CN111499387A - High-strength silicon nitride composite silicon carbide ceramic and preparation method and application thereof - Google Patents
High-strength silicon nitride composite silicon carbide ceramic and preparation method and application thereof Download PDFInfo
- Publication number
- CN111499387A CN111499387A CN202010322659.4A CN202010322659A CN111499387A CN 111499387 A CN111499387 A CN 111499387A CN 202010322659 A CN202010322659 A CN 202010322659A CN 111499387 A CN111499387 A CN 111499387A
- Authority
- CN
- China
- Prior art keywords
- temperature
- silicon nitride
- silicon
- powder
- silicon carbide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/46—Gases other than oxygen used as reactant, e.g. nitrogen used to make a nitride phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6586—Processes characterised by the flow of gas
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention relates to the field of composite materials, in particular to a high-strength silicon nitride composite silicon carbide ceramic, which is prepared by reasonably proportioning raw materials and combining a nitridation sintering process, adopts a mode of introducing nitrogen when preheating to 800 ℃ of 600 plus materials, so that a raw material mixture is heated in a non-nitrogen atmosphere, silicon powder is preheated, then nitrogen is introduced, and silicon nitride in the raw materials exists, so that the silicon powder is catalyzed and nitrided, the silicon nitride is formed, the silicon powder nitridation rate is improved, the silicon nitride formed by the silicon powder is combined with the silicon nitride in the raw materials in a liquid phase, the interpenetration among silicon carbide powder is realized, the bonding strength of the silicon nitride and the silicon carbide is enhanced, and the compactness of a ceramic material is improved; and nitrogen is introduced for reasonable time, so that the silicon nitride is prevented from being decomposed at more than 1600 ℃, the strength and the compactness of the ceramic material are enhanced, and the density of a sintered product is more than 2.65g/cm3Fine and smooth section, invisible pores, and improved ceramic materialThermal shock resistance and prolonged service life of the ceramic product.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-strength silicon nitride composite silicon carbide ceramic and a preparation method and application thereof.
Background
The silicon nitride composite silicon carbide ceramic material has the advantages of high density, high strength at normal temperature and high temperature, good thermal shock stability, high loaded softening point, high heat conductivity coefficient, high resistivity, good oxidation resistance, strong acid and alkali corrosion resistance and the like, and is widely applied to various fields of aluminum electrolysis baths, metallurgical blast furnaces, copper smelting, zinc smelting, ceramic pipeline products and the like.
At present, the raw materials of the silicon nitride and silicon carbide composite ceramic material are simple substance silicon and silicon carbide, and the silicon nitride and the silicon carbide are obtained after nitridation or are directly prepared by compounding; however, when the product is prepared by nitriding elemental silicon and silicon carbide raw materials in a nitrogen atmosphere, the strength and the compactness of the product are closely related to the silicon powder nitriding rate, and the low silicon powder nitriding rate can cause poor thermal shock resistance, poor room-temperature bending strength and high porosity of the product; the silicon nitride and the silicon carbide are compounded, so that the compounding uniformity of the silicon nitride and the silicon carbide is extremely poor, the distribution of the silicon nitride among the silicon carbide is not ideal, and the thermal shock resistance and the room-temperature bending strength of a product are not ideal, the porosity is high, and the service life of the product is shortened.
