CN111825461A - Graphene modified silicon carbide ceramic material, preparation method thereof and bulletproof armor - Google Patents
Graphene modified silicon carbide ceramic material, preparation method thereof and bulletproof armor Download PDFInfo
- Publication number
- CN111825461A CN111825461A CN202010900783.4A CN202010900783A CN111825461A CN 111825461 A CN111825461 A CN 111825461A CN 202010900783 A CN202010900783 A CN 202010900783A CN 111825461 A CN111825461 A CN 111825461A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- graphene
- ceramic material
- temperature
- carbide ceramic
- 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.)
- Withdrawn
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
-
- 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
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/023—Armour plate, or auxiliary armour plate mounted at a distance of the main armour plate, having cavities at its outer impact surface, or holes, for deflecting the projectile
-
- 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
- C04B2235/422—Carbon
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a graphene modified silicon carbide ceramic material which comprises graphene, alpha-phase silicon carbide and beta-phase silicon carbide, wherein the mass percentage of the graphene in the graphene modified silicon carbide ceramic material is 0.5-1%. The invention also discloses a preparation method of the graphene modified silicon carbide ceramic material, which comprises the following steps: mixing graphene, alpha-phase silicon carbide, a three-dimensional carbon material, alcohol-soluble resin and a solvent to obtain pasty mixed powder; granulating the mixed powder to obtain pre-granules; pressing the pre-granules into a biscuit; and (3) infiltrating liquid metal silicon into the biscuit and sintering, wherein the sintering temperature is 1450-1600 ℃, and the heat preservation time at the sintering temperature is 1.5-2.5 h. The invention also discloses a bulletproof armor.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a graphene modified silicon carbide ceramic material, a preparation method thereof and a bulletproof armor.
Background
Reaction-sintered silicon carbide (RSSC) is a dense sintered ceramic body obtained by infiltrating a carbon-containing silicon carbide ceramic biscuit with molten silicon. The reaction sintering silicon carbide not only has excellent performances of high temperature resistance, wear resistance, oxidation resistance, thermal shock resistance, high hardness, high thermal conductivity and the like of the silicon carbide ceramic, but also has the advantages of simple sintering process, short sintering time, net size sintering and the like, so that the reaction sintering silicon carbide realizes large-scale industrial application and is expected to be used in the fields of aerospace, bulletproof armor, engine blades, nuclear reactor containers and the like.
However, although reaction sintering silicon carbide has many advantages, it is a brittle material in nature, which is mainly caused by the bonds and features of the silicon carbide molecular structure, and more importantly, residual silicon formed by filling pores with liquid silicon at the later stage of sintering can reduce the mechanical properties of silicon carbide ceramic, such as hardness and toughness, and becomes an important factor for limiting the development of RSSC ceramic. Particularly for the field of bulletproof armor with higher requirements on hardness, toughness and friction resistance, reaction sintered silicon carbide materials are basically abandoned, and boron carbide materials with higher performance are used. The cost of boron carbide materials is greatly increased relative to silicon carbide.
Disclosure of Invention
Therefore, it is necessary to provide a graphene modified silicon carbide ceramic material with low cost and high toughness, a preparation method thereof and a bulletproof armor for solving the problem of poor toughness of the conventional reaction sintered silicon carbide.
The graphene-modified silicon carbide ceramic material comprises graphene, alpha-phase silicon carbide and beta-phase silicon carbide, wherein the mass percentage of the graphene in the graphene-modified silicon carbide ceramic material is 0.5% -1%.
In one embodiment, the mass percentage of the alpha-phase silicon carbide in the graphene-modified silicon carbide ceramic material is 60% to 80%, and the mass percentage of the beta-phase silicon carbide in the graphene-modified silicon carbide ceramic material is 20% to 40%.
In one embodiment, the particle size of the graphene is 3-5 layers of carbon.
In one embodiment, the grain size of the silicon carbide is 10-15 μm.
