CN113149676A - Method for sintering in-situ toughened boron carbide-based multiphase ceramic by using two-step method - Google Patents
Method for sintering in-situ toughened boron carbide-based multiphase ceramic by using two-step method Download PDFInfo
- Publication number
- CN113149676A CN113149676A CN202110614993.1A CN202110614993A CN113149676A CN 113149676 A CN113149676 A CN 113149676A CN 202110614993 A CN202110614993 A CN 202110614993A CN 113149676 A CN113149676 A CN 113149676A
- Authority
- CN
- China
- Prior art keywords
- sintering
- boron carbide
- powder
- temperature
- pressure
- 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.)
- Granted
Links
Images
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
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
-
- 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
- C04B35/563—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 boron 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- 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
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- 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
- C04B2235/6567—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
- C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Products (AREA)
Abstract
The invention provides a method for sintering in-situ toughened boron carbide-based multiphase ceramic by using a two-step method, which mainly solves the problems that the production cost of the boron carbide ceramic is high and the high strength and the high toughness are difficult to maintain. The method comprises four key steps of mixing, drying, molding and sintering. The sintering by the two-step method is a hot-pressing sintering process: the first stage process is carried out at the temperature of 1000-1300 ℃ and under the pressure of 30-60 MPa for 0.5-1.5 h; in the second stage, the temperature is raised to 1600-1800 ℃, the pressure is unchanged, and the heat preservation and pressure maintaining are carried out for 0.5-1.5 h. Cooling along with the furnace to obtain the in-situ growth plate strip crystal toughened boron carbide-based complex phase ceramic material. The method has simple and convenient process, the lath-shaped toughening phase synthesized in situ is uniformly dispersed and well combined with a matrix interface, the microstructure is uniform, the density is high, the mechanical property is excellent, the remarkable toughening effect can be achieved while the excellent hardness and bending strength are maintained, and the method is very suitable for industrial mass production.
Description
Technical Field
The invention belongs to the field of superhard material preparation, and particularly relates to a method for preparing high-toughness boron carbide-based multiphase ceramic by sintering boron carbide and a composite sintering aid through a two-step method, wherein a toughening phase is in-situ grown lath-shaped or rod-shaped zirconium boride.
Background
Boron carbide is known as "black diamond" and has a hardness second only to diamond and cubic boron nitride, high temperature hardness: (>30GPa) even better than diamond and cubic boron nitride. Since the fifties of the twentieth century, under the promotion of military and civil demands, many researches on engineering application technology of boron carbide have been carried out. Meanwhile, the boron carbide has lower density of only 2.52g/cm3. And the boron carbide material has low price, rich raw material sources and easy treatment of waste materials. It can become one of the superhard materials that can be applied in practical mass production. Due to the characteristics of high hardness and low density, boron carbide materials are often applied to the fields of light armors, bulletproof vest interlayers, aerospace structural materials and the like; it has been used as a wear-resistant material for sandblasting nozzles, diamond nozzles, nozzles for water jet cutters, industrial abrasives, etc., due to its ultra-high hardness and excellent wear resistance. Boron carbide is used as a reaction raw material to react with metal at high temperature to generate metal boride, has high microhardness and wear resistance, and is used for surface strengthening of metal and alloy.
Because the sintering temperature of boron carbide is high, the realization is difficult, and the search of a proper sintering process for preparing the boron carbide material becomes one of the technical problems to be solved at present. The current sintering process mainly comprises pressureless sintering, hot-pressing sintering and electric spark plasma sintering. Generally, boron carbide is subjected to pressureless sintering at a high temperature of about 2200 ℃, and the compactness can reach about 95%. The hot pressing sintering method and the electric spark plasma sintering method can reduce the sintering temperature to about 2000 ℃ and require the pressure of more than 30MPa, for example, the boron carbide ceramic with the density of more than 95 percent is prepared under the conditions of 2100 ℃ and 40 MPa. The difficulty in sintering boron carbide ceramics is thus seen, which limits their engineering applications to a large extent.
In the existing research, the method is mainly realized by adding a sintering aid, changing a sintering mode and optimizing a process curve. The addition of the sintering aid can effectively promote the sintering densification process of the boron carbide and improve the fracture toughness of the boron carbide. However, the addition of too much sintering aid can reduce the hardness, so that the material loses the characteristic of high hardness of boron carbide. In addition, the design of the sintering process is also a technical problem. The common sintering process is mainly one-step sintering, the process curve is relatively fixed, and optimization does not occur along with the change of raw material components; and the difficulty of designing a reasonable process is higher due to more variable parameters of the two-step sintering. Therefore, by adding a proper amount of other components, improving the sintering process, improving the mutual diffusivity of the boron carbide matrix and the additive components to promote sintering densification and improve the comprehensive mechanical properties of the boron carbide ceramic, the problem of optimization is urgently needed to be solved at present.
