CN106995314A - A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content - Google Patents

A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content Download PDF

Info

Publication number
CN106995314A
CN106995314A CN201710287236.1A CN201710287236A CN106995314A CN 106995314 A CN106995314 A CN 106995314A CN 201710287236 A CN201710287236 A CN 201710287236A CN 106995314 A CN106995314 A CN 106995314A
Authority
CN
China
Prior art keywords
silicon
silicon carbide
carbide powder
biscuit
carbon fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710287236.1A
Other languages
Chinese (zh)
Inventor
鲍崇高
宋索成
陈子晗
邱免
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN201710287236.1A priority Critical patent/CN106995314A/en
Publication of CN106995314A publication Critical patent/CN106995314A/en
Pending legal-status Critical Current

Links

Classifications

    • C04B35/806—
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • 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
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • C04B35/63476—Phenol-formaldehyde condensation polymers
    • 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
    • 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
    • C04B2235/3821—Boron 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6581—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

Abstract

A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, using short carbon fiber as a kind of slow release carbon source, addition boron carbide powder promotes biscuit siliconising abundant.By adding the silicon carbide powder of mass fraction 68.2~33.2%, 6.8~41.8% short carbon fiber, 15% boron carbide powder and 10% phenolic resin are raw material, fiber pretreatment is carried out successively, batch mixing is classified, and Bidirectional-pressure is compressing, baking and curing, reaction-sintered；This method technique is easy, and the silicon carbide reaction-sintered composite ceramics of the residual strong mechanical performance that silicon phase size is small, content is low is prepared by special carbon source selection and certain material composition proportioning.