The preparation method of the graphene modified silicon carbide ceramic material comprises the following steps:
mixing graphene, alpha-phase silicon carbide, a three-dimensional carbon material, alcohol-soluble resin and a solvent to obtain pasty mixed powder;
granulating the mixed powder to obtain pre-granules;
pressing the pre-granules into a biscuit;
and (3) infiltrating liquid metal silicon into the biscuit and sintering, wherein the sintering temperature is 1450-1600 ℃, and the heat preservation time at the sintering temperature is 1.5-2.5 h.
In one embodiment, the sintering temperature is 1450 ℃ to 1550 ℃.
In one embodiment, the sintering process is: the method comprises the steps of raising the temperature from normal temperature to 200 ℃ at a first temperature raising speed, then raising the temperature from 200 ℃ to 300 ℃ at a second temperature raising speed, then raising the temperature from 300 ℃ to 700 ℃ at a third temperature raising speed, then raising the temperature from 700 ℃ to 850 ℃ at a fourth temperature raising speed, and then raising the temperature from 850 ℃ to the sintering temperature at a fifth temperature raising speed, wherein the second temperature raising speed and the fourth temperature raising speed are respectively smaller than the first temperature raising speed, the third temperature raising speed and the fifth temperature raising speed.
In one embodiment, the pressure for pressing into the biscuit is 40-60 MPa.
In one embodiment, the added mass of the three-dimensional carbon material is 10-20% of the total mass of the graphene, the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin.
In one embodiment, the mass of the alcohol-soluble resin is 10% -20% of the total mass of the graphene, the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin.
In one embodiment, the alcohol-soluble resin is a phenolic resin.
In one embodiment, the three-dimensional carbon material is selected from any one or both of graphite and carbon black.
In one embodiment, the step of obtaining a paste-like powder mixture comprises:
mixing graphene with an ethanol solution to obtain a graphene dispersion liquid; and
and mixing the mixture of the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin with the graphene dispersion liquid.
In one embodiment, the step of mixing the mixture of the α -phase silicon carbide, the three-dimensional carbon material, and the alcohol-soluble resin with the graphene dispersion liquid includes: and adding the mixture into the graphene dispersion liquid in batches at an adding speed of 50g/10 min-200 g/10 min.
The bulletproof armor comprises the graphene modified silicon carbide ceramic material or the graphene modified silicon carbide ceramic material prepared by the preparation method.
According to the scheme, the graphene is added into the reaction sintering silicon carbide material, the graphene not only improves the toughness of the reaction sintering silicon carbide material by means of the structure of the graphene, but also takes part of the graphene as a carbon source to participate in reaction in the siliconizing process to form secondary silicon carbide filled pores, and the graphene is connected with the substrate, so that the toughness of the reaction sintering silicon carbide material can be better improved. The graphene modified silicon carbide ceramic material can be used for preparing bulletproof armor.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the invention provides a graphene modified silicon carbide ceramic material which comprises graphene, alpha-phase silicon carbide and beta-phase silicon carbide, wherein the mass percentage of the graphene in the graphene modified silicon carbide ceramic material is 0.5% -1%.
According to the scheme, the graphene is added into the reaction sintering silicon carbide material, the graphene not only improves the toughness of the reaction sintering silicon carbide material by means of the structure of the graphene, but also takes part of the graphene as a carbon source to participate in reaction in the siliconizing process to form secondary silicon carbide filled pores, and the graphene is connected with the substrate, so that the toughness of the reaction sintering silicon carbide material can be better improved. The graphene modified silicon carbide ceramic material can be used for preparing bulletproof armor.
The alpha-phase silicon carbide is originally added in the process of preparing the graphene modified silicon carbide ceramic material by reaction sintering. The beta-phase silicon carbide is formed by the reaction of metal silicon and carbon in the reaction sintering preparation process. In some embodiments, the mass percentage of the alpha-phase silicon carbide in the graphene-modified silicon carbide ceramic material is 60% to 80%, and the mass percentage of the beta-phase silicon carbide in the graphene-modified silicon carbide ceramic material is 20% to 40%.