Disclosure of Invention
The invention aims to provide a method for sintering in-situ toughened boron carbide-based multiphase ceramics by utilizing a two-step method in order to improve the mutual diffusivity of a boron carbide matrix and an additive component to promote sintering densification and improve the comprehensive mechanical property of the boron carbide ceramics.
The purpose of the invention is realized as follows:
the invention provides a method for sintering in-situ toughened boron carbide-based multiphase ceramic by using a two-step method, which comprises the following key steps:
(1) mixing materials: carrying out wet mixing ball milling on boron carbide powder, boron oxide, silicon oxide and silicon carbide raw material powder to obtain precursor slurry;
(2) and (3) drying: putting the precursor slurry into a rotary evaporator for drying and sieving to obtain precursor powder;
(3) molding: adding a carbon source into the obtained ceramic precursor powder, carrying out dry mixing and ball milling, and putting the obtained mixture into a die for prepressing and molding through a mechanical press;
(4) and (3) sintering: carrying out hot-pressing sintering by adopting a two-step method under a vacuum condition, wherein the first-stage process is 1000-1300 ℃, pressurizing in the heating process, and keeping the temperature and the pressure for a period of time; and the second stage of the process is to continue heating to 1600-1800 ℃, keeping the temperature and the pressure for a period of time, and cooling to room temperature along with the furnace. The boron carbide-based multiphase ceramic with excellent comprehensive performance is obtained.
In the step (1), the initial raw material powder of the precursor powder is mixed with the mixed sintering aid powder according to the boron carbide powder ratio and the volume ratio of (7-9) to 1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide, and the molar ratio of (3-9) to (4-6) to 4. And mixing the mixture by using absolute ethyl alcohol as a medium for 12-36 h by using a ball mill. In addition, the selected ball mill is a planetary ball mill, the ball milling tank is a hard alloy tank, the grinding balls are tungsten carbide balls, and the ball-to-material ratio is (10-20): 1.
Putting the precursor slurry into a rotary evaporator for drying at a temperature of more than 70 ℃ for 4-10 hours in the step (2); drying, sieving with 60 mesh sieve.
The carbon source used in the step (3) is phenolic resin, is added in a powder form, and is mixed for 10-24 hours by a planetary ball mill, wherein the adding amount is 1-3 wt% of the precursor powder obtained in the step (2).
The two-step sintering in the step (4) adopts the hot-pressing sintering under the vacuum condition, the temperature rise rate of the first stage is 5-15 ℃/min, the pressure is increased to 30-60 MPa from 600-800 ℃, and the heat preservation and pressure maintaining are carried out for 0.5-1.5 h; in the second stage, the heating rate is 8-20 ℃/min, and the heat preservation and pressure maintaining are carried out for 0.5-1.5 h. The adopted cooling mode of the vacuum atmosphere sintering furnace is circulating water cooling.
The finally obtained boron carbide-based multiphase ceramic product has strip-shaped or rod-shaped zirconium boride uniformly distributed in the material structure of the boron carbide ceramic matrix, contains no oxide, has greatly improved comprehensive mechanical properties, particularly fracture toughness compared with boron carbide pure ceramic, has Vickers hardness higher than 22GPa, bending strength higher than 460MPa and fracture toughness higher than 8 MPa.m1/2。
The patent proposes that the boron carbide-based complex phase ceramic material with higher toughness is prepared by utilizing the in-situ reaction and a hot-pressing sintering mode at lower cost, and the original excellent performance of the boron carbide ceramic is hardly influenced.The method mainly comprises an addition formula of a sintering aid and a two-step hot-pressing sintering process. Adding composite sintering assistant into boron carbide, and smelting B at low temperature under the assistance of external pressure2O3Effectively promotes the deflection rearrangement of the boron carbide particles, improves the mutual contact among the boron carbide particles and the density of a green body, and is beneficial to the later-stage sintering densification of the boron carbide. When the sintering temperature is increased and mechanical pressure is applied at a proper time, other components in the sintering aid are mixed with B2O3Reaction takes place, elimination of B2O3. On one hand, boron oxide is eliminated before blocking sintering, and B is avoided in the later sintering process2O3Effect on boron carbide densification behavior; on the other hand, in-situ reaction is introduced, so that the sintering activity is improved, and the bonding strength of the boron carbide matrix and the toughening phase is facilitated. On the premise of maintaining excellent mechanical properties of boron carbide, the fracture toughness of the final product is greatly improved, and the use safety of the product is enhanced.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention mainly solves the problems that the existing sintering preparation cost for improving the performance of the boron carbide-based multiphase ceramic is high, the period is long, and the performance of the boron carbide-based multiphase ceramic cannot be effectively improved by adopting low-cost metal oxide. The required complex phase ceramic is synthesized by using an oxide additive with lower cost through a two-step sintering method, the process is improved through two angles of improving the rough blank state and improving the reaction activity, and the boron carbide-based complex phase ceramic is remarkably strengthened and toughened.