Description

A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content
Technical field
The present invention relates to the preparation of silicon carbide reaction-sintered composite ceramics, more particularly to a kind of low residual silicon size and content The preparation method of reaction sintering silicon carbide ceramic.
Background technology
Silicon carbide reaction-sintered composite ceramics is a kind of advanced high temperature, corrosion-resistant structure ceramics.Relative to traditional burning Knot method, reaction sintering has that sintering time is short, sintering temperature is low, densified sintering product, can prepare complicated shape, low energy consumption and The advantages of nearly size is molded, therefore reaction sintering is a kind of sintering technology with very big application potential.Reaction-sintered is carbonized Silicon method be generally applied to the fields such as lightweight armor, aerospace material and nuclear reactor vessel, traditional preparation method be by Carborundum (α-SiC) particle is well mixed with carbon dust, and biscuit is pressed into the presence of organic binder bond, biscuit then is placed in into silicon Siliconising is carried out on particle.During reaction-sintered, liquid silicon is penetrated into biscuit in the presence of capillary force by capillary channel, The secondary carborundum (β-SiC) generated after carbon dust silication can connect original carborundum, and liquid-state silicon fills the residual silicon phase of hole formation, most End form is into densified sintering product body.The sintering process of silicon carbide reaction-sintered determines its tissue by three kinds of phase compositions, i.e.,：α-SiC、β- SiC and Si phases.(intensity is less than 100MPa to intensity and toughness of the wherein residual silicon mutually with difference, and toughness is less than 1MPam1/2), how Reduce residual silicon phase size and content is technical problem that silicon carbide reaction-sintered mainly faces.Traditional residual silicon phase content of reduction Method, with the rise of carbon powder content, generates secondary carborundum pole mainly by increasing carbon powder content after carbon dust silication Easily blocking capillary channel, cause biscuit sintering impermeable, therefore find a kind of effective method reduces the size and content of residual silicon phase It is most important for improving silicon carbide reaction-sintered mechanical property.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, present invention aims at provide the anti-of a kind of low residual silicon size and content The preparation method of sintered silicon carbide ceramics is answered, high intensity is prepared by adding slow release carbon source (short carbon fiber) and boron carbide particles With the carbide composite ceramic of high tenacity, the addition of wherein boron carbide assists in biscuit siliconising fully, prepared product With residual silicon phase size and content are low, density is small, the overall merit such as intensity and toughness height.
In order to achieve the above object, the present invention, which is adopted the following technical scheme that, is achieved：
A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, is comprised the steps of：
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, to remove its surface Organic gel, clean with distilled water flushing after taking-up, dry for standby；
Step 2, is classified batch mixing, by the short carbon fiber after silicon carbide powder, processing, phenolic resin, four kinds of boron carbide powder Component is according to weight than 68.2-33.2):(6.8-41.8):10:After 15 weigh, carborundum and boron carbide powder are first put into modeling In pellet grinding jar, phenolic resin is uniformly dissolved with alcohol, phenolic resin and alcohol by volume ratio are 1:50；By the phenol stirred Urea formaldehyde alcoholic solution is poured into plastics ball grinder, adds agate ball, wherein ball material mass ratio is 2:1, in turning for 300r/min The lower ball of speed is mixed 2 hours, and then adds the short carbon fiber anticipated, and continues ball under 100r/min rotating speed mixed 5 hours. Slurry is dried in revolution evaporator, mixed-powder is obtained；
Step 3, Bidirectional-pressure is compressing, under 180MPa pressure that mixed-powder is compressing, and pressuring method is Bidirectional-pressure；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, then 90 DEG C are warming up to, then is incubated 3 hours, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality The silicon grain that 2 times of summation, the biscuit being cured is placed on silicon grain, and graphite crucible is put into vacuum carbon tube furnace and starts to take out Vacuum, begins to warm up when body of heater vacuum is reduced to 0.1Pa, programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900- 1380 DEG C of programming rates are 10 DEG C/min, stop vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of programming rate For 20 DEG C/min, 20 minutes are incubated at 1600 DEG C；In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, is reached Room temperature is cooled to the furnace at 1300 DEG C；
