composite refractory material, the method comprising the steps of:
s1, mixing and stirring corundum, titanium aluminum alloy powder, magnesia and a binding agent according to a certain proportion to prepare pug;
s2, pressing the pug into a composite green body, and drying the green body;
s3, nitriding and sintering the composite green body to obtain the TiN-MgAlON-Al 2 O 3 Composite refractory material.
Specifically, the preparation process of the invention is as follows:
(1) Weighing corundum aggregate, corundum fine powder, magnesia fine powder, titanium-aluminum alloy powder and a binding agent according to a proportion, and uniformly stirring to prepare pug;
(2) Pressing the pug obtained in the step (1) into TiAl-MgO by a pressing machine-Al 2 O 3 The composite green body, wherein TiAl is from titanium aluminum alloy powder, mgO is from magnesia fine powder, al 2 O 3 Drying the composite blank from corundum at 120-200 ℃ for 10-50 hours;
(3) Drying TiAl-MgO-Al 2 O 3 The composite green body is placed in a sagger, the sagger is placed in a nitriding furnace, then nitrogen is introduced into the nitriding furnace, the temperature is raised to 1200-1800 ℃ at the speed of 3-20 ℃/min, and the temperature is kept for 1-8 h for nitriding and sintering.
TiAl-MgO-Al in nitriding sintering process 2 O 3 TiAl alloy particles in the composite blank and N in the atmosphere 2 The chemical reaction is carried out, specifically as shown in the reaction formula (1), tiN and Ti are generated in situ 2 AlN, alN; with the temperature further rising to 1200 ℃ or higher, the newly generated AlN further reacts with active Al in the system 2 O 3 Reacting MgO, specifically as shown in the reaction formula (2), in-situ generating MgAlON reinforcing phase and newly generated Ti 2 Active Al in AlN and System 2 O 3 MgO reacts, specifically as shown in the reaction formula (3), to generate TiN and MgAlON reinforcing phases; in addition, at higher temperatures, i.e. at temperatures greater than or equal to 1200 ℃, the liquid TiAl alloy may be directly alloyed with Al 2 O 3 MgO and N 2 Reacting to generate MgAlON and TiN; finally preparing the corundum composite refractory material compositely combined by TiN and MgAlON through a series of chemical reactions under the nitrogen atmosphere, wherein the composite refractory material is specifically shown as a reaction formula (4) to prepare TiN-MgAlON-Al 2 O 3 Composite refractory material.
TiAl(s)+N 2 (g)→TiN(s)+AlN(s)+Ti 2 AlN(s) (1) (gas-solid reaction)
AlN(s)+Al 2 O 3 (s) +MgO(s) →MgAlON(s) (2) (solid phase reaction)
Ti 2 AlN(s)+Al 2 O 3 (s) +MgO(s) -. MgAlON(s) +TiN(s) (3) (solid)
Phase reaction
TiAl(l)+N 2 (g)+Al 2 O 3 (s)+MgO(s)→MgAlON(s)+TiN(s)(4)
(gas-liquid-solid reaction)
Relative to the prior artThe MgO matrix is adopted in the technology, and corundum is adopted as aggregate, so that the high-temperature vacuum stability is better; the MgO added in the invention is fine powder, has higher reaction activity, is completely converted into MgAlON reinforcing phase in the high-temperature nitriding sintering process, and has better high-temperature stability and chemical stability; compared with the prior art, adopts single metal aluminum as raw material, and utilizes the metal aluminum and N at high temperature 2 Generating AlN by reaction, and further reacting AlN with Al 2 O 3 MgO reacts to form MgAlON reinforcing phase. However, metallic aluminum has a lower melting point (660 ℃) and a severe nitriding temperature of more than 800 ℃. That is, the aluminum powder in the billet has melted before the severe nitriding temperature of the metallic aluminum is reached. On one hand, the formation of molten aluminum in the system causes the reduction of the reactivity of aluminum, on the other hand, the inward diffusion of nitrogen is greatly hindered, the synthesis difficulty and the uneven distribution of AlN mesophase are further hindered, the controllable synthesis and the even distribution of MgAlON are further hindered, and the obtained material has free metallic aluminum, so that the material performance is not ideal, therefore, the invention adopts titanium-aluminum alloy as the raw material, the melting point is far higher than that of the metallic aluminum, as shown in figure 2, when the temperature reaches 800 ℃, the reaction (gas-solid reaction) of the solid titanium-aluminum alloy and nitrogen has more dynamic advantages, the reaction speed is relatively high, the efficient mass production and the even distribution of AlN mesophase are facilitated, and the controllable synthesis of MgAlON at a lower temperature is promoted; according to the invention, the titanium aluminum alloy is used as a raw material, so that the TiN reinforcing phase is further synthesized in situ while the AlN intermediate phase is generated by nitriding metal aluminum, the TiN is a material with excellent wear resistance, and the synergistic effect of the TiN and MgAlON can effectively improve the comprehensive performance of the material, thereby prolonging the service life.