Therefore, in the prior art, a great number of researchers have conducted related studies to achieve the purpose of improving the overall performance of silicon nitride composite silicon carbide ceramic materials, such as: the formula of the casting silicon nitride combined silicon carbide product with the patent application number of 201710473178.1 and the manufacturing method thereof are characterized in that silicon carbide, metal silicon powder, silicon dioxide micropowder, rare earth oxide, bonding agent and curing agent are subjected to batching, vibration casting molding, curing, drying and firing molding; the firing and forming are carried out in the nitrogen atmosphere, the temperature is raised to 1100 ℃ at the speed of 30-40 ℃/h, and the temperature is kept for 2-10 h; then raising the temperature to 1150 ℃ at a speed of 30-40 ℃/h, and preserving the temperature for 2-8 h; heating to 1250 ℃ at the speed of 30-40 ℃/h, and preserving heat for 2-12 h; heating to 1350 ℃ and 1450 ℃ at 30-40 ℃, preserving heat for 2-15h, and naturally cooling to room temperature in the nitrogen atmosphere to obtain the silicon nitride, so that the silicon nitride is generated by in-situ nitridation of the metal silicon powder, weak compounding is realized, the product density and the silicon nitride yield are improved, and the high-temperature breaking strength and the thermal shock resistance of the material are enhanced; however, the heating rate in the process is low, so that the heating and heat-preserving process flow is long, the energy consumption is high, and the obtained product isThe components of simple substance silicon, silicon dioxide and the like in the product are not completely nitrided, so that the nitridation rate of the silicon component is lower, the density of the product is lower, and the product is maintained at 2.5g/cm3In the following, the cross section of the product is easy to have visible air holes. For another example: the kiln furniture material combining silicon nitride and silicon carbide and the preparation method thereof with the patent application number of 201810578403.2 adopt the raw materials of passivated silicon powder, silicon carbide powder, surfactant, sintering aid, binder, water and the like, the silicon powder is soaked by weak oxidizing solution, then the raw materials are evenly mixed, water is added for stirring to prepare ceramic slurry, the slurry is formed by slip casting, drying, nitriding and sintering are carried out, the temperature is kept for 1-2h, and the sintering temperature is raised to 1410-; the sintering temperature rise is to rise to 1000-class 1100 ℃ at the temperature rise speed of 600 ℃/h of 480-class heat, then to rise to 1210-class 1350 ℃ at the temperature rise speed of 480-class heat, the temperature is kept for 2-4h, and the temperature rises to 1410-class heat at the temperature rise speed of 300-class heat, so that a sintering system is established according to the contents of the passivated silicon powder and the silicon carbide and the silicon nitride generation mechanism, the sintering of the nitriding components is complete, the material with excellent performances such as strength is obtained, and the density of the obtained material is 2.58-2.81g/cm3The apparent porosity is 4.8-6.1%, and the normal-temperature compressive strength is 600-; however, the temperature rise rate of the process is high, so that the nitriding efficiency of the elemental silicon component in the material is low, the nitriding effect is not ideal, the thermal shock resistance of the product is poor, the compressive strength of the product is greatly reduced after the product is treated by rapid water cooling, and the application range of the ceramic material is greatly hindered.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a high-strength silicon nitride composite silicon carbide ceramic and a preparation method and application thereof.
The method is realized by the following technical scheme:
the invention aims to provide a preparation method of high-strength silicon nitride composite silicon carbide ceramic, which comprises the following raw materials of 50-70% of silicon carbide powder, 10-30% of silicon powder, 5-15% of silicon nitride powder, 5-15% of sintering aid and 1-5% of binder in percentage by mass;
uniformly mixing the raw materials, molding, heating and sintering, and cooling in a furnace, wherein the heating and sintering is carried out by heating from room temperature to 1000 ℃ within 10-20h, keeping the temperature for 1-2h, and filling nitrogen with the pressure of 1-10MPa into the sintering furnace when the temperature is increased to 800 ℃ of 600-; then raising the temperature from 1000 ℃ to 1300 ℃ within 5-10h, and preserving the heat for 3 h; heating from 1300 ℃ to 1720 ℃ within 5-10h, preserving heat for 2-5h, cooling from 1720 ℃ within 3-8h to 1000 ℃, and cooling to normal temperature along with the furnace to obtain the product.
