CN117164367A - Si (silicon) 2 N 2 O and TiN co-reinforced SiC composite refractory material and preparation method thereof - Google Patents
Si (silicon) 2 N 2 O and TiN co-reinforced SiC composite refractory material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011819 refractory material Substances 0.000 title claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000010703 silicon Substances 0.000 title claims description 13
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 97
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000007767 bonding agent Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000005121 nitriding Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 229910008332 Si-Ti Inorganic materials 0.000 claims description 15
- 229910006749 Si—Ti Inorganic materials 0.000 claims description 15
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 230000035939 shock Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 210000001015 abdomen Anatomy 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GPTXWRGISTZRIO-UHFFFAOYSA-N chlorquinaldol Chemical compound ClC1=CC(Cl)=C(O)C2=NC(C)=CC=C21 GPTXWRGISTZRIO-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 239000011856 silicon-based particle Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
The invention relates to Si 2 N 2 The O and TiN co-reinforced SiC composite refractory material comprises the following steps of weighing silicon carbide, silicon powder and titanium oxide powder serving as raw materials and a bonding agent according to a proportion, and uniformly stirring to prepare pug; pressing the pug into a green body, and drying, nitriding and sintering to obtain Si 2 N 2 O and TiN co-reinforced SiC composite refractory material. The method solves the problems of the prior Si 3 N 4 Free Si and Si are easily generated in the SiC composite material 3 N 4 Poor chemical stability of the bonding phase, poor material use performance and other defects, and Si 3 N 4 In comparison with Si 2 N 2 O and TiN have more excellent chemical stability, wherein TiN also has excellent resistanceErosion and thermal shock resistance, si 2 N 2 O has excellent oxidation resistance.
Description
Technical Field
The invention belongs to the field of refractory materials, and in particular relates to Si 2 N 2 An O and TiN co-reinforced SiC composite refractory material and a preparation method thereof.
Background
Si 3 N 4 The SiC composite material has good alkali corrosion resistance, molten cryolite wettability, oxidation resistance, wear resistance, high thermal conductivity, thermal shock resistance and extremely low electrical conductivity, and can be widely applied to the middle and lower parts of a large-sized blast furnace body, the furnace waist and the furnace abdomen parts, the side wall of an aluminum electrolysis cell, a garbage incinerator and the like.
Si 3 N 4 The main preparation method of the SiC refractory material is as follows: uniformly mixing SiC particles with certain particle size, silicon powder and a binding agent, pressing or vibrating and forming to prepare a green brick, drying the green brick, and sintering in flowing nitrogen atmosphere. During the nitriding sintering process, si and N 2 Reaction to form Si between SiC particles 3 N 4 And the bonding phase is used for leading the bonding phase to have certain strength. The nitriding reaction of Si is an exothermic reaction, and if the reaction is too severe, the heat does not spread out to the outside, resulting in a rapid local temperature rise. If the local temperature is higher than the melting point of Si (1412 ℃), the silicon in the feedstock is melted into a liquid phase and the nitrogen will not better contact the unreacted Si, resulting in incomplete nitridation of the Si and some amount of free silicon in the product. Under the use condition of repeated heating and cooling, free silicon can lead Si to be formed 3 N 4 Cracks develop in the SiC article, affecting its service life.
Further, in recent years, it has been shown that elemental Fe promotes Si at 1000 ℃ or higher 3 N 4 To generate simple substance Si and nitrogen; while Si is easily generated above 1500 ℃ when carbon sources (solid C and CO) are present in the environment 3 N 4 Conversion to SiC is accompanied by volume shrinkage. Therefore, during the service process of the blast furnace, because Fe and CO gas exist in the environment at the same time, under the combined action of the Fe and CO gas, si 3 N 4 The bonding phase is easy to decompose and convert to SiC, so that the product is damaged, and the service life is not ideal. While in aluminum electrolysis cell application, si 3 N 4 The binding phase is also Si 3 N 4 Weak points of SiC composite: 1) Si (Si) 3 N 4 Is easy to react with HF gas to generate SiF 4 And eroded; 2) Si at electrolysis temperature 3 N 4 The aluminum alloy can react with aluminum liquid to generate AlN and Si, so that the AlN is easy to hydrate, and the corrosion and damage of materials can be accelerated; 3) Since there is usually a certain amount of sodium element in the aluminum liquid, the material is liable to sodium vapor permeation and permeation of air and anode gas, thereby leading to Na (g) and Si 3 N 4 Is chemically reacted with each other to generate Na 2 SiO 3 Causing corrosion of the material. In combination with the above, in the aluminum electrolysis process, the gas, electrolyte and aluminum liquid all lead to Si 3 N 4 Unstable transformation occurs, resulting in Si 3 N 4 -SiC composite failure.