Further, the mass fraction of each of the materials is as follows: 65-90 wt% of corundum, 5-20 wt% of titanium aluminum alloy powder and 5-15 wt% of magnesia, wherein 2-5 wt% of binding agent is added into the materials, and the proportion is proportioned according to the performance requirement of the refractory material to be prepared, wherein the aggregate is prepared according to the grain size: fines ≡7:3, preparing, wherein the aggregate adopts corundum, the matrix adopts corundum, aluminum titanium alloy and magnesia mixed powder, the corundum, aluminum titanium alloy and magnesia fine powder of the matrix part have higher activity at high temperature, all participate in the reaction under nitrogen atmosphere, and the aggregate has low activity and hardly participate in the reaction; the binder plays a role in binding and is used for binding raw material particles with different particle sizes together to prepare pugs with certain plasticity so as to facilitate the molding of the composite green body.
Further, the corundum comprises corundum aggregate with granularity of 3-1 mm and less than 1mm, and the granularity ratio is favorable for obtaining a composite blank with a certain porosity after molding; and<the active alumina powder with the granularity less than 5 microns is one of the raw materials adopted by refractory products, has higher activity, and is added into a matrix to be beneficial to participating in the reaction so as to generate MgAlON. Further, in 65 to 90wt% of corundum, the mass percentage of corundum aggregate with the granularity of 3 to 1mm and less than 1mm is 75 to 90 percent, and the mass percentage of the active alumina fine powder is 10 to 25 percent. The corundum aggregate has large particle size and low activity and hardly participates in the reaction; the mass percentage of the active alumina fine powder is 5-30%, and the addition amount of the active alumina fine powder is controlled to control the Al participating in the reaction 2 O 3 Thereby controlling the amount of MgAlON produced.
Preferably, the Ti content in the titanium-aluminum alloy is 2-80% by mass, the Ti content is different, the TiN/MgAlON ratio generated by the reaction is different, and the comprehensive performance of the generated composite material can be regulated and controlled according to the service environment.
Preferably, the bonding agent is a thermosetting phenolic resin bonding agent, the phenolic resin is one of the refractory bonding agents, and the thermosetting phenolic resin bonding agent is wrapped on the surfaces of raw material particles at normal temperature, so that the bonding agent can play a role in bonding and endow the material with certain strength; cracking at high temperature to generate a small amount of residual nano carbon, which is uniformly dispersed in the material to improve the TiAl alloy, mgO and Al 2 O 3 The wettability of the particles thereby promotes the generation of MgAlON.
According to the invention, corundum aggregate, corundum fine powder, titanium-aluminum alloy powder and a binding agent are weighed according to a proportion and uniformly stirred to prepare pug; pressing the pug into a blank by a press, drying and nitriding and sintering at high temperature to enable TiAl alloy and N to be formed 2 With MgO, al 2 O 3 Fully react to obtain TiN andMgAlON synergistically enhanced corundum composite refractory material.
Preferably, the green body is dried for 10 to 50 hours at the temperature of between 120 and 200 ℃, and the drying rate of the green body is moderate in the temperature range and the time range, so that the residual moisture is less than 1 percent, and the cracking of the green body is not easy to cause. If the temperature is too high, the drying rate is too high, and the product is easy to crack; if the temperature is too low or the drying time is too short, the residual moisture is hardly reduced to 1% or less, and the product is cracked during firing, resulting in defects.
Preferably, the high-temperature nitriding is performed by heating to 1200-1800 ℃ at a speed of 3-20 ℃/min under the condition of nitrogen atmosphere in a nitriding furnace, and preserving heat for 1-8 hours.
Preferably, the nitriding furnace comprises a tunnel kiln, a shuttle kiln and an electric kiln, and all the device kilns can be used as preparation sites.
When the system temperature reaches about 800 ℃ in nitrogen atmosphere, tiAl alloy particles begin to be significantly nitrided to generate TiN and Ti 2 AlN and AlN react in a gas-solid reaction mechanism, have higher dynamic advantage, have a relatively high reaction speed, and the reaction product is uniformly distributed; with the temperature further rising to 1200 ℃ or higher, the newly generated AlN further reacts with active Al in the system 2 O 3 Reacting MgO to generate MgAlON reinforcing phase, new Ti 2 Active Al in AlN and System 2 O 3 MgO reacts to form TiN and MgAlON reinforcing phases.