During temperature rising sintering, the temperature rising rate and the heat preservation time are controlled to form 'temperature changing-constant temperature' cross sintering, and when the temperature rises to 600-plus-800 ℃, nitrogen is introduced to change the pressure, so that silicon powder is nitrided to generate silicon nitride, the silicon nitride is combined with the added silicon nitride liquid, the silicon nitride is inserted among silicon carbide powder, the bonding strength of the silicon nitride and the silicon carbide is enhanced, and the compactness is enhanced; silicon nitride is added in the raw material components and is used as a catalyst for converting silicon powder into silicon nitride and a seed crystal to promote the silicon powder to be completely nitrided, so that the silicon component in the raw material is completely nitrided, and the nitriding rate is improved; through the introduction of nitrogen, the decomposition of silicon nitride at a temperature of more than 1600 ℃ is inhibited, the ceramic material is ensured to have higher density, and the strength and the thermal shock resistance are enhanced.
Further, the uniform mixing is to mix the raw materials and homogenize the raw materials by dry grinding or wet grinding. The adopted dry grinding or wet grinding is ball milling in a ball mill for 1-2 h. So that the powders are mixed uniformly.
Furthermore, the forming is to prepare a biscuit by means of grouting, dry pressing or wet isostatic pressing. The grouting is a ball milling process of a ball mill, water is added for ball milling to form slurry, the slurry is injected into a mold, and a biscuit is obtained after molding. The dry pressing or wet isostatic pressing mode is that the mixed powder obtained by ball milling is dried by a dryer and sieved, and then the powder is put into a die sleeve and put into an isostatic pressing machine for compression molding to obtain a biscuit.
Further, the temperature-rising sintering is to place the biscuit in a sintering furnace, vacuumize the furnace until the vacuum surface shows less than 20Pa, and start heating and rising the temperature. Specifically, heating from room temperature to 1000 ℃ within 15h, introducing 2Mpa nitrogen when the temperature reaches 700 ℃, continuing heating, and keeping the temperature at 1000 ℃ for 2 h; heating from 1000 ℃ to 1300 ℃ within 6h, and keeping the temperature for 2 h; after the temperature is raised from 1300 ℃ to 1720 ℃ within 8 hours, the temperature is kept for 2 hours; cooling to 1000 deg.C from 1720 deg.C within 4h, and cooling to normal temperature.
Furthermore, the raw material components comprise, by mass, 50% of silicon carbide powder, 20% of silicon powder, 15% of silicon nitride powder, 10% of sintering aid and 5% of binder. The thermal shock resistance is improved, after the temperature is kept at 1150 ℃ for 15min, the water is cooled rapidly, the extrusion is carried out by adopting 20kg pressure, the circular operation is carried out for 20 times, and the phenomenon of fracture is not generated.
In the invention, the binder is a solid resin, such as a phenolic resin.
In the invention, the sintering aid is one or more of yttrium oxide, europium oxide, cerium oxide, aluminum oxide and magnesium oxide.
The invention also aims to provide the high-strength silicon nitride composite silicon carbide ceramic prepared by the preparation method.
It is a further object of the present invention to provide the use of high strength silicon nitride composite silicon carbide ceramics in the preparation of ceramic structural members, including, but not limited to, refractory bricks, thermocouple protection tubes, metal catheters, heat insulating rings, and the like.
Compared with the prior art, the invention has the technical effects that:
through reasonable proportioning of raw material components, the nitrogen sintering process is combined, the mode of introducing nitrogen when preheating to 600-plus 800 ℃ is adopted, the raw material mixture can be heated in a non-nitrogen atmosphere, so that silicon powder is preheated, then nitrogen is introduced, and the silicon powder is catalyzed and nitrided under the environment of the existence of silicon nitride in the raw material, the formation of silicon nitride is promoted, the nitridation rate of the silicon powder is improved, the silicon nitride formed by the silicon powder is promoted to be combined with the silicon nitride in the raw material under the liquid phase environment, the interpenetration among silicon carbide powder is realized, the bonding strength of the silicon nitride and the silicon carbide is enhanced, and the compactness of the ceramic material is improved; and nitrogen is introduced for reasonable time, so that the silicon nitride is prevented from being decomposed at more than 1600 ℃, the strength and the compactness of the ceramic material are enhanced, and the density of a sintered product is more than 2.65g/cm3Fine and smooth section and invisible poresThe thermal shock resistance of the ceramic material is improved, and the service life of the ceramic product is prolonged.
Detailed Description
The technical solution of the present invention is further defined below with reference to the specific embodiments, but the scope of the claims is not limited to the description.
Example 1
Preparing materials: 500g of silicon carbide powder, 200g of silicon powder, 150g of silicon nitride powder, 50g of magnesium oxide, 50g of yttrium oxide and 50g of phenolic resin;
mixing: putting silicon carbide powder, silicon nitride powder, magnesium oxide, yttrium oxide and phenolic resin into a ball mill, and adding water to ball mill for 2 hours;
molding: grouting and forming to obtain a biscuit;
and (3) sintering: placing the biscuit in a sintering furnace, covering the sintering furnace, vacuumizing the sintering furnace, starting heating when the vacuum surface shows 20Pa, raising the temperature from room temperature to 1000 ℃ within 15h, continuously heating when the temperature reaches 700 ℃, introducing 2MPa nitrogen, and preserving the heat for 2h when the temperature reaches 1000 ℃; then raising the temperature from 1000 ℃ to 1300 ℃ within 6h, and preserving the heat for 2 h; then heating from 1300 ℃ to 1720 ℃ within 8h, and preserving heat for 2 h; and then cooling the mixture from 1720 ℃ to 1000 ℃ within 4h, and cooling the mixture to the normal temperature along with the furnace to obtain the ceramic material.
Example 2
Preparing materials: 700g of silicon carbide powder, 100g of silicon powder, 50g of silicon nitride powder, 50g of aluminum oxide, 50g of cerium oxide and 50g of phenolic resin;
mixing: putting silicon carbide powder, silicon nitride powder, aluminum oxide, cerium oxide and phenolic resin into a ball mill, ball-milling for 1h, and sieving to obtain powder;
molding: putting the powder into a wet isostatic pressing forming machine, and performing compression forming to obtain a biscuit;
and (3) sintering: placing the powder in a sintering furnace, covering the sintering furnace, vacuumizing the sintering furnace, starting heating when the vacuum surface shows 20Pa, raising the temperature from room temperature to 1000 ℃ within 10h, continuously heating when the temperature reaches 600 ℃, introducing 10MPa of nitrogen, and preserving the heat for 1h when the temperature reaches 1000 ℃; then raising the temperature from 1000 ℃ to 1300 ℃ within 5h, and preserving the heat for 3 h; then heating from 1300 ℃ to 1720 ℃ within 5h, and preserving heat for 5 h; and then cooling the mixture from 1720 ℃ to 1000 ℃ within 3h, and cooling the mixture to the normal temperature along with the furnace to obtain the ceramic material.
Example 3
Preparing materials: 500g of silicon carbide powder, 300g of silicon powder, 60g of silicon nitride powder, 50g of magnesium oxide, 80g of europium oxide and 10g of phenolic resin;
mixing: putting silicon carbide powder, silicon nitride powder, magnesium oxide, europium oxide and phenolic resin into a ball mill, ball-milling for 1h, and sieving to obtain powder;
molding: dry-pressing the powder to obtain a biscuit;
and (3) sintering: placing the biscuit in a sintering furnace, covering the sintering furnace, vacuumizing the sintering furnace, starting heating when the vacuum surface shows 20Pa, raising the temperature from room temperature to 1000 ℃ within 20h, continuously heating when the temperature reaches 800 ℃, introducing 1MPa of nitrogen, and preserving the heat for 1.5h when the temperature reaches 1000 ℃; then heating from 1000 ℃ to 1300 ℃ within 10h, and preserving heat for 3 h; then heating from 1300 ℃ to 1720 ℃ within 8h, and preserving heat for 2 h; and then cooling the mixture from 1720 ℃ to 1000 ℃ within 8h, and cooling the mixture to the normal temperature along with the furnace to obtain the ceramic material.
Example 4
Preparing materials: 560g of silicon carbide powder, 100g of silicon powder, 150g of silicon nitride powder, 50g of magnesium oxide, 50g of cerium oxide, 50g of europium oxide and 40g of phenolic resin;
mixing: putting silicon carbide powder, silicon nitride powder, magnesium oxide, cerium oxide, europium oxide and phenolic resin into a ball mill, adding water, ball-milling for 1h, drying and sieving to obtain powder;
molding: dry-pressing the powder to obtain a biscuit;
and (3) sintering: placing the biscuit in a sintering furnace, covering the sintering furnace, vacuumizing the sintering furnace, starting heating when the vacuum surface shows 20Pa, raising the temperature from room temperature to 1000 ℃ within 12h, continuously heating when the temperature reaches 700 ℃, introducing 8MPa nitrogen, and preserving the heat for 1h when the temperature reaches 1000 ℃; then raising the temperature from 1000 ℃ to 1300 ℃ within 8h, and preserving the heat for 3 h; then heating from 1300 ℃ to 1720 ℃ within 5h, and preserving heat for 3 h; and then cooling the mixture from 1720 ℃ to 1000 ℃ within 7h, and cooling the mixture to the normal temperature along with the furnace to obtain the ceramic material.
Example 5
Otherwise, as in example 1, the temperature at which heating was started was raised from room temperature to 1000 ℃ over 8 hours during sintering in a sintering furnace.
Example 6
In the same manner as in example 1, the temperature at which heating was started was raised from room temperature to 1000 ℃ over 25 hours during sintering in a sintering furnace.
Example 7
Otherwise, as in example 2, silicon powder was used instead of silicon nitride powder.
The raw material components in the invention are tested by adopting the raw material components with the purity of more than 98.6 percent.
The ceramic material prepared in the above embodiment is subjected to a thermal shock resistance strength test, and the test method is as follows: heating the obtained product to 1150 ℃, keeping the temperature for 15min, rapidly cooling the product by using normal-temperature cold water, extruding the product for 10min by using 20kg of pressure when the product is treated to the normal temperature, and circulating the product until the product is broken or the product is not broken after circulating for 20 times, wherein the number of times is recorded as 20 times, and the test results are shown in the following table 1.
The density of the product obtained in the above example was measured, and the cross section of the product was observed, and the results are shown in table 1 below.
The products obtained in the above examples were weighed and the results are shown in table 1 below.
TABLE 1
As shown in the data in Table 1, the ceramic material prepared by the method has the advantages of high density, low porosity, fine section and excellent thermal shock resistance, and the density reaches 2.65g/cm3Therefore, the strength of the ceramic product can be greatly improved, and the service life of the product can be prolonged. And areAnd, the present investigators prepared the above-mentioned article as a lift tube, which is: in the low-pressure casting process, the alloy liquid is filled in a pipeline necessary for a casting mold, and the alloy liquid is required to have the advantages of good high-temperature strength, excellent thermal shock resistance, strong high-temperature corrosion resistance and the like. At present, the lift tube is updated for multiple generations and is sequentially made of cast iron, stainless steel, quartz, aluminum titanate and the like, and a high-performance ceramic material has the characteristics of good strength, excellent thermal shock resistance, strong corrosion resistance and the like, is widely researched and applied to the production and preparation of the lift tube, the development cost of the lift tube is moderate, and the service life of the obtained lift tube is maintained at five months. The product prepared by the operation method of the embodiment is prepared into the lift tube for application, the bending strength is more than 100MPa, the actual service life is more than 5 months, after the product is heated to 1150 ℃ and is kept warm for 15min, the product is rapidly cooled to normal temperature by water, 20kg of pressure is pressed on the lift tube, and 20 times of tests are carried out circularly without cracking.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (12)
1. The preparation method of the high-strength silicon nitride composite silicon carbide ceramic is characterized in that the raw material components comprise, by mass, 50-70% of silicon carbide powder, 10-30% of silicon powder, 5-15% of silicon nitride powder, 5-15% of sintering aid and 1-5% of binder;
uniformly mixing the raw materials, molding, heating and sintering, and cooling in a furnace, wherein the heating and sintering is carried out by heating from room temperature to 1000 ℃ within 10-20h, keeping the temperature for 1-2h, and filling nitrogen with the pressure of 1-10MPa into the sintering furnace when the temperature is increased to 800 ℃ of 600-; then raising the temperature from 1000 ℃ to 1300 ℃ within 5-10h, and preserving the heat for 3 h; heating from 1300 ℃ to 1720 ℃ within 5-10h, preserving heat for 2-5h, cooling from 1720 ℃ within 3-8h to 1000 ℃, and cooling to normal temperature along with the furnace to obtain the product.
2. The method of claim 1, wherein the mixing is performed by mixing the raw materials, and homogenizing the mixture by dry or wet milling.
3. The method of claim 1, wherein the forming is by slip casting, dry pressing or wet isostatic pressing to form a green body.
4. The method of claim 1, wherein the elevated temperature sintering is performed by placing the green body in a sintering furnace, evacuating the furnace until a vacuum level of < 20Pa is observed, and heating the green body to elevated temperature.
5. The method for preparing high-strength silicon nitride-silicon carbide composite ceramic according to claim 1, wherein the temperature-rising sintering is carried out by raising the temperature from room temperature to 1000 ℃ for 15 hours, introducing 2Mpa nitrogen when the temperature reaches 700 ℃, continuing heating, and keeping the temperature at 1000 ℃ for 2 hours; heating from 1000 ℃ to 1300 ℃ within 6h, and keeping the temperature for 2 h; after the temperature is raised from 1300 ℃ to 1720 ℃ within 8 hours, the temperature is kept for 2 hours; cooling to 1000 deg.C from 1720 deg.C within 4h, and cooling to normal temperature.
6. The method for preparing the high-strength silicon nitride-silicon carbide composite ceramic according to claim 1, wherein the raw material components comprise, by mass, 50% of silicon carbide powder, 20% of silicon powder, 15% of silicon nitride powder, 10% of sintering aid and 5% of binder.
7. The method of producing a high-strength silicon nitride composite silicon carbide ceramic according to claim 1 or 6, wherein the binder is a solid resin.
8. The method of claim 7, wherein the solid resin is a phenolic resin.
9. The method for preparing the high-strength silicon nitride-silicon carbide composite ceramic according to claim 1 or 6, wherein the sintering aid is one or more of yttrium oxide, europium oxide, cerium oxide, aluminum oxide and magnesium oxide.
10. A high-strength silicon nitride composite silicon carbide ceramic produced by the production method according to any one of claims 1 to 9.
11. Use of the high strength silicon nitride composite silicon carbide ceramic according to claim 10 in the manufacture of a ceramic structural member.