(2) The invention utilizes the in-situ reaction of the oxide with low price to synthesize the boron carbide-based multiphase ceramics with different components by the two-step hot-pressing sintering, compared with the traditional one-step sintering mode, the hot-pressing sintering mode can obviously reduce the sintering cost, and meanwhile, the prepared ceramic product obtains the boride second phase by the in-situ reaction of the oxide residues. Through the difference of the thermal expansion coefficients of the matrix and the boride and the chemical bonding of the matrix and the boride in the in-situ reaction process, the material consumes the energy of crack propagation through phenomena of crack deflection, bridging, bifurcation and the like in the fracture process, and has the characteristic of high toughness under the characteristic of ensuring the original strength of boron carbide.
Although oxide additives are used in a large number in the sintering preparation of boron carbide-based multiphase ceramics, they tend to cause a reduction in the properties of the resulting articles due to the outgassing from their oxidation. In order to make the cheap oxide additive utilized to the maximum, the invention applies a heat-insulating platform to the sintering process at low temperature, expands the effect of the oxide additive at low temperature and improves the rough blank state. Then the oxide is removed through in-situ reaction at medium and high temperature, and the influence that the oxide reacts with carbide at high temperature and gas is released to block the sintering densification process is eliminated. Meanwhile, the strip-shaped zirconium boride is successfully prepared as a toughening reinforcing phase by pressurizing in the temperature rise process and applying a heat preservation platform in a high-temperature interval. Finally, the high-performance ceramic material is prepared by low-cost raw materials and a sintering process, and the comprehensive mechanical properties, particularly the fracture toughness, of the high-performance ceramic material are greatly improved compared with that of boron carbide pure ceramic.
Drawings
FIG. 1 is an XRD pattern of a boron carbide-based complex phase ceramic prepared according to an embodiment of the present invention;
FIG. 2 is an SEM plan view of a boron carbide-based composite ceramic prepared according to an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1:
(1) mixing materials: mixing boron carbide powder (the grain diameter is less than or equal to 2 mu m and the purity is 98%) with mixed sintering aid powder according to the volume ratio of 7.3:1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide (the grain diameter is less than or equal to 5 mu m and the purity is 98%) according to the molar ratio of 3:5: 4. Putting the powder into a ball milling tank, adding absolute ethyl alcohol (with the purity of 99.7%) with the same mass as the powder, and carrying out wet mixing and ball milling. Ball milling is carried out for 18h at the rotating speed of 60r/min with the ball-material ratio of 15: 1;
(2) and (3) drying: and (3) putting the precursor slurry into a rotary evaporator to dry for 6 hours, wherein the water bath temperature is 70 ℃. Drying, sieving by a 80-mesh sieve to obtain precursor powder;
(3) molding: adding phenolic resin serving as a carbon source into the obtained ceramic precursor powder, and carrying out dry mixing and ball milling, wherein the adding amount of the phenolic resin is 3 wt% of the precursor powder obtained in the step (2), and the ball milling time is 10 hours. Putting the mixture obtained after ball milling into a die, and pre-pressing and molding the mixture under the pressure of 120MPa by a mechanical press;
(4) and (3) sintering: hot-pressing sintering is carried out by adopting a two-step method in vacuum condition, the temperature rise rate of the first stage process is 10 ℃/min, the temperature is raised to 1100 ℃, the pressure is increased to 40MPa from 650 ℃, and the heat preservation and pressure maintaining are carried out for 1 h; the temperature rise rate of the second stage process is 10 ℃/min, the second stage process is continuously heated to 1800 ℃, and the temperature and pressure are maintained for 70min, and then the second stage process is cooled to room temperature along with the furnace.