The invention also provides a TiN-MgAlON-Al 2 O 3 The composite refractory material is prepared by adopting the preparation method of the invention, and the phase composition of the composite refractory material is Al 2 O 3 TiN and MgAlON with apparent porosity of 8-16% and normal-temperature compressive strength of 90-400 MPa are used as a carbon-free and chromium-free refractory material, and the refractory material has excellent chemical stability, does not pollute molten steel and has no harm to the environment and human body. Compared with the traditional oxide refractory material, the non-oxide refractory material prepared by the invention has excellent erosion resistance, thermal shock resistance stability and thermochemical stability, and does not pollute molten steel. MgAlON in the composite material is in the Mg-Al-O-N systemThe spinel structure solid solution is a material with excellent molten iron and slag erosion resistance. The TiN has a melting point of 2950 ℃, has a Mohs hardness of 8-9, has good thermal shock resistance and excellent wear resistance, and has excellent thermal shock resistance and erosion resistance of non-oxide and excellent oxidation resistance. Incorporating metallic Al or Ti as a constituent into MgO-Al 2 O 3 In the composite refractory material, the MgAlON or TiN reinforcing phase is hopeful to be synthesized in situ by sintering under the high-temperature nitrogen atmosphere, so that the erosion resistance, thermal shock resistance and wear resistance of the material are synergistically improved, and the service life of the material is prolonged.
The invention also provides a TiN-MgAlON-Al 2 O 3 The application of the composite refractory material as a lining in the RH refining furnace can cooperatively improve the erosion resistance, thermal shock resistance, wear resistance and high-temperature vacuum stability of the RH refining furnace, thereby improving the key service performance of the RH refining furnace and realizing the long-life development of the RH refining furnace.
Example 1
Mixing 70wt.% of corundum aggregate, 20wt.% of alumina powder, 5wt.% of titanium-aluminum alloy powder and 5wt.% of magnesia powder, adding 3wt.% of phenolic resin binder of the mixture, uniformly mixing, and pressing to obtain TiAl-MgO-Al 2 O 3 The composite green body was dried at 120℃for 24 hours. Drying TiAl-MgO-Al 2 O 3 Heating the blank to 1400 ℃ at a heating rate of 10 ℃/min, and preserving heat for 4 hours to burn to obtain TiN-MgAlON-Al 2 O 3 Composite refractory material.
The obtained TiN-MgAlON-Al 2 O 3 The composite refractory material is detected to be Al in phase composition 2 O 3 TiN and MgAlON, the apparent porosity is 12.2%, and the normal temperature compressive strength is 276MPa.
Example 2
Mixing 60wt.% of corundum aggregate, 5wt.% of alumina powder, 20wt.% of titanium-aluminum alloy powder and 15wt.% of magnesia powder, adding 4wt.% of phenolic resin binder into the mixture, uniformly mixing, and pressing to obtain TiAl-MgO-Al 2 O 3 The composite green body was dried at 200℃for 12 hours. Drying TiAl-MgO-Al 2 O 3 Heating the blank to 1600 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours to burn to obtain TiN-MgAlON-Al 2 O 3 Composite refractory material.
The obtained TiN-MgAlON-Al 2 O 3 The composite refractory material is detected to be Al in phase composition 2 O 3 TiN, mgAlON, apparent porosity 9.8%, normal temperature compressive strength 346MPa.
Example 3
Mixing 80wt.% of corundum aggregate, 5wt.% of alumina powder, 8wt.% of titanium-aluminum alloy powder and 7wt.% of magnesia powder, adding 5wt.% of phenolic resin binder into the mixture, uniformly mixing, and pressing to obtain TiAl-MgO-Al 2 O 3 The composite green body was dried at 150℃for 48 hours. Drying TiAl-MgO-Al 2 O 3 Heating the blank to 1200 ℃ at a heating rate of 15 ℃/min, and preserving heat for 8 hours to burn to obtain TiN-MgAlON-Al 2 O 3 Composite refractory material.
The obtained TiN-MgAlON-Al 2 O 3 The composite refractory material is detected to be Al in phase composition 2 O 3 TiN and MgAlON, the apparent porosity is 13.1%, and the normal temperature compressive strength is 197MPa.