Si 3 N 4 SiC composite refractory material easy to generate free silicon problem and Si in preparation process 3 N 4 The problems of poor stability and the like of the combined phase in the corresponding service environment greatly limit the development and application of the combined phase, so that the combined phase is difficult to meet the increasingly severe requirements of high Wen Fuyi.
Si 2 N 2 O has excellent chemical stability and better antioxidant performance than Si 3 N 4 But has a slag erosion resistance slightly inferior to that of Si 3 N 4 . The TiN has high melting point, high hardness, good heat conduction performance, difficult wetting by metal melt, slag and the like, and excellent chemical stability, and is a non-oxide refractory material with high corrosion resistance and high thermal shock resistance. Practical research shows that TiN is deposited on the hearth and the bottom of the blast furnace hearth, can effectively prevent molten iron and slag from eroding the hearth lining, and prolongs the service life of the blast furnace. Si (Si) 2 N 2 The O and TiN co-reinforced SiC composite refractory material is expected to replace the traditional Si 3 N 4 SiC composite materials, widely used in high temperature industry, in particular blast furnace liners, aluminium electrolysis cells and garbage incinerators.
Disclosure of Invention
In order to overcome the problems of the prior art, the present invention provides Si 2 N 2 O and TiN co-reinforced SiC composite refractory material and preparation method thereof, which are used for solving the problems existing in the prior artThe above problems.
Si (silicon) 2 N 2 The preparation method of the O and TiN co-reinforced SiC composite refractory material comprises the following steps:
s1, weighing silicon carbide, silicon powder and titanium oxide powder serving as raw materials and a bonding agent according to a proportion, and uniformly stirring to prepare pug;
s2, pressing the pug in the step S1 into Si-Ti 2 O 3 The Si is prepared by the procedures of drying, nitriding and sintering of the SiC composite blank body 2 N 2 O and TiN co-reinforced SiC composite refractory material.
In the aspects and any possible implementation manner described above, there is further provided an implementation manner, wherein the silicon carbide, the silicon powder and the titanium oxide powder are respectively used as raw materials in mass percentages: 65-90 wt% of silicon carbide, 5-20 wt% of silicon powder and 5-15 wt% of titanium oxide, wherein the mass percentage of the bonding agent is 2-5 wt% of the total amount of the raw materials.
In aspects and any one of the possible implementations described above, there is further provided an implementation, the silicon carbide including a silicon carbide aggregate and a silicon carbide fines.
In aspects and any one of the possible implementations described above, there is further provided an implementation in which the silicon carbide aggregate has a particle size of 3 to 1mm and < 1mm, and the silicon carbide fine powder has a particle size of < 88 μm.
In aspects and any one of the possible implementations described above, there is further provided an implementation, the silicon powder having a particle size of < 88 μm; the granularity of the titanium oxide powder is less than 88 mu m.
Aspects and any one of the possible implementations as described above, further providing an implementation of the method of forming Si-Ti 2 O 3 -drying the SiC composite green body for 12-60 hours at the temperature of 120-300 ℃.
In aspects and any one of the possible implementations as described above, there is further provided an implementation that dries the Si—Ti 2 O 3 Placing the SiC composite blank in a sagger, heating to 1300-1600 ℃ at a speed of 2-10 ℃/min under nitrogen atmosphere, and preserving heat for 3-24 hoursAnd (5) sintering.
In aspects and any one of the possible implementations described above, there is further provided an implementation in which the mass fraction of the silicon carbide aggregate is 60wt.%, the mass fraction of the silicon carbide fine powder is 15wt.%, the mass fraction of the silicon powder is 15wt.%, the mass fraction of the titanium sesquioxide powder is 10wt.%, and the mass fraction of the binder is 5wt.%.
In aspects and any one of the possible implementations described above, there is further provided an implementation in which the mass fraction of the silicon carbide aggregate is 70wt.%, the mass fraction of the silicon carbide fine powder is 5wt.%, the mass fraction of the silicon powder is 18wt.%, the mass fraction of the titanium sesquioxide powder is 7wt.%, and the mass fraction of the binder is 3.5wt.%.
The invention also provides Si 2 N 2 The O and TiN co-reinforced SiC composite refractory material is prepared by adopting the preparation method disclosed by the invention.