(5) Obvious lath-shaped zirconium boride particles are uniformly distributed in the boron carbide matrix under the observation of an electron microscope; the final product is tested for mechanical property, the Vickers hardness is 27.1GPa, the bending strength is 471.3MPa, and the fracture toughness is 8.1 MPa.m1/2。
Example 2:
(1) mixing materials: mixing boron carbide powder (the grain diameter is less than or equal to 2 mu m and the purity is 98%) with mixed sintering aid powder according to the volume ratio of 9:1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide (the grain diameter is less than or equal to 5 mu m and the purity is 98%) in the molar ratio of 2:3: 2. Putting the powder into a ball milling tank, adding absolute ethyl alcohol (with the purity of 99.7%) with the same mass as the powder, and carrying out wet mixing and ball milling. Ball milling is carried out for 12 hours at the rotating speed of 100r/min with the ball-material ratio of 15: 1;
(2) and (3) drying: and (3) putting the precursor slurry into a rotary evaporator to dry for 8h, wherein the water bath temperature is 75 ℃. Drying, and sieving with a 120-mesh sieve to obtain precursor powder;
(3) molding: adding phenolic resin serving as a carbon source into the obtained ceramic precursor powder, and carrying out dry mixing and ball milling, wherein the adding amount of the phenolic resin is 3 wt% of the precursor powder obtained in the step (2), and the ball milling time is 10 hours. Putting the mixture obtained after ball milling into a die, and pre-pressing and molding the mixture under the pressure of 150MPa by a mechanical press;
(4) and (3) sintering: hot-pressing sintering is carried out by adopting a two-step method in a vacuum condition, the temperature rise rate of the first-stage process is 15 ℃/min, the temperature is raised to 1200 ℃, the pressure is increased to 60MPa from 600 ℃, and the heat preservation and pressure maintaining are carried out for 1 h; the temperature rise rate of the second stage process is 12 ℃/min, the second stage process is continuously heated to 1800 ℃, and the temperature and pressure are kept for 1h, and then the second stage process is cooled to room temperature along with the furnace.
(5) Obvious lath-shaped zirconium boride particles are uniformly distributed in the boron carbide matrix under the observation of an electron microscope; the final product is tested for mechanical property, the Vickers hardness is 26.3GPa, the bending strength is 500.4MPa, and the fracture toughness is 8.8 MPa.m1/2。
Example 3:
(1) mixing materials: mixing boron carbide powder (the grain diameter is less than or equal to 2 mu m and the purity is 98%) with mixed sintering aid powder according to the volume ratio of 5.7:1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide (the grain diameter is less than or equal to 5 mu m and the purity is 98%) according to the molar ratio of 5:4: 4. Putting the powder into a ball milling tank, adding absolute ethyl alcohol (with the purity of 99.7%) with the same mass as the powder, and carrying out wet mixing and ball milling. Ball milling is carried out for 12 hours at the rotating speed of 100r/min with the ball-material ratio of 15: 1;
(2) and (3) drying: and (3) putting the precursor slurry into a rotary evaporator to dry for 6 hours, wherein the water bath temperature is 70 ℃. Drying, and sieving with a 120-mesh sieve to obtain precursor powder;
(3) molding: adding phenolic resin serving as a carbon source into the obtained ceramic precursor powder, and carrying out dry mixing and ball milling, wherein the adding amount of the phenolic resin is 2 wt% of the precursor powder obtained in the step (2), and the ball milling time is 6 h. Putting the mixture obtained after ball milling into a die, and pre-pressing and molding the mixture under the pressure of 150MPa by a mechanical press;
(4) and (3) sintering: hot-pressing sintering is carried out by adopting a two-step method in vacuum condition, the temperature rise rate of the first stage process is 8 ℃/min, the temperature is raised to 1200 ℃, the pressure is increased to 30MPa from 700 ℃, and the heat preservation and pressure maintaining are carried out for 1.5 h; the temperature rise rate of the second stage process is 10 ℃/min, the second stage process is continuously heated to 1750 ℃, and the temperature and pressure are kept for 1h, and then the second stage process is cooled to the room temperature along with the furnace.
(5) Obvious lath-shaped zirconium boride particles are uniformly distributed in the boron carbide matrix under the observation of an electron microscope; the final product is tested for mechanical property, the Vickers hardness is 24.7GPa, the bending strength is 485.8MPa, and the fracture toughness is 8.0 MPa.m1/2。
Example 4:
(1) mixing materials: mixing boron carbide powder (the grain diameter is less than or equal to 2 mu m and the purity is 98%) with mixed sintering aid powder according to the volume ratio of 9:1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide (the grain diameter is less than or equal to 5 mu m and the purity is 98%) according to the molar ratio of 9:6: 4. Putting the powder into a ball milling tank, adding absolute ethyl alcohol (with the purity of 99.7%) with the same mass as the powder, and carrying out wet mixing and ball milling. Ball milling is carried out for 24 hours at the rotating speed of 300r/min with the ball-material ratio of 15: 1;
(2) and (3) drying: and (3) putting the precursor slurry into a rotary evaporator to dry for 6 hours, wherein the water bath temperature is 70 ℃. Drying, and sieving with a 120-mesh sieve to obtain precursor powder;
(3) molding: adding phenolic resin serving as a carbon source into the obtained ceramic precursor powder, and carrying out dry mixing and ball milling, wherein the adding amount of the phenolic resin is 3 wt% of the precursor powder obtained in the step (2), and the ball milling time is 10 hours. Putting the mixture obtained after ball milling into a die, and pre-pressing and molding the mixture under the pressure of 180MPa by a mechanical press;
(4) and (3) sintering: hot-pressing sintering is carried out by adopting a two-step method in vacuum condition, the temperature rise rate of the first stage process is 10 ℃/min, the temperature is raised to 1150 ℃, the pressure is increased to 60MPa from 800 ℃, and the heat preservation and pressure maintaining are carried out for 1 h; the temperature rise rate of the second stage process is 10 ℃/min, the second stage process is continuously heated to 1800 ℃, and the temperature and pressure are kept for 1h, and then the second stage process is cooled to room temperature along with the furnace.