The particle diameter of described silicon carbide powder is 10-15 μm, and the particle diameter of the boron carbide powder is less than 2 μm.
Described silicon grain particle diameter is 2mm.
Described short carbon fiber length is less than 4mm, and diameter is less than 7 μm.
The short carbon fiber provides reaction-sintered primary carbon source, due to volume after the high carbon density silicification reaction of short carbon fiber Expansion rate is big, promotes residual silicone content to reduce.And according to dissolution precipitation mechanism, its residual Silicon forms presentation strip after the completion of reacting Distribution, this helps to reduce residual silicon phase size.Mass fraction is to ensure that liquid silicon can lead to glibly for the addition of 15% boron carbide Cross capillary channel.Because carborundum and boron carbide lattice constant are inconsistent, carborundum will not grow up on boron carbide particles, carbonization The capillary channel of boron particles formation will not be blocked.And carborundum is compared to, boron carbide has more excellent mechanical property Can, on the one hand tiny carborundum be to strengthen mechanism to improve organization mechanicses performance with particle, is on the other hand reduction of tissue and puts down Equal crystallite dimension.
The short carbon fiber best in quality fraction is 31.6%, and it is 40%, the bending resistance of complex phase ceramic to be scaled volume fraction Intensity, fracture toughness highest.When short carbon fiber addition mass fraction is 31.6%, residual silicon volume fraction is at least 6%.Short carbon When fiber quality fraction is 41.8%, because the carbon source of addition is excessive, tissue occurs in that un-sintered phenomenon of osmosis, mechanical property Difference.
The beneficial effects of the invention are as follows：
The present invention utilizes reaction-sintered principle, in boron carbide/silicon carbide slurry in plus the big short carbon fiber of carbon density make For carbon source, the advantages of residual silicon is distributed is controlled in course of reaction using cubical expansivity after short carbon fiber silicification reaction greatly, and it is tiny The features such as addition of boron carbide particles can promote liquid silicon to penetrate into so as to cause densified sintering product, particle enhancing and structure refinement.Burn Knot body has the small (2.72-3.04g/cm of density3), bending strength and fracture toughness height (472MPa and 7.4MPam1/2), sexual valence Than high overall merit.Its bending strength and fracture toughness compare to be respectively increased with traditional silicon carbide reaction-sintered performance 86% and 114%.
Brief description of the drawings
Fig. 1 is biscuit sintering curre figure.
Strong mechanical performance ceramic material bending strengths and Fracture Toughness comparison of the Fig. 2 for one-embodiment of embodiment five.
Fig. 3 is with mixed acid (7HNO3:Heterogeneity sample microscopic appearance after residual silicon phase 1HF) is eroded, wherein figure (I) For the fracture apperance of embodiment two；Scheme the fracture apperance that (II) is embodiment three；Scheme the fracture apperance that (III) is example IV；Figure (IV) it is the fracture apperance partial enlarged drawing of example IV；Scheme the surface topography that (V) is example IV.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment one
A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, is comprised the steps of：
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, to remove its surface Organic gel, then clean with distilled water flushing, dry for standby at 50 DEG C；
Step 2, is classified batch mixing, by silicon carbide powder, phenolic resin, four kinds of components of boron carbide powder according to weight ratio 68.2:6.8:10:After 15 weigh, first carborundum and boron carbide powder are put into plastics ball grinder, with alcohol by phenolic resin It is uniformly dissolved, phenolic resin and alcohol by volume ratio are 1:50；The phenolic resin alcoholic solution stirred is poured into plastics ball milling In tank, agate ball is added, wherein ball material mass ratio is 2:1, ball is mixed 2 hours under 300r/min rotating speed, and then adds pre- The short carbon fiber first handled well, continues ball mixed 5 hours under 100r/min rotating speed.Slurry is dried in revolution evaporator, Mixed-powder is obtained, biscuit composition is shown in Table 1.
The biscuit composition of table 1
Step 3, Bidirectional-pressure is compressing, under 180MPa pressure that mixed-powder is compressing, and pressuring method is Bidirectional-pressure；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, then 90 DEG C are warming up to, then is incubated 3 hours, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality The silicon grain that 2 times of summation, the biscuit being cured is placed on silicon grain, and graphite crucible is put into vacuum carbon tube furnace and starts to take out Vacuum, begins to warm up when body of heater vacuum is reduced to 0.1Pa, programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900- 1380 DEG C of programming rates are 10 DEG C/min, stop vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of programming rate For 20 DEG C/min, 20 minutes are incubated at 1600 DEG C；In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, is reached Room temperature is cooled to the furnace at 1300 DEG C；
The particle diameter of described silicon carbide powder is 10-15 μm, and the particle diameter of the boron carbide powder is less than 2 μm.
Described silicon grain particle diameter is 2mm.
Described short carbon fiber length is less than 4mm, and diameter is less than 7 μm.
Embodiment two
A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, is comprised the steps of：
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, to remove its surface Organic gel, then clean with distilled water flushing, dry for standby at 50 DEG C；
Step 2, be classified batch mixing, by silicon carbide powder, short carbon fiber, phenolic resin, four kinds of components of boron carbide powder according to Weight compares 60.8:14.2:10:After 15 weigh, first carborundum and boron carbide powder are put into plastics ball grinder, with alcohol by phenol Urea formaldehyde is uniformly dissolved, and phenolic resin and alcohol by volume ratio are 1:50；The phenolic resin alcoholic solution stirred is poured into modeling In pellet grinding jar, agate ball is added, wherein ball material mass ratio is 2:1, ball is mixed 2 hours under 300r/min rotating speed, and then The short carbon fiber anticipated is added, continues ball under 100r/min rotating speed mixed 5 hours.Slurry in revolution evaporator Dry, obtain mixed-powder, biscuit composition is shown in Table 2.
The biscuit composition of table 2
Step 3, Bidirectional-pressure is compressing, and it is 50 × 5mm's that the granule for the 2.00g that weighs, which is uniformly filled in cross section, It is compressing with semi-automatic pressure forming machine under 180MPa pressure in grinding tool, biscuit is made, pressuring method adds to be two-way Pressure；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, then 90 DEG C are warming up to, then is incubated 3 hours, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality The biscuit being cured, is then placed on silicon grain, graphite crucible is put into vacuum carbon tube furnace and opened by the silicon grain that 2 times of summation Beginning vacuumizes, and is begun to warm up when body of heater vacuum is reduced to 0.1Pa.Programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900-1380 DEG C of programming rate is 10 DEG C/min, stops vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of heating Speed is 20 DEG C/min, is incubated 20 minutes at 1600 DEG C.In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, Room temperature is cooled to the furnace when reaching 1300 DEG C.
The particle diameter of described silicon carbide powder is 10-15 μm, and the particle diameter of the boron carbide powder is less than 2 μm.
Described silicon grain particle diameter is 2mm.
Described short carbon fiber length is less than 4mm, and diameter is less than 7 μm.
Embodiment three
A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, is comprised the steps of：
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, to remove its surface Organic gel, then clean with distilled water flushing, dry for standby at 50 DEG C；
Step 2, is classified batch mixing, by silicon carbide powder, phenolic resin, four kinds of components of boron carbide powder according to weight ratio 52.6:22.4:10:After 15 weigh, first carborundum and boron carbide powder are put into plastics ball grinder, with alcohol by phenolic resin It is uniformly dissolved, phenolic resin and alcohol by volume ratio are 1:50；The phenolic resin alcoholic solution stirred is poured into plastics ball milling In tank, agate ball is added, wherein ball material mass ratio is 2:1, ball is mixed 2 hours under 300r/min rotating speed, and then adds pre- The short carbon fiber first handled well, continues ball mixed 5 hours under 100r/min rotating speed.Slurry is dried in revolution evaporator, Mixed-powder is obtained, biscuit composition is shown in Table 3.
The biscuit composition of table 3
Step 3, Bidirectional-pressure is compressing, and it is 50 × 5mm's that the granule for the 2.00g that weighs, which is uniformly filled in cross section, It is compressing with semi-automatic pressure forming machine under 180MPa pressure in grinding tool, biscuit is made, pressuring method adds to be two-way Pressure；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, then 90 DEG C are warming up to, then is incubated 3 hours, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality The biscuit being cured, is then placed on silicon grain, graphite crucible is put into vacuum carbon tube furnace and opened by the silicon grain that 2 times of summation Beginning vacuumizes, and is begun to warm up when body of heater vacuum is reduced to 0.1Pa.Programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900-1380 DEG C of programming rate is 10 DEG C/min, stops vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of heating Speed is 20 DEG C/min, is incubated 20 minutes at 1600 DEG C.In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, Room temperature is cooled to the furnace when reaching 1300 DEG C.
The particle diameter of described silicon carbide powder is 10-15 μm, and the particle diameter of the boron carbide powder is less than 2 μm.
Described silicon grain particle diameter is 2mm.
Described short carbon fiber length is less than 4mm, and diameter is less than 7 μm.
Example IV
A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, is comprised the steps of：
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, to remove its surface Organic gel, then clean with distilled water flushing, dry for standby at 50 DEG C；
Step 2, is classified batch mixing, by silicon carbide powder, phenolic resin, four kinds of components of boron carbide powder according to weight ratio 43.4:31.6:10:After 15 weigh, first carborundum and boron carbide powder are put into plastics ball grinder, with alcohol by phenolic resin It is uniformly dissolved, phenolic resin and alcohol by volume ratio are 1:50；The phenolic resin alcoholic solution stirred is poured into plastics ball milling In tank, agate ball is added, wherein ball material mass ratio is 2:1, ball is mixed 2 hours under 300r/min rotating speed, and then adds pre- The short carbon fiber first handled well, continues ball mixed 5 hours under 100r/min rotating speed.Slurry is dried in revolution evaporator, Mixed-powder is obtained, biscuit composition is shown in Table 4.
The biscuit composition of table 4
Step 3, Bidirectional-pressure is compressing, and it is 50 × 5mm's that the granule for the 2.00g that weighs, which is uniformly filled in cross section, It is compressing with semi-automatic pressure forming machine under 180MPa pressure in grinding tool, biscuit is made, pressuring method adds to be two-way Pressure；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, then 90 DEG C are warming up to, then is incubated 3 hours, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality The biscuit being cured, is then placed on silicon grain, graphite crucible is put into vacuum carbon tube furnace and opened by the silicon grain that 2 times of summation Beginning vacuumizes, and is begun to warm up when body of heater vacuum is reduced to 0.1Pa.Programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900-1380 DEG C of programming rate is 10 DEG C/min, stops vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of heating Speed is 20 DEG C/min, is incubated 20 minutes at 1600 DEG C.In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, Room temperature is cooled to the furnace when reaching 1300 DEG C.
The particle diameter of described silicon carbide powder is 10-15 μm, and the particle diameter of the boron carbide powder is less than 2 μm.
Described silicon grain particle diameter is 2mm.
Described short carbon fiber length is less than 4mm, and diameter is less than 7 μm.
Embodiment five
A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, is comprised the steps of：
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, to remove its surface Organic gel, then clean with distilled water flushing, dry for standby at 50 DEG C；
Step 2, is classified batch mixing, by silicon carbide powder, phenolic resin, four kinds of components of boron carbide powder according to weight 33.2: 41.8:10:After 15 weigh, first carborundum and boron carbide powder are put into plastics ball grinder, phenolic resin is dissolved with alcohol Uniformly, phenolic resin and alcohol by volume ratio are 1:50；The phenolic resin alcoholic solution stirred is poured into plastics ball grinder, Agate ball is added, wherein ball material mass ratio is 2:1, ball is mixed 2 hours under 300r/min rotating speed, and then adds and anticipates Good short carbon fiber, continues ball mixed 5 hours under 100r/min rotating speed.Slurry is dried in revolution evaporator, mixed Powder is closed, biscuit composition is shown in Table.
The biscuit composition of table 5
Step 3, Bidirectional-pressure is compressing, and it is 50 × 5mm's that the granule for the 2.00g that weighs, which is uniformly filled in cross section, It is compressing with semi-automatic pressure forming machine under 180MPa pressure in grinding tool, biscuit is made, pressuring method adds to be two-way Pressure；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, then 90 DEG C are warming up to, then is incubated 3 hours, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality The biscuit being cured, is then placed on silicon grain, graphite crucible is put into vacuum carbon tube furnace and opened by the silicon grain that 2 times of summation Beginning vacuumizes, and is begun to warm up when body of heater vacuum is reduced to 0.1Pa.Programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900-1380 DEG C of programming rate is 10 DEG C/min, stops vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of heating Speed is 20 DEG C/min, is incubated 20 minutes at 1600 DEG C.In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, Room temperature is cooled to the furnace when reaching 1300 DEG C.
The particle diameter of described silicon carbide powder is 10-15 μm, and the particle diameter of the boron carbide powder is less than 2 μm.
Described silicon grain particle diameter is 2mm.
Described short carbon fiber length is less than 4mm, and diameter is less than 7 μm.
Fig. 1 is biscuit sintering curre figure, and Fig. 2 is the strong mechanical performance ceramic material bending strength of embodiment 1- embodiments 5 And Fracture Toughness comparison, Fig. 3 is embodiment 2-4 fracture surface of sample and the surface topography of embodiment 4, the short carbon fiber volume fractions of Fig. 3 I 20%；The short carbon fiber volume fractions 30% of Fig. 3 II；The short carbon fiber volume fractions 40% of Fig. 3 III；The short carbon fiber volume integrals of Fig. 3 IV Number 40%, for the ease of confirming residual silicone content and fracture mode, using mixed acid (volume ratio 10HNO3:1HF) reaction is eroded Residual silicon.Its fracture mode and residual silicone content can be shown that fracture mode is typical brittle fracture by Fig. 3.Scheme (I) and figure (II) In perforated be residual silicon position, it is seen that using short carbon fiber as carbon source, residual silicon shape in tissue is strip.According to molten PRECIPITATION MECHANISM is solved, fibrous outer gradually dissolves generates secondary carborundum with liquid pasc reaction, and secondary carborundum is on former carborundum Deposition is grown up.Final residual silicon instead of the original position of short carbon fiber, and this form helps to reduce residual silicon phase size, is conducive to carrying High sintered body mechanical property.From Fig. 3 (I) and Fig. 3 (II) it can be seen that silicon-carbide particle is in transgranular fracture pattern, boron carbide particles Crystal formation is complete, and its fracture mode is grain boundary fracture (particle extraction).Fig. 3 (III) is that short carbon fiber volume fraction is in biscuit 40%, figure Hole region is significantly reduced, and residual silicon volume fraction is about 8%.Fig. 3 (IV) amplifies for Fig. 3 (III) perforated, hole The generation for having twin carborundum is observed in hole, the short carbon fiber of 40% volume fraction of addition is suitable carbon source addition, In course of reaction, short carbon fiber and liquid-state silicon react generation carborundum, and this process is along with volumetric expansion, secondary carbon SiClx is not only filled with most of hole, has also filled up the position of former short carbon fiber, by the control of residual silicon volume fraction 6%. Figure V is 40% short carbon fiber specimen surface pattern of addition, it is seen that residual silicone content is very low, and this is consistent with conclusion above.Due to Secondary carborundum is connected to original carborundum, and to form silicon-carbide particle in ceramic continuous skeleton, fracture process main with transgranular fracture Based on, there is cleavage step to be formed after partially carbonized silicon grain fracture, the absorption for helping to energy of cleavage step is broken tough Property value rise.And the grain size being added is the features such as be less than high intensity and the tiny particle that 2 μm of boron carbide has due to it, Fracture process is main based on grain boundary fracture.Grain boundary fracture pattern adds the path of crack propagation, adds Crack Extension Resistance, strengthens toughness of material.According to Hall Page formula, when organizing average grain size reduction, its toughness and tenacity can Improve.This is also to add the first purpose that grain size is less than 2 μm of boron carbides.Analyzed more than, it is believed that the high-strength low residual silicon of performance The fracture mechanism for measuring silicon carbide/carbon boron composite ceramics is based on carborundum transgranular fracture, supplemented by boron carbide grain boundary fracture Combined rupture form.
Before Mechanics Performance Testing, all samples are first roughly ground with grinding machine, diamond disk fine grinding, finally with 0.1 μm of gold Hard rock abrasive pastes polish chamfering.Every group of sample Mechanics Performance Testing number of times is all higher than 6 times.Finally give containing the examination of 40% short carbon fiber Sample has highest toughness and tenacity, respectively 472MPa and 7.4MPam1/2.Its bending strength compares with fracture toughness 86% and 114% has been respectively increased with traditional silicon carbide reaction-sintered performance.