In some embodiments, the graphene has a particle size of 3 to 5 layers of carbon thick. Specifically, the particle size of the graphene may be 3, 4, or 5 layers of carbon thick. The graphene can be better matched with alpha-phase silicon carbide and beta-phase silicon carbide within the particle size range, so that the overall fracture toughness, bending strength and wear resistance of the material can be improved.
In some embodiments, the silicon carbide has a particle size of 10 μm to 15 μm. Specifically, the grain size of the alpha-phase silicon carbide is 10 to 11 μm, 11 to 12 μm, 12 to 13 μm, 13 to 14 μm, or 14 to 15 μm.
The embodiment of the invention also provides a preparation method of the graphene modified silicon carbide ceramic material, which comprises the following steps:
mixing graphene, alpha-phase silicon carbide, a three-dimensional carbon material, alcohol-soluble resin and a solvent to obtain pasty mixed powder;
granulating the mixed powder to obtain pre-granules;
pressing the pre-granules into a biscuit;
and (3) infiltrating liquid metal silicon into the biscuit and sintering, wherein the sintering temperature is 1450-1600 ℃, and the heat preservation time at the sintering temperature is 1.5-2.5 h.
According to the embodiment, the sintering temperature is controlled to be 1450-1600 ℃, so that all three-dimensional carbon materials, alcohol-soluble resin carbides and a small amount of graphene fully react with metal silicon to form beta-phase silicon carbide, the beta-phase silicon carbide is inserted into the whole material as a cross-linking network, the graphene is not physically combined in a base material only through pressing, and the small amount of graphene is combined in the base body through the reaction with silicon, so that the overall compactness of the material and the combination firmness of all components can be improved, and the reinforcing effect of the graphene on the overall fracture toughness, bending strength and wear resistance of the material is fully exerted.
In step a, the step of obtaining a paste-like powder mixture may comprise: mixing graphene with a solvent to obtain a graphene dispersion liquid, wherein the solvent can be selected from ethanol; and then mixing the mixture of the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin with the graphene dispersion liquid.
Preferably, the mixing of the mixture of the α -phase silicon carbide, the three-dimensional carbon material, and the alcohol-soluble resin with the graphene dispersion may include: and adding the mixture into the graphene dispersion liquid in batches at an adding speed of 50g/10 min-200 g/10 min.
In some embodiments, the added mass of the alcohol-soluble resin is 10% to 20% of the total mass of the graphene, the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin. Preferably, the alcohol-soluble resin is a phenolic resin. In this example, the phenolic resin has three main functions: firstly, phenolic resin is used as a binder to bind all components in a biscuit into an integral structure; secondly, the phenolic resin is carbonized in the sintering process and reacts with the metallic silicon to form beta-phase silicon carbide as a supplementary carbon source; and thirdly, the phenolic resin is decomposed in the sintering process to form a pore structure, the pore structure can be used as a siliconizing channel, so that the metal silicon permeates into the biscuit through the pore structure and reacts with the three-dimensional carbon material, the carbide of the phenolic resin and the graphitized product of a small part of diamond to form beta-phase silicon carbide, the pore structure accelerates the siliconizing process and increases the carbon-silicon binding sites, the binding network density of the beta-phase silicon carbide in the graphene modified silicon carbide ceramic material is increased, and the mechanical strength of the modified silicon carbide is finally improved.
The three-dimensional carbon material is used as a carbon source in the raw material and reacts with liquid metal silicon to form beta-phase silicon carbide. In some embodiments, the three-dimensional carbon material may be selected from either or both of graphite and carbon black. In some embodiments, the particle size of the three-dimensional carbon material is 5 μm to 10 μm. For example, the thickness may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm. In some embodiments, the added mass of the three-dimensional carbon material is 10% -20% of the total mass of the graphene, the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin.
The granulation process in step b may be spray granulation. Through granulation, all components are uniformly mixed and locked in the granules, so that the sedimentation of partial components in the treatment process is avoided, and the materials are not uniformly mixed.
In the step c, the pressure for pressing the biscuit can be 40-60 MPa. Specifically, the pressure can be 40MPa to 45MPa, 45MPa to 50MPa, 50MPa to 55MPa or 55MPa to 60 MPa.