(5) Obvious lath-shaped zirconium boride particles are uniformly distributed in the boron carbide matrix under the observation of an electron microscope; the final product is tested for mechanical property, the Vickers hardness is 29.5GPa, the bending strength is 518.2MPa, and the fracture toughness is 8.9 MPa.m1/2。
Example 5:
(1) mixing materials: mixing boron carbide powder (the grain diameter is less than or equal to 2 mu m and the purity is 98%) with mixed sintering aid powder according to the volume ratio of 8.5:1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide (the grain diameter is less than or equal to 5 mu m and the purity is 98%) according to the molar ratio of 7:5: 4. Putting the powder into a ball milling tank, adding absolute ethyl alcohol (with the purity of 99.7%) with the same mass as the powder, and carrying out wet mixing and ball milling. Ball milling is carried out for 20 hours at the rotating speed of 400r/min with the ball-material ratio of 18: 1;
(2) and (3) drying: and (3) putting the precursor slurry into a rotary evaporator to dry for 6 hours, wherein the water bath temperature is 70 ℃. Drying, sieving by a 80-mesh sieve to obtain precursor powder;
(3) molding: adding phenolic resin serving as a carbon source into the obtained ceramic precursor powder, and carrying out dry mixing and ball milling, wherein the adding amount of the phenolic resin is 3 wt% of the precursor powder obtained in the step (2), and the ball milling time is 5 h. Putting the mixture obtained after ball milling into a die, and pre-pressing and molding the mixture under the pressure of 120MPa by a mechanical press;
(4) and (3) sintering: hot-pressing sintering is carried out by adopting a two-step method in vacuum condition, the temperature rise rate of the first-stage process is 10 ℃/min, the temperature is raised to 1300 ℃, the pressure is increased to 50MPa from 700 ℃, and the heat preservation and pressure maintaining are carried out for 1.5 h; the temperature rise rate of the second stage process is 15 ℃/min, the second stage process is continuously heated to 1800 ℃, and after heat preservation and pressure maintaining for 0.5h, the second stage process is cooled to room temperature along with the furnace.
(5) Obvious lath-shaped zirconium boride particles are uniformly distributed in the boron carbide matrix under the observation of an electron microscope; the final product is tested for mechanical property, the Vickers hardness is 26.9GPa, the bending strength is 587.3MPa, and the fracture toughness is 8.5 MPa.m1/2。
Example 6:
(1) mixing materials: mixing boron carbide powder (the grain diameter is less than or equal to 2 mu m and the purity is 98%) with mixed sintering aid powder according to the volume ratio of 7.2:1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide (the grain diameter is less than or equal to 5 mu m and the purity is 98%) according to the molar ratio of 3:5: 4. Putting the powder into a ball milling tank, adding absolute ethyl alcohol (with the purity of 99.7%) with the same mass as the powder, and carrying out wet mixing and ball milling. Ball milling is carried out for 24 hours at the rotating speed of 400r/min with the ball-material ratio of 20: 1;
(2) and (3) drying: and (3) putting the precursor slurry into a rotary evaporator to dry for 8h, wherein the water bath temperature is 75 ℃. Drying, and sieving with a 120-mesh sieve to obtain precursor powder;
(3) molding: adding phenolic resin serving as a carbon source into the obtained ceramic precursor powder, and carrying out dry mixing and ball milling, wherein the adding amount of the phenolic resin is 3 wt% of the precursor powder obtained in the step (2), and the ball milling time is 8 h. Putting the mixture obtained after ball milling into a die, and pre-pressing and molding the mixture under the pressure of 180MPa by a mechanical press;
(4) and (3) sintering: hot-pressing sintering is carried out by adopting a two-step method in vacuum condition, the temperature rise rate of the first stage process is 15 ℃/min, the temperature is raised to 1250 ℃, the pressure is increased to 60MPa from 800 ℃, and the heat preservation and pressure maintaining are carried out for 1 h; the temperature rise rate of the second stage process is 8 ℃/min, the second stage process is continuously heated to 1800 ℃, and the temperature and pressure are kept for 1.5h, and then the second stage process is cooled to room temperature along with the furnace.