The beneficial effects of the invention are that
Si of the invention 2 N 2 The preparation method of the O and TiN co-reinforced SiC composite refractory material comprises the following steps: s1, weighing silicon carbide, silicon powder and titanium oxide powder serving as raw materials and a bonding agent according to a proportion, and uniformly stirring to prepare pug; s2, pressing the pug in the step S1 into a green body, and drying, nitriding and sintering to obtain Si 2 N 2 O and TiN co-reinforced SiC composite refractory material. The method solves the problems of the prior Si 3 N 4 Free Si and Si are easily generated in the SiC composite material 3 N 4 The poor chemical stability of the bonding phase, poor material use performance and the like, wherein the bonding phase aims at the existing Si 3 N 4 Free silicon is easy to generate in the preparation process of the SiC composite material, and Si 3 N 4 The invention uses silicon carbide, silicon powder and titanium oxide powder as raw materials to prepare Si-Ti 2 O 3 -a SiC composite green body, the dried green body being fired under nitrogen atmosphere by gas-liquid-solid reaction at high temperature: 6Si+Ti 2 O 3 +N 2 ＝3Si 2 N 2 O+2TiN to obtain Si 2 N 2 O and TiN co-reinforced SiC composite refractory material. With Si 3 N 4 In comparison with Si 2 N 2 O and TiN have more excellent chemical stability, wherein TiN also has excellent erosion resistance and thermal shock resistance, si 2 N 2 O has excellent oxidation resistance. The concrete steps are as follows:
(1) Si in the prior art 3 N 4 Si is easy to melt at a higher temperature in the production and preparation process of the SiC composite material, and liquid Si is difficult to react with nitrogen to generate Si 3 N 4 Eventually remaining in the material as free Si. In the invention, ti is further introduced into the Si-SiC green body 2 O 3 Powder, ti 2 O 3 Is easy to react with liquid Si and is converted into more stable Si in nitrogen atmosphere 2 N 2 O and TiN, on one hand, the residue of free Si is avoided, and on the other hand, a high-performance TiN reinforcing phase is introduced, so that the performance of the material can be greatly improved;
(2) Can obtain TiN reinforced phase with better erosion resistance and thermal shock resistance and Si with better oxidation resistance 2 N 2 And the O reinforcing phase play a role together, so that the high-temperature performance of the material is greatly improved.
Drawings
FIG. 1 is a flow chart of the preparation method of the 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, one Si of the present invention 2 N 2 The preparation method of the O and TiN co-reinforced SiC composite refractory material comprises the following steps:
s1, weighing silicon carbide, silicon powder, titanium oxide powder and a binding agent according to a proportion to obtain a composite material, and uniformly stirring to prepare pug;
s2, pressing the pug in the step S1 into Si-Ti by a press 2 O 3 The Si is prepared by the procedures of drying, nitriding and sintering of the SiC composite blank body 2 N 2 O and TiN co-reinforced SiC composite refractory material.
Wherein, the silicon carbide, the silicon powder and the titanium oxide powder are used as raw materials with the mass fractions as follows: 65-90 wt% of silicon carbide, 5-20 wt% of silicon powder and 5-15 wt% of titanium oxide, wherein the mass percentage of the bonding agent is 2-5 wt% of the total amount of all the raw materials.
Further, the silicon carbide comprises silicon carbide aggregate with the granularity of 3-1 (also can be recorded as 1-3) mm and less than 1mm, and silicon carbide fine powder with the granularity of less than 88 mu m, wherein the mass percent of the silicon carbide aggregate with the granularity of 3-1 mm and less than 1mm is 60-85%, and the mass percent of the silicon carbide fine powder is 5-30%; the granularity of the silicon powder is less than 88 mu m; the granularity of the titanium oxide powder is less than 88 mu m. The above grain size composition can make the blank obtain necessary porosity (5% -25%), and has a certain air hole, which is favorable for improving the thermal shock resistance, but too high porosity will reduce the strength and erosion resistance of the material, so the invention can balance the thermal shock resistance and erosion resistance of the product through reasonable grain grading.
Preferably, the binder is a thermosetting phenolic resin binder. The thermosetting phenolic resin has higher viscosity (0.02-100 Pa.s) at normal temperature (25 ℃)With SiC, ti 2 O 3 Si particles are good in wettability, can be uniformly coated on the surfaces of the particles at normal temperature, and are used as bonding agents to endow Si-Ti 2 O 3 The SiC composite green body has higher strength; when the green body is further dried and sintered at high temperature, the phenolic resin binder is heated and decomposed at 200-800 ℃ to leave a small amount of residual carbon, namely resin residual carbon which has the characteristics of high dispersibility, high activity, superfine property and the like, and can greatly improve the effect of liquid Si on Ti 2 O 3 Thereby promoting the wettability of Si with Ti 2 O 3 Chemical reaction between them.