Example 4
Mixing 85wt.% of corundum aggregate, 5wt.% of alumina powder, 5wt.% of titanium-aluminum alloy powder and 5wt.% of magnesia powder, adding 4.5wt.% of phenolic resin binder of the mixture, uniformly mixing, and pressing to obtain TiAl-MgO-Al 2 O 3 The composite green body was dried at 120℃for 50 hours. Drying TiAl-MgO-Al 2 O 3 Heating the blank to 1700 ℃ at a heating rate of 20 ℃/min, and preserving heat for 2 hours to burn to obtain TiN-MgAlON-Al 2 O 3 Composite refractory material.
The obtained TiN-MgAlON-Al 2 O 3 The composite refractory material is detected to be Al in phase composition 2 O 3 TiN and MgAlON, the apparent porosity is 11.6%, and the normal temperature compressive strength is 159MPa.
Example 5
72wt.% corundum aggregate, 8wt.% alumina powder, 10 wt.%.% of titanium-aluminum alloy powder and 10wt.% of magnesia powder are mixed, 3.5wt.% of phenolic resin binder is added to the mixture, the mixture is uniformly mixed, and the TiAl-MgO-Al is prepared by compression molding 2 O 3 The composite green body was dried at 200℃for 10 hours. Drying TiAl-MgO-Al 2 O 3 Heating the blank to 1800 ℃ at a heating rate of 3 ℃/min, and preserving heat for 1h to burn to obtain TiN-MgAlON-Al 2 O 3 Composite refractory material.
The obtained TiN-MgAlON-Al 2 O 3 The composite refractory material is detected to be Al in phase composition 2 O 3 TiN and MgAlON, the apparent porosity is 14.1%, and the normal temperature compressive strength is 282MPa.
While the foregoing description illustrates and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as limited to other embodiments, and is capable of numerous other combinations, modifications and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein, either as a result of the foregoing teachings or as a result of the knowledge or technology of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.

Claims (10)

1. TiN-MgAlON-Al 2 O 3 A method of preparing a composite refractory material, the method comprising the steps of:
s1, mixing and stirring corundum, titanium aluminum alloy powder, magnesia raw materials and a binding agent according to a certain proportion to prepare pug;
s2, pressing the pug into a composite green body, and drying the green body;
s3, nitriding and sintering the composite green body to obtain the TiN-MgAlON-Al 2 O 3 Composite refractory material.
2. The TiN-MgAlON-Al of claim 1 2 O 3 The preparation method of the composite refractory material is characterized in that the S1 corundum, titanium aluminum alloy powder and magnesiaThe mass fraction ratio is as follows: 65 to 90 weight percent of corundum and 5 to 20 weight percent of titanium aluminum alloy powder; 5-15 wt% of magnesia; the mass fraction ratio of the binding agent is 2-5 wt%.
3. The TiN-MgAlON-Al according to claim 2 2 O 3 The preparation method of the composite refractory material is characterized in that the corundum comprises corundum aggregate with the granularity of 3-1 mm and less than 1mm and active alumina fine powder with the granularity of less than 5 mu m.
4. The TiN-MgAlON-Al of claim 3 2 O 3 The preparation method of the composite refractory material is characterized in that in the mass fraction range of the corundum, the mass percentage of corundum aggregate with the granularity of 3-1 mm and less than 1mm is 75-90%, and the mass percentage of alumina fine powder is 10-25%.
5. The TiN-MgAlON-Al of claim 1 2 O 3 The preparation method of the composite refractory material is characterized in that the drying in S2 comprises the following steps: and drying the composite green body at the temperature of 120-200 ℃ for 10-50 hours.
6. The TiN-MgAlON-Al of claim 1 2 O 3 The preparation method of the composite refractory material is characterized in that the nitriding sintering in the step S3 comprises the following steps: and placing the dried composite green body in a sagger, placing the sagger in a nitriding furnace filled with nitrogen, heating to 1200-1800 ℃ at a speed of 3-20 ℃/min, and preserving heat for 1-8 h for nitriding and firing.
7. The TiN-MgAlON-Al according to claim 2 2 O 3 The preparation method of the composite refractory material is characterized in that the mass percentage of Ti in the titanium-aluminum alloy is 2% -80%.
8. The TiN-MgAlON-Al of claim 1 2 O 3 A preparation method of a composite refractory material,the adhesive is characterized in that the adhesive is a thermosetting phenolic resin adhesive.
9. TiN-MgAlON-Al 2 O 3 A composite refractory material characterized in that the TiN-MgAlON-Al 2 O 3 A composite refractory material produced by the production method according to any one of claims 1 to 8.
10. A TiN-MgAlON-Al as claimed in claim 9 2 O 3 Use of a composite refractory material as a lining in an RH refining furnace.
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