In the step d, the step of infiltrating the liquid metal silicon into the biscuit may be pressing the solid metal silicon into a sheet shape, and then overlapping the sheet metal silicon on the biscuit, so that the solid metal silicon is melted and infiltrated into the biscuit during the sintering heating process.
The sintering temperature is crucial to the preparation of the graphene modified silicon carbide ceramic material of the present invention, and the purpose of the present invention is to react a small amount of graphene with silicon metal. If the sintering temperature is too high, a large amount of graphene reacts to form silicon carbide, and the original strong mechanical property of the graphene is lost; if the sintering temperature is too low, no graphene and silicon are combined and reacted, and the combination fastness of the graphene in the material matrix is not enough. Preferably, the sintering temperature is 1450-1550 ℃, for example 1450-1500 ℃ or 1500-1550 ℃.
Preferably, the sintering process is as follows: the method comprises the steps of raising the temperature from normal temperature to 200 ℃ at a first temperature raising speed, then raising the temperature from 200 ℃ to 300 ℃ at a second temperature raising speed, then raising the temperature from 300 ℃ to 700 ℃ at a third temperature raising speed, then raising the temperature from 700 ℃ to 850 ℃ at a fourth temperature raising speed, and then raising the temperature from 850 ℃ to the sintering temperature at a fifth temperature raising speed, wherein the second temperature raising speed and the fourth temperature raising speed are respectively smaller than the first temperature raising speed, the third temperature raising speed and the fifth temperature raising speed. According to the embodiment, the temperature rise speed is reduced within the temperature range of 200-300 ℃ and 700-850 ℃, the cross-linking and decomposition processes of the resin are respectively carried out in the two sections, so that the material stays in the two sections for a longer time, the cross-linking and decomposition of the resin can be better completed, the resin is decomposed to form a pore structure with a more uniform structure, the siliconizing uniformity is improved, the component uniformity of the whole material is improved, and the improvement of the integral hardness, the fracture toughness, the bending strength and the wear resistance is finally reflected. Preferably, the second temperature rise speed and the fourth temperature rise speed are respectively 2 ℃/min-5 ℃/min. The first temperature rise speed, the third temperature rise speed and the fifth temperature rise speed are respectively 10-30 ℃/min.
Preferably, the vacuum degree during sintering is less than or equal to 10 pa.
In some embodiments, the sintering step further comprises a cooling step after completion, wherein the cooling step eliminates internal stress in the material.
In some embodiments, the method further comprises a step of removing silicon from the graphene-modified silicon carbide ceramic material after the cooling step, wherein silicon slag which does not penetrate into the biscuit or is unreacted is removed from the material. In one embodiment, the step of removing silicon may be grit blasting.
The embodiment of the invention also provides a bulletproof armor, which comprises the graphene modified silicon carbide ceramic material in any embodiment or the graphene modified silicon carbide ceramic material prepared by the preparation method of the graphene modified silicon carbide ceramic material in any embodiment. The bulletproof armor prepared from the graphene modified silicon carbide ceramic material has the performance of resisting multiple impacts (such as bullets, sharp instruments and the like).
The following are specific examples.
Example 1:
(1) mixing: respectively taking alpha-phase silicon carbide (the particle size is about 10 mu m, the alpha-phase silicon carbide accounts for 60% of the total solid mass of the mixed powder), graphene (5 layers of graphene with the carbon thickness, the graphene accounts for 0.7% of the total solid mass of the mixed powder), graphite (the particle size is about 5 mu m, and the graphite accounts for 10% of the total solid mass of the mixed powder) and phenolic resin, and weighing; placing graphene in a beaker, pouring alcohol, and ultrasonically dispersing for 0.5h in an ultrasonic cell crushing instrument to obtain graphene dispersion liquid; and (3) uniformly mixing alpha-phase silicon carbide, diamond, graphite and phenolic resin to obtain a mixture, adding the mixture into the graphene dispersion liquid subjected to ultrasonic dispersion in batches (100 g/10 min), and mixing for 1h in a device with the rotating speed of 100r/min and the heating temperature of 40 ℃ to obtain semi-solid pasty mixed powder.