Preferably, si-Ti 2 O 3 The SiC composite green body is dried for 12 to 60 hours at the temperature of 120 to 300 ℃ until the residual moisture in the green body is slowly evaporated to below 1 percent.
Preferably, the dried green body is placed in a sagger, and heated to 1300 ℃ to 1600 ℃ at a speed of 2 to 10 ℃/min under the nitrogen atmosphere, and the temperature is kept for 3 to 24 hours for sintering, so that Si and Ti are obtained 2 O 3 Is fully reacted and converted into Si 2 N 2 O and TiN. In the high temperature sintering process, si and Ti in the green body 2 O 3 With N in the atmosphere 2 The gas-liquid-solid reaction takes place: 6Si+Ti 2 O 3 +N 2 ＝3Si 2 N 2 O+2TiN. In one aspect, solid Ti 2 O 3 The diffusion rate between the Si and the liquid Si is higher, so that the rate of the Si participating in the reaction can be greatly improved, and the existence of free Si is reduced; on the other hand, in this reaction, si as a reducing agent promotes Ti 2 O 3 To convert it to stable TiN non-oxide. As the reaction proceeds, si itself absorbs Ti 2 O 3 Is not less than (1) oxygen and N in the atmosphere 2 Finally preparing Si 2 N 2 O and TiN co-reinforced SiC composite refractory material. With Si 3 N 4 In comparison with Si 2 N 2 O and TiN have more excellent chemical stability, wherein TiN also has excellent erosion resistance and thermal shock resistance, si 2 N 2 O has excellent oxidation resistance. Thus, the process of the present invention is carried out during the preparation processRaw silicon is melted, and liquid silicon can be further mixed with Ti 2 O 3 Liquid-solid reaction and conversion to Si 2 N 2 O, thereby avoiding the residue of free silicon.
Further, the mass fraction of the silicon carbide aggregate is 60 wt%, the mass fraction of the silicon carbide fine powder is 15wt%, the mass fraction of the silicon powder is 15wt%, the mass fraction of the titanium sesquioxide powder is 10 wt%, and the mass fraction of the binder is 5wt%.
Further, the mass fraction of the silicon carbide aggregate is 70wt.%, the mass fraction of the silicon carbide fine powder is 5wt.%, the mass fraction of the silicon powder is 18wt.%, the mass fraction of the titanium sesquioxide powder is 7wt.%, and the mass fraction of the binder is 3.5wt.%.
The invention also provides Si 2 N 2 The O and TiN co-reinforced SiC composite refractory material is prepared by adopting the preparation method provided by the invention, and has excellent high-temperature oxidation resistance, thermal shock resistance and erosion resistance.
The following are several specific examples.
Example 1
Mixing 60wt.% of silicon carbide aggregate, 15wt.% of silicon carbide fine powder, 15wt.% of silicon powder and 10wt.% of titanium sesquioxide powder, adding 5wt.% of phenolic resin binder into the mixture, uniformly mixing, and pressing to obtain Si-Ti 2 O 3 -SiC composite green body and dried at 200 ℃ for 12 hours. Drying the Si-Ti 2 O 3 The SiC composite material blank is heat-preserving for 4h and burned at 1300 ℃ to prepare Si 2 N 2 O and TiN co-reinforced SiC composite refractory material.
Si obtained 2 N 2 The SiC composite refractory material co-reinforced by O and TiN has the apparent porosity of 12.3 percent and the volume density of 2.80g/cm through detection 3 The normal temperature compressive strength is 171MPa, and meets the use requirements of the middle and lower parts of the large blast furnace body, the furnace waist and the furnace abdomen parts, the side wall of the aluminum electrolysis cell, the garbage incinerator and the like.
Example 2
70wt.% silicon carbide aggregate, 5wt.%Mixing silicon carbide fine powder, 18wt.% silicon powder and 7wt.% titanium sesquioxide powder, adding 3.5wt.% phenolic resin binder of the mixture, uniformly mixing, and pressing to obtain Si-Ti 2 O 3 -SiC composite green body and dried at 150 ℃ for 24 hours. Drying the Si-Ti 2 O 3 The SiC composite material blank is heat-preserved for 8 hours at 1450 ℃ in nitrogen atmosphere to prepare Si 2 N 2 O and TiN co-reinforced SiC composite refractory material.