Obvious lath-shaped zirconium boride particles are uniformly distributed in the boron carbide matrix under the observation of an electron microscope; the final product is tested for mechanical property, the Vickers hardness is 30.2GPa, the bending strength is 575.8MPa, and the fracture toughness is 9.2 MPa.m1/2。
In summary, the following steps: the invention discloses a method for sintering in-situ toughened boron carbide-based multiphase ceramic by using a two-step method, relates to the field of preparation of superhard materials, and aims to solve the problems that the production cost of boron carbide ceramic is high, and high strength and high toughness are difficult to maintain. The method mainly comprises four key steps of mixing, drying, molding and sintering. The sintering by the two-step method is a hot-pressing sintering process: the first stage process is carried out at the temperature of 1000-1300 ℃ and under the pressure of 30-60 MPa for 0.5-1.5 h; in the second stage, the temperature is raised to 1600-1800 ℃, the pressure is unchanged, and the heat preservation and pressure maintaining are carried out for 0.5-1.5 h. Cooling along with the furnace to obtain the in-situ growth plate strip crystal toughened boron carbide-based complex phase ceramic material. The method has the advantages of simple and convenient process, uniform dispersion of the in-situ synthesized lath-shaped toughening phase, good combination with a matrix interface, uniform microstructure, high density and excellent mechanical property. The high-hardness and high-bending-resistance composite material can achieve a remarkable toughening effect while maintaining excellent hardness and bending strength, and is very suitable for industrial mass production.
Claims (6)
1. A method for sintering in-situ toughened boron carbide-based multiphase ceramic by using a two-step method is characterized in that a strip-shaped zirconium boride reinforced multiphase ceramic product is prepared by adopting a two-step method solid phase sintering process, and the method comprises the following key steps:
(1) mixing materials: carrying out wet mixing ball milling on boron carbide powder, boron oxide, silicon oxide and silicon carbide raw material powder to obtain precursor slurry;
(2) and (3) drying: putting the precursor slurry into a rotary evaporator for drying and sieving to obtain precursor powder;
(3) molding: adding a carbon source into the obtained ceramic precursor powder, carrying out dry mixing and ball milling, and putting the obtained mixture into a die for prepressing and molding through a mechanical press;
(4) and (3) sintering: carrying out hot-pressing sintering by adopting a two-step method under a vacuum condition, wherein the first-stage process is 1000-1300 ℃, pressurizing in the heating process, and keeping the temperature and the pressure for a period of time; and the second stage of the process is to continue heating to 1600-1800 ℃, keeping the temperature and pressure for a period of time, and then cooling to room temperature along with the furnace to obtain the boron carbide-based multiphase ceramic with excellent comprehensive performance.
2. The two-step method for sintering in-situ toughened boron carbide-based multiphase ceramic according to claim 1, wherein: mixing the initial raw material powder of the precursor powder in the step (1) according to the boron carbide powder ratio, mixing and sintering aid powder according to the volume ratio of (7-9): 1, wherein the mixed sintering aid comprises three powders of boron oxide, silicon carbide and zirconium oxide in the molar ratio of (3-9): 4-6): 4, mixing the mixture by using a ball mill for 12-36 h by using absolute ethyl alcohol as a medium, and in addition, the selected ball mill is a planetary ball mill, the ball mill tank is a hard alloy tank, the grinding balls are tungsten carbide balls, and the ball-to-material ratio is (10-20): 1.
3. The two-step method for sintering in-situ toughened boron carbide-based multiphase ceramic according to claim 1, wherein: putting the precursor slurry into a rotary evaporator for drying at a temperature of more than 70 ℃ for 4-10 hours in the step (2); drying, sieving with 60 mesh sieve.
4. The two-step method for sintering in-situ toughened boron carbide-based multiphase ceramic according to claim 1, wherein: the carbon source used in the step (3) is phenolic resin, is added in a powder form, and is mixed for 10-24 hours by a planetary ball mill, wherein the adding amount is 1-3 wt% of the precursor powder obtained in the step (2).
5. The two-step method for sintering in-situ toughened boron carbide-based multiphase ceramic according to claim 1, wherein: the two-step sintering in the step (4) adopts the hot-pressing sintering under the vacuum condition, the temperature rise rate of the first stage is 5-15 ℃/min, the pressure is increased to 30-60 MPa from 600-800 ℃, and the heat preservation and pressure maintaining are carried out for 0.5-1.5 h; and in the second stage, the heating rate is 8-20 ℃/min, the heat preservation and pressure maintaining are carried out for 0.5-1.5 h, and the adopted cooling mode of the vacuum atmosphere sintering furnace is circulating water cooling.