(2) And (3) granulation: and carrying out spray granulation on the mixed powder to obtain pre-granules of the raw materials.
(3) Pressing: pouring the pre-granules into a grinding tool, and pressing under the pressure of 40MPa to prepare a biscuit.
(4) Preparing silicon: and pressing the metal silicon powder with the silicon content of more than 99% into the silicon cake.
(5) And (3) sintering: overlapping the silicon cakes on the biscuit, placing the biscuit in a vacuum furnace for sintering, wherein the sintering temperature is 1500 ℃, the vacuum degree is less than or equal to 10pa, and the sintering time is 2 h; the sintering process is as follows: heating from normal temperature to 200 ℃ at a first heating rate, then heating from 200 ℃ to 300 ℃ at a second heating rate, then heating from 300 ℃ to 700 ℃ at a third heating rate, then heating from 700 ℃ to 850 ℃ at a fourth heating rate, and then heating from 850 ℃ to the sintering temperature at a fifth heating rate, wherein the second heating rate and the fourth heating rate are respectively 3 ℃/min, and the first heating rate, the third heating rate and the fifth heating rate are respectively 20 ℃/min.
(6) And (3) cooling: and cooling the sintered and formed plate along with the furnace, cooling to normal temperature and taking out.
(7) Silicon removal: and carrying out sand blasting treatment on the silicon slag remained on the surface.
Example 2:
(1) mixing: respectively taking alpha-phase silicon carbide (the particle size is about 10 mu m, the alpha-phase silicon carbide accounts for 70% of the total solid mass of the mixed powder), graphene (5 layers of graphene with the carbon thickness, the graphene accounts for 1.2% of the total solid mass of the mixed powder), graphite (the particle size is about 10 mu m, and the graphite accounts for 10% of the total solid mass of the mixed powder) and phenolic resin, and weighing; placing graphene in a beaker, pouring alcohol, and ultrasonically dispersing for 0.5h in an ultrasonic cell crushing instrument to obtain graphene dispersion liquid; and (3) adding a mixture obtained by uniformly mixing alpha-phase silicon carbide, diamond, graphite and phenolic resin into the graphene dispersion liquid subjected to ultrasonic dispersion in batches (80 g/10 min), and mixing for 1h in a device with the rotating speed of 100r/min and the heating temperature of 40 ℃ to obtain semi-solid pasty mixed powder.
(2) And (3) granulation: and carrying out spray granulation on the mixed powder to obtain pre-granules of the raw materials.
(3) Pressing: pouring the pre-granules into a grinding tool, and pressing into a biscuit under the pressure of 60 MPa.
(4) Preparing silicon: and pressing the metal silicon powder with the silicon content of more than 99% into the silicon cake.
(5) And (3) sintering: and (3) overlapping the silicon cakes on the biscuit, placing the biscuit in a vacuum furnace for sintering, wherein the sintering temperature is 1550 ℃, the vacuum degree is less than or equal to 10pa, and the sintering time is 1.5 h.
(6) And (3) cooling: and cooling the sintered and formed plate along with the furnace, cooling to normal temperature and taking out.
(7) Silicon removal: and carrying out sand blasting treatment on the silicon slag remained on the surface.
Example 3:
(1) mixing: respectively taking alpha-phase silicon carbide (the particle size is about 10 mu m, the alpha-phase silicon carbide accounts for 60% of the total solid mass of the mixed powder), graphene (5 layers of graphene with the carbon thickness, the graphene accounts for 0.7% of the total solid mass of the mixed powder), graphite (the particle size is about 5 mu m, and the graphite accounts for 10% of the total solid mass of the mixed powder) and phenolic resin, and weighing; adding alcohol into graphene, alpha-phase silicon carbide, graphite and phenolic resin, and mixing for 1h in a device with the rotating speed of 100r/min and the heating temperature of 45 ℃ to obtain semi-solid pasty mixed powder.
(2) And (3) granulation: and carrying out spray granulation on the mixed powder to obtain pre-granules of the raw materials.
(3) Pressing: pouring the pre-granules into a grinding tool, and pressing under the pressure of 40MPa to prepare a biscuit.
(4) Preparing silicon: and pressing the metal silicon powder with the silicon content of more than 99% into the silicon cake.
(5) And (3) sintering: and (3) overlapping the silicon cakes on the biscuit, placing the biscuit in a vacuum furnace for sintering, wherein the sintering temperature is 1500 ℃, the vacuum degree is less than or equal to 10pa, and the sintering time is 2 h.
(6) And (3) cooling: and cooling the sintered and formed plate along with the furnace, cooling to normal temperature and taking out.
(7) Silicon removal: and carrying out sand blasting treatment on the silicon slag remained on the surface.
Comparative example 1:
comparative example 1 is essentially the same as example 1 except that: in the step (1), the mixed powder is replaced by the same amount of alpha-phase silicon carbide without adding graphene.
Comparative example 2:
comparative example 2 is essentially the same as example 1 except that: the sintering temperature in the step (5) is 1700 ℃.
Comparative example 3:
comparative example 3 is essentially the same as example 1 except that: the sintering temperature in the step (5) is 1350 ℃.
Comparative example 4
Comparative example 4 is essentially the same as example 1 except that: in the step (5), the temperature is increased to the sintering temperature from the normal temperature at a temperature rising speed of 30 ℃/min.
The silicon carbide materials prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to mechanical property measurement under the same test conditions, and the results are shown in table 1.
TABLE 1
| Group of | Hardness of | Fracture toughness | Bending strength | Resistance to rubbing |
| Example 1 | ++ | ++ | ++ | ++ |
| Example 2 | +++ | +++ | +++ | +++ |
| Example 3 | ++ | + | + | ++ |
| Comparative example 1 | + | + | + | + |
| Comparative example 2 | + | ++ | + | + |
| Comparative example 3 | + | ++ | + | + |
| Comparative example 4 | + | + | + | + |
Note: "+" indicates the strength of the mechanical property, and the more "+" indicates the stronger the property.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. The graphene-modified silicon carbide ceramic material is characterized by comprising 0.5-1% of graphene, alpha-phase silicon carbide and beta-phase silicon carbide by mass.
2. The graphene-modified silicon carbide ceramic material according to claim 1, wherein the alpha-phase silicon carbide is 60 to 80 mass% of the graphene-modified silicon carbide ceramic material, and the beta-phase silicon carbide is 20 to 40 mass% of the graphene-modified silicon carbide ceramic material.
3. The graphene-modified silicon carbide ceramic material according to any one of claims 1 to 2, wherein the particle size of the graphene is 3 to 5 carbon layers thick.
4. The graphene-modified silicon carbide ceramic material according to any one of claims 1 to 2, wherein the particle size of the silicon carbide is 10 to 15 μm.
5. A method for preparing the graphene-modified silicon carbide ceramic material according to any one of claims 1 to 4, comprising the steps of:
mixing graphene, alpha-phase silicon carbide, a three-dimensional carbon material, alcohol-soluble resin and a solvent to obtain pasty mixed powder;
granulating the mixed powder to obtain pre-granules;
pressing the pre-granules into a biscuit;
and (3) infiltrating liquid metal silicon into the biscuit and sintering, wherein the sintering temperature is 1450-1600 ℃, and the heat preservation time at the sintering temperature is 1.5-2.5 h.
6. The preparation method of the graphene-modified silicon carbide ceramic material as claimed in claim 5, wherein the sintering temperature is 1450-1550 ℃.
7. The preparation method of the graphene-modified silicon carbide ceramic material according to claim 5, wherein the sintering process comprises: the method comprises the steps of raising the temperature from normal temperature to 200 ℃ at a first temperature raising speed, then raising the temperature from 200 ℃ to 300 ℃ at a second temperature raising speed, then raising the temperature from 300 ℃ to 700 ℃ at a third temperature raising speed, then raising the temperature from 700 ℃ to 850 ℃ at a fourth temperature raising speed, and then raising the temperature from 850 ℃ to the sintering temperature at a fifth temperature raising speed, wherein the second temperature raising speed and the fourth temperature raising speed are respectively smaller than the first temperature raising speed, the third temperature raising speed and the fifth temperature raising speed.
8. The preparation method of the graphene-modified silicon carbide ceramic material according to claim 5, wherein the pressure for pressing into the biscuit is 40MPa to 60 MPa.
9. The preparation method of the graphene-modified silicon carbide ceramic material according to claim 5, wherein the mass of the three-dimensional carbon material is 10-20% of the total mass of the graphene, the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin; and/or the mass of the alcohol-soluble resin is 10-20% of the total mass of the graphene, the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin.
10. The method for preparing the graphene-modified silicon carbide ceramic material according to claim 5, wherein the alcohol-soluble resin is a phenolic resin.
11. The method for preparing a graphene-modified silicon carbide ceramic material according to claim 5, wherein the three-dimensional carbon material is selected from any one or two of graphite and carbon black.
12. The method for preparing a graphene-modified silicon carbide ceramic material according to claim 5, wherein the step of obtaining a paste-like mixed powder material comprises:
mixing graphene with an ethanol solution to obtain a graphene dispersion liquid; and
and mixing the mixture of the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin with the graphene dispersion liquid.
13. The method for preparing a graphene-modified silicon carbide ceramic material according to claim 12, wherein the step of mixing the mixture of the alpha-phase silicon carbide, the three-dimensional carbon material and the alcohol-soluble resin with the graphene dispersion liquid comprises: and adding the mixture into the graphene dispersion liquid in batches at an adding speed of 50g/10 min-200 g/10 min.
14. A bulletproof armor comprising the graphene-modified silicon carbide ceramic material according to any one of claims 1 to 4 or the graphene-modified silicon carbide ceramic material prepared by the method of any one of claims 5 to 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010900783.4A CN111825461A (en) | 2020-09-01 | 2020-09-01 | Graphene modified silicon carbide ceramic material, preparation method thereof and bulletproof armor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010900783.4A CN111825461A (en) | 2020-09-01 | 2020-09-01 | Graphene modified silicon carbide ceramic material, preparation method thereof and bulletproof armor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111825461A true CN111825461A (en) | 2020-10-27 |
Family
ID=72918634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010900783.4A Withdrawn CN111825461A (en) | 2020-09-01 | 2020-09-01 | Graphene modified silicon carbide ceramic material, preparation method thereof and bulletproof armor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111825461A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114216372A (en) * | 2021-11-23 | 2022-03-22 | 中航装甲科技有限公司 | Graphene composite bulletproof plate and preparation method thereof |
| CN116409998A (en) * | 2023-03-02 | 2023-07-11 | 宁夏北伏科技有限公司 | Silicon carbide graphene composite bulletproof ceramic and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150246851A1 (en) * | 2012-09-20 | 2015-09-03 | The Penn State Research Foundation | Process For Production Of Graphene/Silicon Carbide Ceramic Composites |
| CN104926313A (en) * | 2015-06-29 | 2015-09-23 | 山东大学 | High-thermal-conductivity reaction-sintered silicon carbide ceramic material and preparation method thereof |
| CN107602131A (en) * | 2017-09-18 | 2018-01-19 | 山东理工大学 | A kind of carborundum composite-phase ceramic |
| CN107778011A (en) * | 2017-11-17 | 2018-03-09 | 北京林业大学 | A kind of preparation method of graphene composite SiC wood ceramics material |
| CN107778012A (en) * | 2017-09-18 | 2018-03-09 | 山东理工大学 | A kind of preparation method of carborundum composite-phase ceramic |
| CN110698205A (en) * | 2019-11-19 | 2020-01-17 | 中国核动力研究设计院 | Preparation method of graphene-toughened silicon carbide ceramic |
-
2020
- 2020-09-01 CN CN202010900783.4A patent/CN111825461A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150246851A1 (en) * | 2012-09-20 | 2015-09-03 | The Penn State Research Foundation | Process For Production Of Graphene/Silicon Carbide Ceramic Composites |
| CN104926313A (en) * | 2015-06-29 | 2015-09-23 | 山东大学 | High-thermal-conductivity reaction-sintered silicon carbide ceramic material and preparation method thereof |
| CN107602131A (en) * | 2017-09-18 | 2018-01-19 | 山东理工大学 | A kind of carborundum composite-phase ceramic |
| CN107778012A (en) * | 2017-09-18 | 2018-03-09 | 山东理工大学 | A kind of preparation method of carborundum composite-phase ceramic |
| CN107778011A (en) * | 2017-11-17 | 2018-03-09 | 北京林业大学 | A kind of preparation method of graphene composite SiC wood ceramics material |
| CN110698205A (en) * | 2019-11-19 | 2020-01-17 | 中国核动力研究设计院 | Preparation method of graphene-toughened silicon carbide ceramic |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114216372A (en) * | 2021-11-23 | 2022-03-22 | 中航装甲科技有限公司 | Graphene composite bulletproof plate and preparation method thereof |
| CN116409998A (en) * | 2023-03-02 | 2023-07-11 | 宁夏北伏科技有限公司 | Silicon carbide graphene composite bulletproof ceramic and preparation method thereof |
| CN116409998B (en) * | 2023-03-02 | 2024-04-05 | 宁夏北伏科技有限公司 | Silicon carbide graphene composite bulletproof ceramic and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102618955B (en) | Preparation method and application of ultrahigh molecular weight polyethylene/graphene composite fiber | |
| CN102219536B (en) | B4C/SiC whisker/SiC multiphase ceramic matrix composite and preparation method thereof | |
| CN102747243B (en) | Process for preparing grapheme modified hard alloy | |
| CN110304923B (en) | Preparation method of boron carbide-based ceramic composite material based on particle grading | |
| CN111825461A (en) | Graphene modified silicon carbide ceramic material, preparation method thereof and bulletproof armor | |
| CN110396632A (en) | A kind of Ti (C, N) based ceramic metal and preparation method thereof with homogeneous ring core structure | |
| CN113121237B (en) | Boron carbide-based composite ceramic and preparation process thereof | |
| CN112321301A (en) | High-thermal-conductivity low-expansion graphite for rocket engine nozzle and preparation method thereof | |
| CN112194492B (en) | Silicon nitride ceramic material, preparation method and application thereof, and bulletproof flashboard | |
| CN113121242A (en) | Short carbon fiber toughened silicon carbide composite material and preparation method thereof | |
| CN111825462A (en) | Diamond graphene modified silicon carbide ceramic material, preparation method thereof and bulletproof armor | |
| CN110183231B (en) | Preparation method of high-strength high-toughness boron carbide-based ceramic material and ceramic material thereof | |
| CN109354504B (en) | Boron carbide-based composite ceramic sintering aid and sintering process | |
| CN113416077B (en) | High-temperature ceramic cutter material with double composite structure and preparation method and application thereof | |
| KR20190048811A (en) | Method for manufacturing silicon carbide dense bodies having excellent thermal conductivity and thermal durability | |
| US6261692B1 (en) | Carbon-carbon composites containing ceramic power and method for preparing the same | |
| CN111892414A (en) | Short carbon fiber reinforced boron carbide composite material and preparation method thereof | |
| CN112645713B (en) | High-strength and high-toughness ceramic composite material and preparation method thereof | |
| CN1046317C (en) | Technique for mfg. cermet | |
| CN110981489B (en) | TiNx-Ti3SiC2Composite material and preparation method thereof | |
| CN111254336B (en) | Preparation method of WC-Ni hard alloy | |
| CN115259859A (en) | Boron carbide bulletproof ceramic material and preparation method thereof | |
| CN114573351B (en) | Boron carbide-based composite material and preparation method thereof | |
| CN107619290A (en) | A kind of preparation method of CNT enhancing zirconium diboride ceramics based composites | |
| CN113563096A (en) | Preparation method of chopped carbon fiber reinforced graphite-based C/C composite material |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201027 |
|
| WW01 | Invention patent application withdrawn after publication |