Si obtained 2 N 2 The SiC composite refractory material co-reinforced by O and TiN has the apparent porosity of 10.9 percent and the volume density of 2.76g/cm through detection 3 The normal temperature compressive strength is 124MPa, and meets the use requirements of the middle and lower parts of the large blast furnace body, the furnace waist and the furnace abdomen parts, the side wall of the aluminum electrolysis cell, the garbage incinerator and the like.
Example 3
Mixing 85wt.% of silicon carbide aggregate, 5wt.% of silicon carbide fine powder, 7wt.% of silicon powder and 3wt.% of titanium sesquioxide powder, adding 4wt.% of phenolic resin binder into the mixture, uniformly mixing, and pressing to obtain Si-Ti 2 O 3 -SiC composite green body and dried at 200 ℃ for 12 hours. Drying the Si-Ti 2 O 3 The SiC composite material blank is heat-preserved for 3 hours in nitrogen atmosphere at 1600 ℃ to prepare Si 2 N 2 O and TiN co-reinforced SiC composite refractory material.
Si obtained 2 N 2 The SiC composite refractory material co-reinforced by O and TiN has the apparent porosity of 11.3 percent and the volume density of 2.73g/cm through detection 3 The normal temperature compressive strength is 178MPa, and meets the use requirements of the middle and lower parts of the large blast furnace body, the furnace waist and the furnace abdomen parts, the side wall of the aluminum electrolysis cell, the garbage incinerator and the like.
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. Si (silicon) 2 N 2 The preparation method of the O and TiN co-reinforced SiC composite refractory material is characterized by comprising the following steps:
s1, weighing silicon carbide, silicon powder and titanium oxide powder serving as raw materials and a bonding agent according to a proportion, and uniformly stirring to prepare pug;
s2, pressing the pug in the step S1 into Si-Ti 2 O 3 The Si is prepared by the procedures of drying, nitriding and sintering of the SiC composite blank body 2 N 2 O and TiN co-reinforced SiC composite refractory material.
2. Si according to claim 1 2 N 2 The preparation method of the SiC composite refractory material co-reinforced by O and TiN is characterized in that the silicon carbide, silicon powder and titanium oxide powder are used as raw materials in mass percent respectively: 65-90 wt% of silicon carbide, 5-20 wt% of silicon powder and 5-15 wt% of titanium oxide, wherein the mass percentage of the bonding agent is 2-5 wt% of the total amount of the raw materials.
3. Si according to claim 1 2 N 2 The preparation method of the O and TiN co-reinforced SiC composite refractory material is characterized in that the silicon carbide comprises silicon carbide aggregate and silicon carbide fine powder.
4. The Si according to claim 3 2 N 2 The preparation method of the SiC composite refractory material co-reinforced by O and TiN is characterized in that the granularity of the silicon carbide aggregate is 3-1 mm and less than 1mm, and the granularity of the silicon carbide fine powder is less than 88 mu m.
5. Si according to claim 4 2 N 2 The preparation method of the O and TiN co-reinforced SiC composite refractory material is characterized in that the granularity of the silicon powder is less than 88μm; the granularity of the titanium oxide powder is less than 88 mu m.
6. Si according to claim 1 2 N 2 A process for preparing the composite refractory material of SiC reinforced by O and TiN features that Si-Ti 2 O 3 -drying the SiC composite green body for 12-60 hours at the temperature of 120-300 ℃.
7. Si according to claim 6 2 N 2 The preparation method of the SiC composite refractory material co-reinforced by O and TiN is characterized in that the dried Si-Ti 2 O 3 Placing the SiC composite blank in a sagger, heating to 1300-1600 ℃ at a speed of 2-10 ℃/min under the nitrogen atmosphere, and preserving heat for 3-24 hours to burn.
8. The Si according to claim 3 2 N 2 The preparation method of the SiC composite refractory material co-reinforced by O and TiN is characterized in that the mass fraction of the silicon carbide aggregate is 60 wt%, the mass fraction of the silicon carbide fine powder is 15wt%, the mass fraction of the silicon powder is 15wt%, the mass fraction of the titanium sesquioxide powder is 10 wt%, and the mass fraction of the bonding agent is 5wt%.
9. Si according to claim 4 2 N 2 The preparation method of the SiC composite refractory material co-reinforced by O and TiN is characterized in that the mass fraction of the silicon carbide aggregate is 70 wt%, the mass fraction of the silicon carbide fine powder is 5wt%, the mass fraction of the silicon powder is 18 wt%, the mass fraction of the titanium sesquioxide powder is 7 wt%, and the mass fraction of the bonding agent is 3.5 wt%.
10. Si (silicon) 2 N 2 An O and TiN co-reinforced SiC composite refractory obtained by the method of any one of claims 1 to 9.
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