6. The two-step method for sintering in-situ toughened boron carbide-based multiphase ceramic according to claim 1, wherein: the boron carbide-based multiphase ceramic product obtained in the step (4) has strip-shaped or rod-shaped zirconium boride uniformly distributed in the material structure, does not contain oxides in the components of the product, has greatly improved comprehensive mechanical properties, particularly fracture toughness compared with boron carbide pure ceramic, has Vickers hardness higher than 22GPa, bending strength higher than 460MPa and fracture toughness higher than 8 MPa.m1/2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110614993.1A CN113149676B (en) | 2021-06-02 | 2021-06-02 | Method for sintering in-situ toughened boron carbide-based multiphase ceramic by using two-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110614993.1A CN113149676B (en) | 2021-06-02 | 2021-06-02 | Method for sintering in-situ toughened boron carbide-based multiphase ceramic by using two-step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113149676A true CN113149676A (en) | 2021-07-23 |
| CN113149676B CN113149676B (en) | 2022-12-13 |
Family
ID=76875503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110614993.1A Active CN113149676B (en) | 2021-06-02 | 2021-06-02 | Method for sintering in-situ toughened boron carbide-based multiphase ceramic by using two-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149676B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163243A (en) * | 2021-11-30 | 2022-03-11 | 东北大学 | Method for preparing boron carbide ceramic material by taking crystalline silicon cutting waste as auxiliary agent |
| CN115233066A (en) * | 2022-08-09 | 2022-10-25 | 湖南省冶金材料研究院有限公司 | Ceramic material and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298073A (en) * | 1988-05-25 | 1989-12-01 | Toray Ind Inc | Boride-based ceramics |
| CN101844925A (en) * | 2010-05-21 | 2010-09-29 | 李艳 | Process for preparing multilayer ZrB2-SiC complex phase ultrahigh temperature ceramic wafer material by tape casting |
| CN102050628A (en) * | 2011-01-04 | 2011-05-11 | 上海大学 | Method for preparing superfine zirconium boride powder |
| CN102173813A (en) * | 2011-02-23 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of complex phase ceramic material containing zirconium boride |
| CN102515772A (en) * | 2011-12-28 | 2012-06-27 | 牡丹江金钢钻碳化硼有限公司 | Boron carbide-zirconium boride composite ceramic material and preparation method thereof |
| CN103848625A (en) * | 2012-11-30 | 2014-06-11 | 中国科学院上海硅酸盐研究所 | Method for preparing zirconium boride powder with rod-like morphology |
| CN103864085A (en) * | 2014-03-26 | 2014-06-18 | 山东理工大学 | Preparation method of rod-like zirconium boride powder |
| CN103922360A (en) * | 2014-03-26 | 2014-07-16 | 山东理工大学 | Process of preparing rod-like zirconium boride powder at low temperature |
| CN105692642A (en) * | 2016-03-14 | 2016-06-22 | 武汉科技大学 | Nano rodlike zirconium boride powder and preparation method thereof |
| CN105948752A (en) * | 2016-05-06 | 2016-09-21 | 河北工程大学 | Boron carbide composite ceramic with nanometer-submicron scale zirconium boride adding phase and preparation method thereof |
| BG3190U1 (en) * | 2019-02-11 | 2019-06-28 | Краси- Мир Иванов Илиев | Composition for production of composite materials based on silicon carbide |
| CN110655408A (en) * | 2019-11-13 | 2020-01-07 | 哈尔滨工业大学 | Preparation method of single-phase carborundum solid solution ceramic material |
| CN216348724U (en) * | 2021-10-28 | 2022-04-19 | 山东鹏程陶瓷新材料科技有限公司 | High-density zirconium boride ceramic electrode detection equipment |
-
2021
- 2021-06-02 CN CN202110614993.1A patent/CN113149676B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298073A (en) * | 1988-05-25 | 1989-12-01 | Toray Ind Inc | Boride-based ceramics |
| CN101844925A (en) * | 2010-05-21 | 2010-09-29 | 李艳 | Process for preparing multilayer ZrB2-SiC complex phase ultrahigh temperature ceramic wafer material by tape casting |
| CN102050628A (en) * | 2011-01-04 | 2011-05-11 | 上海大学 | Method for preparing superfine zirconium boride powder |
| CN102173813A (en) * | 2011-02-23 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of complex phase ceramic material containing zirconium boride |
| CN102515772A (en) * | 2011-12-28 | 2012-06-27 | 牡丹江金钢钻碳化硼有限公司 | Boron carbide-zirconium boride composite ceramic material and preparation method thereof |
| CN103848625A (en) * | 2012-11-30 | 2014-06-11 | 中国科学院上海硅酸盐研究所 | Method for preparing zirconium boride powder with rod-like morphology |
| CN103864085A (en) * | 2014-03-26 | 2014-06-18 | 山东理工大学 | Preparation method of rod-like zirconium boride powder |
| CN103922360A (en) * | 2014-03-26 | 2014-07-16 | 山东理工大学 | Process of preparing rod-like zirconium boride powder at low temperature |
| CN105692642A (en) * | 2016-03-14 | 2016-06-22 | 武汉科技大学 | Nano rodlike zirconium boride powder and preparation method thereof |