Claims (5)

1. a kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content, it is characterised in that comprising following Step：
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, organic to remove its surface Glue, clean with distilled water flushing after taking-up, dry for standby；
Step 2, is classified batch mixing, by the short carbon fiber after silicon carbide powder, processing, phenolic resin, four kinds of components of boron carbide powder According to weight ratio (68.2-33.2):(6.8-41.8):10:After 15 weigh, carborundum and boron carbide powder are first put into baton round In grinding jar, phenolic resin is uniformly dissolved with alcohol, phenolic resin and alcohol by volume ratio are 1:50；By the phenolic aldehyde tree stirred Fat alcoholic solution is poured into plastics ball grinder, adds agate ball, wherein ball material mass ratio is 2:1, under 300r/min rotating speed Ball is mixed 2 hours, and then adds the short carbon fiber anticipated, and continues ball under 100r/min rotating speed and mixes 5 hours, slurry Material is dried in revolution evaporator, obtains mixed-powder；
Step 3, Bidirectional-pressure is compressing, under 180MPa pressure that mixed-powder is compressing, and pressuring method is two-way Pressurization；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, is then heated up To 90 DEG C, then 3 hours are incubated, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality summation 2 times of silicon grain, the biscuit being cured is placed on silicon grain, and graphite crucible is put into vacuum carbon tube furnace and starts to take out true Sky, begins to warm up when body of heater vacuum is reduced to 0.1Pa, programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900- 1380 DEG C of programming rates are 10 DEG C/min, stop vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of programming rate For 20 DEG C/min, 20 minutes are incubated at 1600 DEG C；In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, is reached Room temperature is cooled to the furnace at 1300 DEG C.
2. the preparation method of the reaction sintering silicon carbide ceramic of a kind of low residual silicon size and content according to claim 1, Characterized in that, the particle diameter of described silicon carbide powder is 10-15 μm, the particle diameter of the boron carbide powder is less than 2 μm.
3. the preparation method of the reaction sintering silicon carbide ceramic of a kind of low residual silicon size and content according to claim 1, Characterized in that, described silicon grain particle diameter is 2mm.
4. the preparation method of the reaction sintering silicon carbide ceramic of a kind of low residual silicon size and content according to claim 1, Characterized in that, described short carbon fiber length is less than 4mm, diameter is less than 7 μm.
5. the preparation method of the reaction sintering silicon carbide ceramic of a kind of low residual silicon size and content according to claim 1, Characterized in that,
Step one, fiber is pre-processed, and short carbon fiber is placed in into sonic oscillation 20min in absolute alcohol, organic to remove its surface Glue, then clean with distilled water flushing, dry for standby at 50 DEG C；
Step 2, is classified batch mixing, silicon carbide powder, phenolic resin, four kinds of components of boron carbide powder is compared into 43.4 according to weight: 31.6:10:After 15 weigh, first carborundum and boron carbide powder are put into plastics ball grinder, phenolic resin is dissolved with alcohol Uniformly, phenolic resin and alcohol by volume ratio are 1:50；The phenolic resin alcoholic solution stirred is poured into plastics ball grinder, Agate ball is added, wherein ball material mass ratio is 2:1, ball is mixed 2 hours under 300r/min rotating speed, and then adds and anticipates Good short carbon fiber, continues ball mixed 5 hours under 100r/min rotating speed.Slurry is dried in revolution evaporator, mixed Close powder；
Step 3, Bidirectional-pressure is compressing, and the granule for the 2.00g that weighs is uniformly filled in the grinding tool that cross section is 50 × 5mm In, it is compressing with semi-automatic pressure forming machine under 180MPa pressure, biscuit is made, pressuring method is Bidirectional-pressure；
Step 4, drying, solidification, the biscuit suppressed is placed in drying baker, is incubated 3 hours at 40 DEG C, is then heated up To 90 DEG C, then 3 hours are incubated, finally rising to 150 DEG C with 1 DEG C per minute of programming rate is incubated 10 hours；
Step 5, reaction-sintered adds graphite paper in graphite crucible bottom, then uniform to place biscuit and graphite paper quality summation The biscuit being cured, is then placed on silicon grain by 2 times of silicon grain, and graphite crucible is put into vacuum carbon tube furnace and starts to take out Vacuum, begins to warm up when body of heater vacuum is reduced to 0.1Pa.Programming rate from room temperature at 900 DEG C be 5 DEG C/min, 900- 1380 DEG C of programming rates are 10 DEG C/min, stop vacuumizing when furnace temperature reaches 1380 DEG C, 1380-1600 DEG C of programming rate For 20 DEG C/min, 20 minutes are incubated at 1600 DEG C；In temperature-fall period, cooling rate is 5 DEG C/min at 1600-1300 DEG C, is reached Room temperature is cooled to the furnace at 1300 DEG C；
The particle diameter of described silicon carbide powder is 10-15 μm, and the particle diameter of the boron carbide powder is less than 2 μm；
Described silicon grain particle diameter is 2mm；
Described short carbon fiber length is less than 4mm, and diameter is less than 7 μm.
CN201710287236.1A 2017-04-27 2017-04-27 A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content Pending CN106995314A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710287236.1A CN106995314A (en) 2017-04-27 2017-04-27 A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710287236.1A CN106995314A (en) 2017-04-27 2017-04-27 A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content

Publications (1)

Publication Number Publication Date
CN106995314A true CN106995314A (en) 2017-08-01

Family

ID=59435513

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710287236.1A Pending CN106995314A (en) 2017-04-27 2017-04-27 A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content

Country Status (1)

Country Link
CN (1) CN106995314A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180195A (en) * 2018-09-30 2019-01-11 威海威林特电控科技有限公司 One kind is based on adding obdurability porous ceramic composite and its preparation process made of infiltrated metal method
CN112430113A (en) * 2020-12-31 2021-03-02 泰州华航精密铸造有限公司 Novel reaction sintering SiC ceramic material and preparation method thereof
CN116727214A (en) * 2023-06-14 2023-09-12 湖南搏盛天弘新材料技术有限公司 Silicon carbide coating on surface of carbon fiber thermal insulation material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101314543A (en) * 2007-06-01 2008-12-03 哈尔滨工业大学 High-quality short carbon fiber toughened silicon carbide composite material, preparation and application thereof
JP2012254917A (en) * 2011-05-18 2012-12-27 Covalent Materials Corp Crucible, and method for producing the same
CN103508734A (en) * 2013-09-25 2014-01-15 西安交通大学 Preparation method of bulletproof boron carbide/silicon carbide composite ceramic

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101314543A (en) * 2007-06-01 2008-12-03 哈尔滨工业大学 High-quality short carbon fiber toughened silicon carbide composite material, preparation and application thereof
JP2012254917A (en) * 2011-05-18 2012-12-27 Covalent Materials Corp Crucible, and method for producing the same
CN103508734A (en) * 2013-09-25 2014-01-15 西安交通大学 Preparation method of bulletproof boron carbide/silicon carbide composite ceramic

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
鲍崇高等: "反应烧结碳化硅陶瓷中碳化硼-碳纤维联合增强机制", 《稀有金属材料与工程》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180195A (en) * 2018-09-30 2019-01-11 威海威林特电控科技有限公司 One kind is based on adding obdurability porous ceramic composite and its preparation process made of infiltrated metal method
CN112430113A (en) * 2020-12-31 2021-03-02 泰州华航精密铸造有限公司 Novel reaction sintering SiC ceramic material and preparation method thereof
CN116727214A (en) * 2023-06-14 2023-09-12 湖南搏盛天弘新材料技术有限公司 Silicon carbide coating on surface of carbon fiber thermal insulation material

Similar Documents

Publication Publication Date Title
CN102219536B (en) B4C/SiC whisker/SiC multiphase ceramic matrix composite and preparation method thereof
CN100478302C (en) High intensity ceramic ball made from compact silicon carbide and preparation method
CN105130438B (en) A kind of method that boron carbide ceramics composite is prepared based on reaction-sintered
CN106986649B (en) A kind of high-performance SiC/W cermet combining nozzle and preparation method thereof
CN106866151B (en) Method for preparing carbon fiber toughened zirconium boride-silicon carbide composite material by slurry injection process
CN103030396B (en) Boron carbide silicon carbide composite ceramic and preparation method thereof
CN106002666B (en) A kind of multi-functional resins grinding wheel and preparation method thereof
CN106995314A (en) A kind of preparation method of the reaction sintering silicon carbide ceramic of low residual silicon size and content
CN110498685B (en) Preparation method of carbon fiber reinforced ceramic matrix composite
CN103288468A (en) Preparation method for fiber reinforced carbon-silicon carbide-zirconium carbide-based composite material
CN102161594B (en) SiC whisker reinforced SiC ceramic matrix composite and preparation method thereof
CN107399988A (en) A kind of method for preparing alumina carbon SiClx composite porous ceramic using aluminium silicon systems industrial residue
CN108706973A (en) A kind of preparation method of high intensity high-heat conductivity graphite material
CN102731093A (en) Method for low-temperature densification sintering of boron carbide-based ceramic material
CN105315006A (en) Method for preparing gradient porous silicon nitride ceramic
CN112321300A (en) High-thermal-conductivity low-porosity graphite for curved glass hot bending die and preparation method thereof
CN110202131A (en) A kind of preparation method of diamond composition
CN113416076A (en) Preparation method of self-reinforced silicon carbide ceramic material
CN112830798A (en) Preparation method of boron carbide granulation powder for pressureless sintering
CN105503192A (en) Injection molding reactive sintering B4C/SiC composite ceramic material and preparation method thereof
CN105967712A (en) Method for preparing carbon fiber reinforced silicon carbide (Csf/C-SiC) composite material
CN111892414A (en) Short carbon fiber reinforced boron carbide composite material and preparation method thereof
CN107500776B (en) Polycrystalline cubic boron nitride cutter material and preparation method thereof
CN101734920A (en) Titanium nitride porous ceramics and preparation method thereof
CN103073299A (en) High-tenacity zirconium diboride-carborundum complex phase ceramic material taking carbon spheres as additive 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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170801