12. The use of claim 10, wherein the ceramic structural members comprise refractory bricks, thermocouple protection tubes, metal catheters, and heat insulation rings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010322659.4A CN111499387A (en) | 2020-04-22 | 2020-04-22 | High-strength silicon nitride composite silicon carbide ceramic and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010322659.4A CN111499387A (en) | 2020-04-22 | 2020-04-22 | High-strength silicon nitride composite silicon carbide ceramic and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111499387A true CN111499387A (en) | 2020-08-07 |
Family
ID=71874560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010322659.4A Pending CN111499387A (en) | 2020-04-22 | 2020-04-22 | High-strength silicon nitride composite silicon carbide ceramic and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111499387A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825477A (en) * | 2020-08-13 | 2020-10-27 | 中钢南京环境工程技术研究院有限公司 | Preparation method of anti-oxidation silicon carbide kiln furniture |
| CN114853500A (en) * | 2022-04-29 | 2022-08-05 | 中国科学院上海硅酸盐研究所 | Silicon nitride and silicon carbide combined complex phase ceramic and preparation method and application thereof |
| CN115417673A (en) * | 2022-10-14 | 2022-12-02 | 广州市拓道新材料科技有限公司 | High-wear-resistance silicon nitride/silicon carbide composite ceramic and preparation method and application thereof |
| CN115417674A (en) * | 2022-10-14 | 2022-12-02 | 郴州市拓道新材料科技有限公司 | Wear-resistant silicon nitride/silicon carbide composite ceramic and preparation method and application thereof |
| CN115894058A (en) * | 2022-11-25 | 2023-04-04 | 南京航空航天大学 | Method for flash-burning rapid densification of SiC/SiC composite material |
| CN116573940A (en) * | 2023-04-28 | 2023-08-11 | 合肥陶陶新材料科技有限公司 | High-toughness silicon carbide ceramic material and preparation method thereof |
| CN116730725A (en) * | 2023-06-05 | 2023-09-12 | 衡阳凯新特种材料科技有限公司 | Silicon nitride composite ceramic material for lift tube, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423877A (en) * | 2008-11-28 | 2009-05-06 | 辽宁科技大学 | Non-metal drill bit for tap hole of blast furnace and method for producing the same |
| CN103288062A (en) * | 2012-02-22 | 2013-09-11 | 中国科学院理化技术研究所 | Method for synthesizing silicon nitride powder in ordinary pressure nitridation reaction mode |
| CN103332662A (en) * | 2013-07-11 | 2013-10-02 | 上海大学 | Method for preparing alpha phase and beta phase silicon nitride powder by improved direct nitriding method |
| CN105727755A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院金属研究所 | Gradient-pore silicon nitride and silicon carbide combined film tube and preparation method therefor |
| CN107540392A (en) * | 2017-08-23 | 2018-01-05 | 中国人民解放军海军工程大学 | The vacuum vibration casting forming method of silicon nitride combined silicon carbide refractory |
| CN108975921A (en) * | 2018-08-16 | 2018-12-11 | 南通通州湾新材料科技有限公司 | A kind of preparation method and its ceramic copper-clad plate of silicon nitride ceramics |
-
2020
- 2020-04-22 CN CN202010322659.4A patent/CN111499387A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423877A (en) * | 2008-11-28 | 2009-05-06 | 辽宁科技大学 | Non-metal drill bit for tap hole of blast furnace and method for producing the same |
| CN103288062A (en) * | 2012-02-22 | 2013-09-11 | 中国科学院理化技术研究所 | Method for synthesizing silicon nitride powder in ordinary pressure nitridation reaction mode |
| CN103332662A (en) * | 2013-07-11 | 2013-10-02 | 上海大学 | Method for preparing alpha phase and beta phase silicon nitride powder by improved direct nitriding method |
| CN105727755A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院金属研究所 | Gradient-pore silicon nitride and silicon carbide combined film tube and preparation method therefor |
| CN107540392A (en) * | 2017-08-23 | 2018-01-05 | 中国人民解放军海军工程大学 | The vacuum vibration casting forming method of silicon nitride combined silicon carbide refractory |
| CN108975921A (en) * | 2018-08-16 | 2018-12-11 | 南通通州湾新材料科技有限公司 | A kind of preparation method and its ceramic copper-clad plate of silicon nitride ceramics |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825477A (en) * | 2020-08-13 | 2020-10-27 | 中钢南京环境工程技术研究院有限公司 | Preparation method of anti-oxidation silicon carbide kiln furniture |
| CN111825477B (en) * | 2020-08-13 | 2022-05-10 | 中钢南京环境工程技术研究院有限公司 | Preparation method of anti-oxidation silicon carbide kiln furniture |
| CN114853500A (en) * | 2022-04-29 | 2022-08-05 | 中国科学院上海硅酸盐研究所 | Silicon nitride and silicon carbide combined complex phase ceramic and preparation method and application thereof |
| CN115417673A (en) * | 2022-10-14 | 2022-12-02 | 广州市拓道新材料科技有限公司 | High-wear-resistance silicon nitride/silicon carbide composite ceramic and preparation method and application thereof |
| CN115417674A (en) * | 2022-10-14 | 2022-12-02 | 郴州市拓道新材料科技有限公司 | Wear-resistant silicon nitride/silicon carbide composite ceramic and preparation method and application thereof |
| CN115417674B (en) * | 2022-10-14 | 2023-06-09 | 湖南省拓道新材料科技有限公司 | Wear-resistant silicon nitride/silicon carbide composite ceramic and preparation method and application thereof |
| CN115417673B (en) * | 2022-10-14 | 2023-08-08 | 广州市拓道新材料科技有限公司 | High-wear-resistance silicon nitride/silicon carbide composite ceramic and preparation method and application thereof |
| CN115894058A (en) * | 2022-11-25 | 2023-04-04 | 南京航空航天大学 | Method for flash-burning rapid densification of SiC/SiC composite material |
| CN116573940A (en) * | 2023-04-28 | 2023-08-11 | 合肥陶陶新材料科技有限公司 | High-toughness silicon carbide ceramic material and preparation method thereof |
| CN116730725A (en) * | 2023-06-05 | 2023-09-12 | 衡阳凯新特种材料科技有限公司 | Silicon nitride composite ceramic material for lift tube, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111499387A (en) | High-strength silicon nitride composite silicon carbide ceramic and preparation method and application thereof | |
| CN104973865B (en) | Preparation method of high-thermal-conductivity aluminum nitride ceramic | |
| CN110590377B (en) | High beta-phase compact silicon nitride ceramic and low-temperature preparation method | |
| CN107034378B (en) | A kind of preparation method of hollow alumina ball/silicon carbide collaboration reinforced aluminum matrix composites | |
| CN109553419A (en) | A kind of air pressure solid-phase sintering boron carbide complex phase ceramic and preparation method thereof | |
| CN105399426A (en) | Preparation method of boron nitride ceramic | |
| CN101323536A (en) | Boron nitride porous ceramic thermal insulation material, preparation and use thereof | |
| CN107162597A (en) | A kind of formula of moulding by casting silicon nitride products based on silicon carbide and preparation method thereof | |
| CN104909765A (en) | Method for rapidly preparing high-performance Si3N4 ceramic ball at low cost | |
| CN106987752B (en) | A kind of gradient hard alloy preparation method of case-carbonizing | |
| CN101654362A (en) | Silicon oxynitride combined carborundum high-temperature ceramic material and preparation method thereof | |
| CN107963890B (en) | Preparation method of titanium nitride porous conductive ceramic | |
| CN115838290B (en) | Pressureless liquid phase sintering silicon carbide ceramic and preparation method thereof | |
| CN103820691B (en) | A kind of normal pressure-sintered preparation method of FeAl/TiC matrix material | |
| CN105294160A (en) | Method for preparing porous silicon nitride ceramics through gel casting and microwave sintering | |
| CN107697916B (en) | Preparation method of metal-silicon-carbon compound nano powder | |
| CN104177087A (en) | Method for preparing silicon carbide bonded silicon nitride composite material by using microwave sintering process | |
| CN101734920B (en) | Titanium nitride porous ceramics and preparation method thereof | |
| CN112209722A (en) | Silicon nitride composite material, preparation method thereof and heating element | |
| CN100465132C (en) | Preparation method of carborundum composite-phase ceramic | |
| CN105967692A (en) | Manufacturing method of silicon-nitride-combined silicon carbide ceramic crucible | |
| CN107142404B (en) | The in-situ preparation method of surface self-lubricating Ti (C, N) based ceramic metal | |
| CN108147834A (en) | Regulatable lightweight silicon nitride antenna house of dielectric constant and preparation method thereof | |
| CN1092165C (en) | Low temp. sintering of aluminum nitride ceramics | |
| JPS605550B2 (en) | Manufacturing method of silicon carbide sintered body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200807 |