| CN105948752A (en) * | 2016-05-06 | 2016-09-21 | 河北工程大学 | Boron carbide composite ceramic with nanometer-submicron scale zirconium boride adding phase and preparation method thereof |
| BG3190U1 (en) * | 2019-02-11 | 2019-06-28 | Краси- Мир Иванов Илиев | Composition for production of composite materials based on silicon carbide |
| CN110655408A (en) * | 2019-11-13 | 2020-01-07 | 哈尔滨工业大学 | Preparation method of single-phase carborundum solid solution ceramic material |
| CN216348724U (en) * | 2021-10-28 | 2022-04-19 | 山东鹏程陶瓷新材料科技有限公司 | High-density zirconium boride ceramic electrode detection equipment |
Non-Patent Citations (5)
| Title |
|---|
| 吕工兵: "碳还原法硼化锆粉体的制备研究", 《陶瓷》 * |
| 张国军等: "原位合成板晶增强复相陶瓷", 《硅酸盐学报》 * |
| 李少峰: "B_4C-SiC复合材料的制备及性能研究", 《佛山陶瓷》 * |
| 王海龙等: "纳米SiC晶须和SiC颗粒混合增韧ZrB_2陶瓷性能", 《复合材料学报》 * |
| 马成良等: "二硼化锆粉体的工业合成", 《硅酸盐通报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163243A (en) * | 2021-11-30 | 2022-03-11 | 东北大学 | Method for preparing boron carbide ceramic material by taking crystalline silicon cutting waste as auxiliary agent |
| CN115233066A (en) * | 2022-08-09 | 2022-10-25 | 湖南省冶金材料研究院有限公司 | Ceramic material and preparation method and application thereof |
| CN115233066B (en) * | 2022-08-09 | 2023-11-03 | 湖南省冶金材料研究院有限公司 | Ceramic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113149676B (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109879669B (en) | High-entropy ceramic composite material with high strength and preparation method and application thereof | |
| CN113149676B (en) | Method for sintering in-situ toughened boron carbide-based multiphase ceramic by using two-step method | |
| CN104609865A (en) | Preparation method of silicon nitride-based conductive ceramic and molding method of silicon nitride-based conductive ceramic cutting tool | |
| CN108439995B (en) | Complex phase ceramic and preparation method thereof | |
| CN112250442B (en) | Preparation method of high-toughness binderless nanocrystalline hard alloy | |
| CN112645726B (en) | Silicon carbide whisker ceramic with typical long particle morphology and rich in stacking faults and twin crystals and preparation method thereof | |
| CN114315359A (en) | Method for preparing high-strength and high-toughness complex-phase high-entropy ceramic by using solid solution coupling method and application | |
| CN102731093A (en) | Method for low-temperature densification sintering of boron carbide-based ceramic material | |
| CN115180960B (en) | Silicon nitride ceramic sintered body and preparation method thereof | |
| CN104817327A (en) | Silicon nitride composite ceramic die material, and preparation method and application thereof | |
| CN114736022B (en) | High-density, high-strength and ultrahigh-hardness boron carbide/high-entropy diboride complex phase ceramic and preparation method thereof | |
| CN110436928A (en) | High-performance nano twin boron carbide ceramics block materials and preparation method thereof | |
| CN115536403A (en) | High-toughness silicon nitride ceramic material and preparation method thereof | |
| CN113416077A (en) | High-temperature ceramic cutter material with double composite structures and preparation method and application thereof | |
| CN116217233B (en) | Complex-phase ceramic of SiC whisker and high-entropy boride hardened and toughened high-entropy carbide, and preparation method and application thereof | |
| CN109231990A (en) | A kind of preparation method of tungsten carbide-diamond composite | |
| CN115557793B (en) | High-entropy ceramic with fine grains, high hardness and high toughness, and preparation method and application thereof | |
| CN113582698A (en) | Preparation method of ZrB2-SiC toughened B4C bulletproof piece | |
| CN113292343A (en) | Method for preparing boron carbide-based multiphase ceramic through in-situ reaction pressureless sintering | |
| CN106830941A (en) | Al2O3With the covalent key compound sintered body of multicomponent magnesium-yttrium-transition metal and preparation method thereof | |
| CN109956754B (en) | Graphene nanosheet toughened TiB2Ceramic-based cutter material and preparation process thereof | |
| CN116178034B (en) | Whisker toughened high-entropy carbide complex-phase ceramic and preparation method and application thereof | |
| JPS632913B2 (en) | ||
| CN110483058B (en) | Superhard high-strength boride ceramic and preparation method and application thereof | |
| CN115959909B (en) | B (B) 4 C-mullite-NbB 2 Composite ceramic and preparation method thereof |
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 | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Guanqi Inventor after: Chen Shixing Inventor after: Yan Xiangyu Inventor after: Fu Yudong Inventor after: Wang Yujin Inventor before: Liu Guanqi Inventor before: Chen Shixing Inventor before: Yan Xiangyu Inventor before: Fu Yudong Inventor before: Wang Yujin |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |