CN105948754A - Method for preparing fine-grain silicon carbide ceramic through reaction sintering - Google Patents
Method for preparing fine-grain silicon carbide ceramic through reaction sintering Download PDFInfo
- Publication number
- CN105948754A CN105948754A CN201610290514.4A CN201610290514A CN105948754A CN 105948754 A CN105948754 A CN 105948754A CN 201610290514 A CN201610290514 A CN 201610290514A CN 105948754 A CN105948754 A CN 105948754A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- powder
- silicon
- high temperature
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—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
- C04B2235/42—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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/614—Gas infiltration of green bodies or pre-forms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing fine-grain silicon carbide ceramic through reaction sintering. The method sequentially comprises the following steps: preparing a main material comprising 75-90wt% of silicon carbide micro-powder and 10-15wt% of active carbon powder; adding a dispersant and deionized water to the main material, sequentially adding an aqueous solution of organic matters containing high temperature carbon residue and a water-soluble polymer binder solution, and stirring and mixing above materials in a ball mill to prepare a uniformly-dispersed water-based silicon carbide slip; and sequentially carrying out spray granulation, dry press molding, dewaxing, vehicle working, high temperature siliconising sintering and alkali treatment desilication to obtain the silicon carbide ceramic.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, relate to a kind of reaction-sintered and prepare silicon carbide ceramics (fine grain silicon carbide ceramics)
Manufacture method.
Background technology
Thyrite was born since century more than one, and reaction sintering silicon carbide ceramic material, because both having silicon carbide ceramics
The characteristics such as anti-thermal shock, high temperature resistant, wear-resistant, heat shock resistance, highly thermally conductive, high rigidity, antioxidation and resistance to chemical corrosion, again
Have than pressureless sintering and hot-pressing sintering technique equipment is simple, sintering time is short, sintering temperature is low, cost is little and shrinkage factor is little
(＜ 1%) can the advantage such as net-shape-sinter, this makes RBSiC achieve large-scale industrial production, and the most extensively should
Every field under the rigor condition such as high temperature, high pressure, burn into radiation, abrasion.
The ultimate principle of reaction sintering silicon carbide ceramic is: under the high temperature of 1430～1700 DEG C, has the liquid Hunan silicon of reactivity
Or silicon alloy or gas-phase silicon, under the effect of capillary force, penetrate into the porous ceramics biscuit of carbon containing, and react generation with carbon therein
Carborundum, newly-generated silicon B-carbide combines original alpha-silicon carbide granule in biscuit in situ, and the impregnant-silicon of excess is filled in element
Residual pore in base, completes the process of densification.The final thing of reaction sintering silicon carbide ceramic is main by carborundum grain and trip mutually
Form from silicon, contain minimal amount of free carbon simultaneously.
Chinese patent discloses one " reaction sintering silicon carbide ceramic and production application thereof " on August 19th, 2009
(CN10508570A), its scheme is: 5～8 weight portion granularities be the carborundum powder of 10～90 μm, 2～3 weight portion granularity be
The carborundum powder of 0.1～10 μm, 0～1 part by weight of carbon black powder, 0.3～0.8 parts by weight of graphite powder and 0.1～0.3 weight account polyethylene alcohol
Or methylcellulose liquid (weight concentration is 50～70%) and distilled water dispensing slurrying, injection forming, be dried, repaired biscuit shove charge,
1400～2200 DEG C are incubated vacuum-sinterings in 4～5 hours and go silicon oxidation and check and accept, material volume density 3.02g/cm of preparation3Above,
Mainly be made up of coarse granule and fine grained SiC, metal Si, the porosity < 0.1, bending strength (20 DEG C) 250MPa, springform
Amount (20 DEG C) 330GPa, hardness (Mohs' hardness) 13, heat conductivity (1200 DEG C) 45w/m.k, in microstructure thick
Grain is relatively big (about 45 μm), and contents of free si more (about 12wt%) and size are relatively big (30-50 μm).
Although reaction sintering silicon carbide ceramic has formed large-scale production, but existing reaction sintering silicon carbide ceramic product grains
Thick, contents of free si is more and size is relatively big, and microhomogeneity is bad.There are some researches show that the fusing point of silicon is relatively low
(1410 DEG C), intensity the least (less than 100MPa), much lower compared with the mechanical property of carborundum, therefore free silica granule is big
Little and content affects the mechanical performance of reaction sintering silicon carbide ceramic.The particle diameter of free silica granule is the biggest, suffered by silicon-carbide particle
Residual stress is the biggest, and the mechanical strength of material is decreased obviously and corrosion-resistant, constrains its usage range.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that reaction-sintered prepares fine grain silicon carbide ceramics.
In order to solve above-mentioned technical problem, the present invention provides a kind of reaction-sintered to prepare the preparation method of silicon carbide ceramics, enters successively
Row following steps:
1), preparation major ingredient:
Major ingredient is grouped into by the one-tenth of following weight content: silicon carbide micro-powder 75%～90% (preferably 80～90%), activated carbon powder
10%～25% (preferably 10～20%)；
The grain diameter of described silicon carbide micro-powder (SiC micropowder) is 3～10 μm (for example, 5 μm)；
The grain diameter of described activated carbon powder is 20～100nm；
2), ball mill mixing:
In major ingredient, it is initially charged dispersant, deionized water, is then sequentially added into the organic aqueous solution of high temperature carbon residue, water-soluble
Property high polymer binder solution, stirring mixing in ball mill, thus be prepared as homodisperse water base silicon carbide slurry；
Described dispersant is 0.5～2% (preferably 1%) with the weight ratio of major ingredient；
Described deionized water is 35～55% (preferably 50%) with the weight ratio of major ingredient；
It is described that to have the organic aqueous solution of high temperature carbon residue and the weight ratio of major ingredient be 10～25% (preferably 15%)；
Described water soluble polymer binding agent is 5～15% (preferably 10%) with the weight ratio of major ingredient；
In the described organic aqueous solution having high temperature carbon residue, the organic mass concentration of high temperature carbon residue is 15～25% (preferably
20%)；
In described water soluble polymer binder solution, the mass concentration of water soluble polymer binding agent is 10～15% (preferably
12%)；
Remarks illustrate: this step is with deionization water as solvent, and carborundum ball, as ball-milling medium, carries out wet ball grinding batch mixing；
3), mist projection granulating:
Use atomizer granulating and drying machine to step 2) obtained by water base silicon carbide slurry carry out pelletize, gained pelletizing
Granularity be 60～400 mesh (the most about 38～250 μm), percent water be 0.8wt%～2wt% (for example, 1.5wt%)；
4), dry-pressing formed:
By step 3) obtained by old prior to room temperature lower seal 4～6 days of pelletizing (preferably 5 days), then in 10～30MPa
Pressure under dry-pressing formed (can by four-column hydraulic press dry-pressing formed)；
5), de-waxing:
By step 4) prepare base substrate in a vacuum furnace, in 800～1000 DEG C be incubated (preferably 900 DEG C insulations in 0.5～1.5 hour
0.5 hour, it is therefore an objective to get rid of the volatile components such as moisture in base substrate, binding agent and other organic additives)；
6), car system:
By step 5) prepare de-waxing after base substrate (there is the base substrate of some strength) car make required form (that is, according to drawing
Certain shape made by car), obtain biscuit；
7), high temperature siliconising sintering:
First on graphite lining plate (being provided with boron nitride coating), uniformly put one layer of silicon chip, on silicon chip, then put biscuit, press
Mode according to one layer of silicon chip, a laminin base is overlapped, and the superiors are silicon chip；Eventually load vacuum sintering furnace, in vacuum
Under the conditions of be incubated 2～6h (for example, 1600 DEG C insulation 2h) at 1400～1700 DEG C, obtain reaction sintering silicon carbide ceramic；
Described every laminin base is 1:1～2.0 (preferably 1:1.5) with the weight ratio of every layer of silicon chip；
Silicon chip cross-sectional area is less than (being slightly less than) biscuit；
8), alkali processes except silicon:
The silicon first using mechanical system (such as grinder buffing) tentatively to remove reaction sintering silicon carbide ceramic surface (includes bulk silicon
With silicon chip residue), be then placed in the sodium hydroxide solution of 300～400 DEG C soaking (thus further realize except silicon), finally in
Water soaks (washing), obtains silicon carbide ceramics.
Remarks illustrate: the silicon on above-mentioned preliminary removal reaction sintering silicon carbide ceramic surface, refer to fall reaction-sintered carbon with grinder buffing
The silicon (including bulk silicon and silicon chip residue) of SiClx ceramic surface, as long as guaranteeing do not have bulk silicon and residue；
Silicon and sodium hydroxide reaction generate sodium silicate, therefore put into immersion in sodium hydroxide solution and can realize further removing carborundum
The silicon of product surface；Owing to sodium silicate is dissolved in water, therefore can finally realize removing the silicon on silicon carbide articles surface.
The improvement of the preparation method of silicon carbide ceramics is prepared as the reaction-sintered of the present invention:
Described silicon carbide micro-powder is the particle diameter green silicon carbide powder in 3～10 μm；
Described activated carbon is white carbon black or activated carbon powder；
Described dispersant is polymine (PEI), Tetramethylammonium hydroxide, sodium hydroxide；
The described Organic substance having high temperature carbon residue is starch, lignocellulose；
Described water soluble polymer binding agent is polyvinyl alcohol (PVA), Polyethylene Glycol or methylcellulose.
The further improvement of the preparation method of silicon carbide ceramics is prepared as the reaction-sintered of the present invention:
Described step 7) the preparation method of silicon chip be: by the silicon of powder, powder 2123 resins with ethanol according to 88:8:4
Weight ratio uniformly mix after, be pressed into flap-type and (flap-type can be pressed on mo(u)ldenpress, such as, can be the circle of φ 60*10mm
Shape sheet).
The further improvement of the preparation method of silicon carbide ceramics is prepared as the reaction-sintered of the present invention:
Described step 8) in put in the sodium hydroxide solution of 300～400 DEG C and soak, (soak till not regeneration sodium silicate
Time is about 30～40min).
Described step 3) in, use atomizer granulating and drying machine to step 2) obtained by water base silicon carbide slurry spray
Mist is dried, and water base silicon carbide slurry is directly transported to atomizing disk by peristaltic pump, and atomizing disk high speed rotating is slip under centrifugal action
Become droplet and hot air, after moisture evaporation, form spherical particle.By regulation drying machine parameter, it is spray-dried and prepares
Granularity be 60～400 mesh (i.e. 38～250 μm), percent water be the spherical silicon carbide reaction-sintered spray of 0.8wt%～2wt%
Mist pelletizing.
The proportioning raw materials that the present invention uses is scientific and reasonable, safe production process, it is provided that a kind of fine grain high-performance reaction-sintered carbon
The preparation technology of SiClx ceramic material, is the upgrading products of existing thyrite.Existing reaction sintering silicon carbide ceramic is deposited
In following defect: (1) use original SiC grain size of micropowder about 10～90 μm, product microcosmic coarse grains prepared by (2),
Contents of free si more (8%～14%), and silicon point granule is relatively big, microhomogeneity is bad, and the mechanical strength of material is obvious
Declining, hardness reduces.
And fine grain reaction sintering silicon carbide ceramic material prepared by the present invention, there is following technical advantage: it is original that (1) uses
SiC micro powder granule particle diameter is in 3～10 μm, and grain diameter is less, and the gap between granule and granule is less, silicon point after high temperature siliconising
The least, overall microstructure is uniform, and contents of free si is below 6%；(2) with the highest activated carbon powder of activity and residual containing high temperature
The Organic substance of charcoal is carbon source, improves the reactivity of C and metal Si, can rise during the organic solution batch mixing of high temperature carbon residue simultaneously
To the effect of binding agent, after high temperature de-waxing processes, the network-like structure of formation, the mechanical strength of base substrate can be improved；(3) add
Add the Organic substance (starch, lignocellulose) of the high temperature carbon residue of nontoxic, environmental protection, working environment can be improved.
The content of fine grain sintered silicon carbide ceramics material silicon carbide prepared by the present invention more than 94%, bending strength up to
410MPa (20 DEG C), hardness (HRA) improves to more than 90, and bulk density is 3.05～3.10g/cm3Between.
The present invention uses thin silicon carbide micro-powder to be to prepare fine grain and contents of free si is few, and silicon speckle particle diameter is little, microstructure uniformly,
Mechanical strength is high, one of the key of high-performance silicon carbide reaction-sintered material of good corrosion resistance.
In sum, the defect that the present invention exists to overcome existing silicon carbide reaction-sintered goods, use the carbonization that particle diameter is less
Silicon powder and activated carbon are raw material, add nontoxic, the organic additive of environmental protection containing carbon residue, with deionized water as solvent,
By wet ball grinding batch mixing, through the technique mistake such as mist projection granulating, dry-pressing formed, de-waxing, car system, vacuum siliconising sintering, alkali process
Journey is prepared for a kind of fine grain silicon carbide reaction-sintered, and more existing preparation technology greatly reduces the free silica in goods, its content
Reduced to less than 6% by 8%～14%, and the performance such as the bulk density of material, hardness, corrosion resistance, bending strength is the most
Improve.Silicon carbide reaction-sintered prepared by the present invention has mechanical strength and the hardness of approximation pressureless sintering carborundum, and reacts burning
Knot carborundum sintering temperature point is low, can have huge prospect with dead size molding in commercial Application afterwards.
Detailed description of the invention
Embodiment 1, a kind of reaction-sintered prepare the production method of fine grain silicon carbide ceramics, follow the steps below successively:
1), preparation major ingredient:
Described major ingredient is grouped into by the one-tenth of following weight content: green silicon carbide powder (SiC micropowder) 85%, activated carbon powder 15%；
Described green silicon carbide powder D50=5 μm；
The grain diameter of described activated carbon micropowder is 20～100nm；
2), ball mill mixing:
With deionization water as solvent, carborundum ball, as ball-milling medium, carries out wet ball grinding batch mixing；Specific as follows:
In 100 portions of major ingredients, it is initially charged 1 part of dispersant and 50 parts of deionized waters, is then sequentially added into 15 parts and has high temperature carbon residue
Organic aqueous solution (in this aqueous solution, the organic mass concentration having high temperature carbon residue is 20%), 10 parts of water solublity high scores
Sub-adhesive solution (in this aqueous solution, the mass concentration of water soluble polymer binding agent is 12%), in ball mill, stirring is mixed
Close (rotating speed is 60r/min, and the time is 4h), thus be prepared as homodisperse water base silicon carbide slurry；Above-mentioned part is weight portion.
Dispersant is polymine (PEI)；
The Organic substance having high temperature carbon residue is starch；Starch such as can be selected for corn starch；
Polyvinyl alcohol (PVA) selected by water soluble polymer binding agent；
3), mist projection granulating:
Use atomizer granulating and drying machine to step 2) obtained by water base silicon carbide slurry be spray-dried, water base carbon
SiClx slip is directly transported to atomizing disk by peristaltic pump, and atomizing disk high speed rotating slip under centrifugal action becomes droplet and heat
Air contact, forms spherical particle after moisture evaporation.By regulating drying machine parameter, inlet temperature 250 DEG C, outlet temperature 120 DEG C,
Slip flow 15kg/h, atomizing disk rotating speed 10000r/min, being spray-dried and preparing granularity is that 60～400 mesh, percent water are
The spherical silicon carbide reaction-sintered mist projection granulating powder (abbreviation pelletizing) of 1.5wt%.
4), dry-pressing formed:
By step 3) obtained by spherical silicon carbide reaction-sintered mist projection granulating powder, old prior to Room-temperature seal 5 days, then lead to
Cross four-column hydraulic press dry-pressing formed with the pressure of 10～30MPa；
5), de-waxing:
By step 4) base substrate for preparing in a vacuum furnace, heat up with the heating rate of 300 DEG C/h, be incubated 0.5 hour at 900 DEG C,
Thus get rid of the volatile components such as moisture in base substrate, binding agent and other organic additives；
6), car system:
By step 5) prepare the base substrate with some strength make certain shape according to drawing car, obtain biscuit.
7), high temperature siliconising sintering:
First on graphite lining plate (being provided with boron nitride coating, coating layer thickness for example, 3～5mm), uniformly put one layer of silicon chip, then
Putting biscuit on silicon chip, be overlapped according to the mode of one layer of silicon chip, a laminin base, the superiors are silicon chip；Eventually
Load vacuum sintering furnace, under vacuum condition, be incubated 2h at 1600 DEG C, obtain reaction sintering silicon carbide ceramic；
Described every laminin base is 1:1.5 with the weight ratio of every layer of silicon chip；
The preparation method of above-mentioned silicon chip is: by silica flour (mean diameter 100 μm), 2123 resin-oatmeals (mean diameter is 75 μm),
After ethanol mixes according to the weight ratio of 88:8:4, on mo(u)ldenpress, the different-diameter circle silicon chip of compacting is (for example: φ
60*10mm、φ100*20mm).Silicon chip cross-sectional area is slightly less than biscuit.
8), alkali processes
The bulk silicon on reaction sintering silicon carbide ceramic and silicon chip residue is fallen, it is ensured that do not have bulk silicon and residue with grinder buffing,
The product polished is loaded circular rustless steel basket, puts into alkali and process in stove, alkali liquor (certain density sodium hydroxide solution,
The most saturated sodium hydroxide solution) temperature controls at about 350 DEG C, and product soaks 40min (silicon and sodium hydroxide in alkali liquor
Reaction generates sodium silicate), the most not regeneration sodium silicate, basket is proposed together with product, treats that temperature is reduced to room temperature, then will
Product is together put into water tank and is soaked together with basket, and sodium silicate is dissolved in water, thus removes the silicon on silicon carbide articles surface.
Obtain silicon carbide ceramics.
9), performance detection
Drainage detection bulk density is 3.06g/cm3, contents of free si 5.0%, bending strength is at 410MPa, Rockwell hardness
(HRA)92.5。
Embodiment 2, by embodiment 1 step 1) in " green silicon carbide powder (SiC micropowder) 85%, activated carbon powder 15% "
Change " green silicon carbide powder (SiC micropowder) 90%, activated carbon powder 10% " into；Remaining is equal to embodiment 1；Its performance detects
Result is: drainage detection bulk density is 3.03g/cm3, contents of free si 8.0%, bending strength is at 370MPa, and Rockwell is hard
Degree (HRA) 91.
Embodiment 3: by embodiment 1 step 1) in " green silicon carbide powder (SiC micropowder) 85%, activated carbon powder 15% "
Remaining is equal to embodiment 1 to change " green silicon carbide powder (SiC micropowder) 80%, activated carbon powder 20% " into；Its performance detection knot
Fruit is: drainage detection bulk density is 3.08g/cm3, contents of free si 4.0%, bending strength is at 390MPa, Rockwell hardness
(HRA)92.0。
Comparative example 1-1, cancel embodiment 1 step 2) in the use of " 15 parts have high temperature carbon residue organic aqueous solution ", remaining
It being equal to embodiment 1, but in step 6) during car system, base substrate is easy to cracking, it is impossible to normal turnery processing, is primarily due to
The high temperature carbon residue Organic substance of the present invention is cracked into network carbon in de-waxing process, enhances the intensity of base substrate.
Comparative example 1-2, by embodiment 1 step 2) in " consumption having high temperature carbon residue organic aqueous solution is made into 30 parts by 15 parts "；
Remaining is equal to embodiment 1, but in step 5) during de-waxing, there is a lot of micropores and micro-crack in billet surface, is primarily due to
High temperature carbon residue Organic substance thermal cracking during de-waxing, concentrates volatilization with Organic substance in time base substrate, causes base substrate to receive thermal shock,
A lot of micro-crack occurs, causes base substrate to use.
Comparative example 1-3, by embodiment 1 step 1) in " green silicon powder D50=5 μm " make " green silicon carbide powder D into50=14 μm "
Remaining is equal to embodiment 1；Its performance test results is: drainage detection bulk density is 3.05g/cm3, contents of free si 10%,
Bending strength is at 360MPa.Rockwell hardness (HRA) 91.0.
Comparative example 1-4, by embodiment 1 step 1) in " silicon carbide micro-powder D50=5 μm " make " silicon carbide micro-powder D50=1 μm " into
Remaining is equal to embodiment 1；Its performance test results is: drainage detection bulk density is 2.98g/cm3, contents of free si 8%,
Bending strength is at 280MPa.Rockwell hardness (HRA) 90.0.
Comparative example 1-5, by embodiment 1 step 1) in major ingredient make into " green silicon carbide powder (SiC micropowder) 70%, activity
Powdered carbon 30%, described green silicon carbide powder D50=45 μm；The grain diameter of described activated carbon micropowder is 3 μm；" remaining is equal to
Embodiment 1；Its performance test results is: drainage detection bulk density is 3.03g/cm3, contents of free si 12%, bending resistance is strong
Degree is at 300MPa.Rockwell hardness (HRA) 90.0.
The performance test results of above-mentioned case is as shown in table 1 below.
Table 1. embodiment and comparative example product properties parameter lookup table
Finally, in addition it is also necessary to be only several specific embodiments of the present invention it is noted that listed above.Obviously, the present invention is not
It is limited to above example, it is also possible to have many deformation.Those of ordinary skill in the art directly can lead from present disclosure
The all deformation gone out or associate, are all considered as protection scope of the present invention.
Claims (4)
1. reaction-sintered prepares the preparation method of silicon carbide ceramics, it is characterized in that following the steps below successively:
1), preparation major ingredient:
Major ingredient is grouped into by the one-tenth of following weight content: silicon carbide micro-powder 75%～90%, activated carbon powder 10%～25%；
The grain diameter of described silicon carbide micro-powder is 3～10 μm；
The grain diameter of described activated carbon powder is 20～100nm；
2), ball mill mixing:
In major ingredient, it is initially charged dispersant, deionized water, is then sequentially added into the organic aqueous solution of high temperature carbon residue, water-soluble
Property high polymer binder solution, stirring mixing in ball mill, thus be prepared as homodisperse water base silicon carbide slurry；
Described dispersant is 0.5～2% with the weight ratio of major ingredient；
Described deionized water is 35～55% with the weight ratio of major ingredient；
It is described that to have the organic aqueous solution of high temperature carbon residue and the weight ratio of major ingredient be 10～25%；
Described water soluble polymer binding agent is 5～15% with the weight ratio of major ingredient；
In the described organic aqueous solution having high temperature carbon residue, the organic mass concentration of high temperature carbon residue is 15～25%；
In described water soluble polymer binder solution, the mass concentration of water soluble polymer binding agent is 10～15%；
3), mist projection granulating:
Use atomizer granulating and drying machine to step 2) obtained by water base silicon carbide slurry carry out pelletize, gained pelletizing
Granularity be 60～400 mesh, percent water be 0.8wt%～2wt%；
4), dry-pressing formed:
By step 3) obtained by old prior to room temperature lower seal 4～6 days of pelletizing, then dry under the pressure of 10～30MPa
Molded；
5), de-waxing:
By step 4) prepare base substrate in a vacuum furnace, in 800～1000 DEG C be incubated 0.5～1.5 hour；
6), car system:
By step 5) prepare de-waxing after base substrate car make required form, obtain biscuit；
7), high temperature siliconising sintering:
First on graphite lining plate, uniformly put one layer of silicon chip, on silicon chip, then put biscuit, according to one layer of silicon chip, a laminin
The mode of base is overlapped, and the superiors are silicon chip；Eventually load vacuum sintering furnace, at 1400～1700 DEG C under vacuum condition
Insulation 2～6h, obtains reaction sintering silicon carbide ceramic；
Described every laminin base is 1:1～2.0 with the weight ratio of every layer of silicon chip；
8), alkali processes except silicon:
First use mechanical system tentatively to remove the silicon on reaction sintering silicon carbide ceramic surface, be then placed in the hydroxide of 300～400 DEG C
Sodium solution soaks, finally soaks in water, obtain silicon carbide ceramics.
Reaction-sintered the most according to claim 1 prepares the preparation method of silicon carbide ceramics, it is characterized in that:
Described silicon carbide micro-powder is the particle diameter green silicon carbide powder in 3～10 μm；
Described activated carbon is white carbon black or activated carbon powder；
Described dispersant is polymine, Tetramethylammonium hydroxide, sodium hydroxide；
The described Organic substance having high temperature carbon residue is starch, lignocellulose；
Described water soluble polymer binding agent is polyvinyl alcohol, Polyethylene Glycol or methylcellulose.
Reaction-sintered the most according to claim 2 prepares the preparation method of silicon carbide ceramics, it is characterized in that:
Described step 7) the preparation method of silicon chip be: by the silicon of powder, powder 2123 resins with ethanol according to 88:8:4
Weight ratio uniformly mix after, be pressed into flap-type.
Reaction-sintered the most according to claim 2 prepares the preparation method of silicon carbide ceramics, it is characterized in that:
Described step 8) in put in the sodium hydroxide solution of 300～400 DEG C and soak, till not regeneration sodium silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290514.4A CN105948754B (en) | 2016-05-03 | 2016-05-03 | The method that reaction-sintered prepares fine grain silicon carbide ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290514.4A CN105948754B (en) | 2016-05-03 | 2016-05-03 | The method that reaction-sintered prepares fine grain silicon carbide ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105948754A true CN105948754A (en) | 2016-09-21 |
| CN105948754B CN105948754B (en) | 2019-02-22 |
Family
ID=56913968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610290514.4A Active CN105948754B (en) | 2016-05-03 | 2016-05-03 | The method that reaction-sintered prepares fine grain silicon carbide ceramics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105948754B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478105A (en) * | 2016-09-26 | 2017-03-08 | 西安交通大学 | A kind of method that multistep reaction sintering process prepares the thyrite of low residual silicon |
| CN106673661A (en) * | 2016-12-26 | 2017-05-17 | 上海工程技术大学 | Thick-plate silicon carbide ceramic material and preparation method and application thereof |
| CN106915966A (en) * | 2017-03-22 | 2017-07-04 | 宁波伏尔肯陶瓷科技有限公司 | A kind of preparation method of reaction sintering silicon carbide ceramic product |
| CN106966732A (en) * | 2017-03-09 | 2017-07-21 | 平顶山学院 | A kind of fine powder silicon carbide ceramics and preparation method thereof |
| CN107244920A (en) * | 2017-07-04 | 2017-10-13 | 黑龙江科技大学 | Carborundum injection forming sintering method |
| CN107353007A (en) * | 2017-07-13 | 2017-11-17 | 华通信安(北京)科技发展有限公司 | A kind of diamond/silicon carbide composite 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 |
| CN108706977A (en) * | 2018-06-04 | 2018-10-26 | 陕西固勤材料技术有限公司 | A kind of shove charge method of silicon carbide reaction-sintered |
| CN109536768A (en) * | 2018-11-23 | 2019-03-29 | 中南大学 | A kind of three-dimensional network silicon carbide enhancing metal-base composites and preparation method |
| CN109776094A (en) * | 2017-11-10 | 2019-05-21 | 中国建筑材料科学研究总院有限公司 | Ultraprecise ceramic guide rail and preparation method thereof |
| CN110734287A (en) * | 2019-10-31 | 2020-01-31 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of silicon/silicon carbide composite ceramics |
| CN111269016A (en) * | 2020-02-26 | 2020-06-12 | 上海德宝密封件有限公司 | Silicon carbide product sintering method |
| CN112159232A (en) * | 2020-09-29 | 2021-01-01 | 南通三责精密陶瓷有限公司 | High-purity high-density silicon carbide ceramic and manufacturing method thereof |
| CN112341202A (en) * | 2020-10-27 | 2021-02-09 | 上海德宝密封件有限公司 | Granulation powder for improving performance of reaction sintered silicon carbide and preparation method thereof |
| CN113185297A (en) * | 2021-04-27 | 2021-07-30 | 湖北中烟工业有限责任公司 | Ceramic material for electric heating and application thereof |
| CN113698215A (en) * | 2020-05-20 | 2021-11-26 | 中国科学院金属研究所 | Compact layered silicon carbide ceramic and preparation method thereof |
| CN114591085A (en) * | 2022-01-19 | 2022-06-07 | 宁波伏尔肯科技股份有限公司 | Silicon carbide ceramic and preparation method thereof |
| CN115057707A (en) * | 2022-06-15 | 2022-09-16 | 中国科学院上海硅酸盐研究所 | High-performance reaction-sintered silicon carbide ceramic material with low free silicon content and preparation method thereof |
| CN115403388A (en) * | 2022-10-14 | 2022-11-29 | 郴州市拓道新材料科技有限公司 | Wear-resistant silicon dioxide/silicon carbide composite ceramic and preparation method and application thereof |
| CN116023148A (en) * | 2021-10-25 | 2023-04-28 | 中国科学院上海硅酸盐研究所 | Preparation method of silicon carbide ceramic and silicon carbide ceramic material prepared by preparation method |
| CN116283301A (en) * | 2023-03-23 | 2023-06-23 | 长春工程学院 | Silicon carbide semiconductor material and preparation process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289319A (en) * | 2008-06-03 | 2008-10-22 | 浙江东新密封有限公司 | Reaction sintering silicon carbide ceramic and production method thereof |
| CN103496697A (en) * | 2013-09-30 | 2014-01-08 | 四川大学 | Method for preparing activated carbon by utilizing rice hull pyrolytic carbon |
| CN104030686A (en) * | 2014-04-28 | 2014-09-10 | 宁波东联密封件有限公司 | High-toughness silicon carbide ceramic and preparation method thereof |
-
2016
- 2016-05-03 CN CN201610290514.4A patent/CN105948754B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289319A (en) * | 2008-06-03 | 2008-10-22 | 浙江东新密封有限公司 | Reaction sintering silicon carbide ceramic and production method thereof |
| CN103496697A (en) * | 2013-09-30 | 2014-01-08 | 四川大学 | Method for preparing activated carbon by utilizing rice hull pyrolytic carbon |
| CN104030686A (en) * | 2014-04-28 | 2014-09-10 | 宁波东联密封件有限公司 | High-toughness silicon carbide ceramic and preparation method thereof |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478105B (en) * | 2016-09-26 | 2019-04-09 | 西安交通大学 | A kind of method that multistep reaction sintering process prepares the thyrite of low residual silicon |
| CN106478105A (en) * | 2016-09-26 | 2017-03-08 | 西安交通大学 | A kind of method that multistep reaction sintering process prepares the thyrite of low residual silicon |
| CN106673661A (en) * | 2016-12-26 | 2017-05-17 | 上海工程技术大学 | Thick-plate silicon carbide ceramic material and preparation method and application thereof |
| CN106966732A (en) * | 2017-03-09 | 2017-07-21 | 平顶山学院 | A kind of fine powder silicon carbide ceramics and preparation method thereof |
| CN106966732B (en) * | 2017-03-09 | 2021-03-23 | 平顶山学院 | Fine powder silicon carbide ceramic and preparation method thereof |
| CN106915966A (en) * | 2017-03-22 | 2017-07-04 | 宁波伏尔肯陶瓷科技有限公司 | A kind of preparation method of reaction sintering silicon carbide ceramic product |
| CN107244920A (en) * | 2017-07-04 | 2017-10-13 | 黑龙江科技大学 | Carborundum injection forming sintering method |
| CN107353007A (en) * | 2017-07-13 | 2017-11-17 | 华通信安(北京)科技发展有限公司 | A kind of diamond/silicon carbide composite 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 |
| CN109776094A (en) * | 2017-11-10 | 2019-05-21 | 中国建筑材料科学研究总院有限公司 | Ultraprecise ceramic guide rail and preparation method thereof |
| CN108706977A (en) * | 2018-06-04 | 2018-10-26 | 陕西固勤材料技术有限公司 | A kind of shove charge method of silicon carbide reaction-sintered |
| CN109536768A (en) * | 2018-11-23 | 2019-03-29 | 中南大学 | A kind of three-dimensional network silicon carbide enhancing metal-base composites and preparation method |
| CN109536768B (en) * | 2018-11-23 | 2020-06-12 | 中南大学 | Three-dimensional network silicon carbide reinforced metal matrix composite material and preparation method thereof |
| CN110734287A (en) * | 2019-10-31 | 2020-01-31 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of silicon/silicon carbide composite ceramics |
| CN111269016A (en) * | 2020-02-26 | 2020-06-12 | 上海德宝密封件有限公司 | Silicon carbide product sintering method |
| CN113698215A (en) * | 2020-05-20 | 2021-11-26 | 中国科学院金属研究所 | Compact layered silicon carbide ceramic and preparation method thereof |
| CN112159232A (en) * | 2020-09-29 | 2021-01-01 | 南通三责精密陶瓷有限公司 | High-purity high-density silicon carbide ceramic and manufacturing method thereof |
| CN112341202A (en) * | 2020-10-27 | 2021-02-09 | 上海德宝密封件有限公司 | Granulation powder for improving performance of reaction sintered silicon carbide and preparation method thereof |
| CN113185297A (en) * | 2021-04-27 | 2021-07-30 | 湖北中烟工业有限责任公司 | Ceramic material for electric heating and application thereof |
| CN116023148A (en) * | 2021-10-25 | 2023-04-28 | 中国科学院上海硅酸盐研究所 | Preparation method of silicon carbide ceramic and silicon carbide ceramic material prepared by preparation method |
| CN114591085A (en) * | 2022-01-19 | 2022-06-07 | 宁波伏尔肯科技股份有限公司 | Silicon carbide ceramic and preparation method thereof |
| CN115057707A (en) * | 2022-06-15 | 2022-09-16 | 中国科学院上海硅酸盐研究所 | High-performance reaction-sintered silicon carbide ceramic material with low free silicon content and preparation method thereof |
| CN115403388A (en) * | 2022-10-14 | 2022-11-29 | 郴州市拓道新材料科技有限公司 | Wear-resistant silicon dioxide/silicon carbide composite ceramic and preparation method and application thereof |
| CN115403388B (en) * | 2022-10-14 | 2023-06-13 | 湖南省拓道新材料科技有限公司 | Wear-resistant silicon dioxide/silicon carbide composite ceramic and preparation method and application thereof |
| CN116283301A (en) * | 2023-03-23 | 2023-06-23 | 长春工程学院 | Silicon carbide semiconductor material and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105948754B (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105948754A (en) | Method for preparing fine-grain silicon carbide ceramic through reaction sintering | |
| CN102814188B (en) | Activated carbon coating/foam silicon carbide structural catalyst and preparation method thereof | |
| CN105130438B (en) | A kind of method that boron carbide ceramics composite is prepared based on reaction-sintered | |
| CN101591177B (en) | Method for preparing magnesium silicate porous ceramic | |
| CN106478105A (en) | A kind of method that multistep reaction sintering process prepares the thyrite of low residual silicon | |
| CN102115330A (en) | Preparation method of solid phase sintering silicon carbide ceramics taking phenolic resin as carbon source | |
| WO2023077709A1 (en) | Solid phase sintered silicon carbide product and preparation method therefor | |
| CN110294633B (en) | Porous ceramic and method for preparing porous ceramic from gasified slag | |
| CN111004034B (en) | Silicon carbide ceramic, method for producing same, and semiconductor component | |
| CN101323536A (en) | Boron nitride porous ceramic thermal insulation material, preparation and use thereof | |
| CN109467436A (en) | A kind of boron carbide ceramics ball and preparation method thereof | |
| CN100436369C (en) | Method for preparing corundum bricks composite with Nano alpha-Al2O3 | |
| TWI439497B (en) | The method for producing spherical spherical furfuryl alcohol resin particles, the spherical polyfuryl alcohol resin particles obtained, and the spherical carbon particles and the spherical active carbon particles | |
| CN109293363A (en) | A kind of preparation method of aluminium boron carbide composite material | |
| CN113880562A (en) | Organic silicon resin combined high-temperature fired aluminum-zirconium-carbon sliding plate brick containing nickel-aluminum alloy and production method thereof | |
| CN107098702A (en) | A kind of preparation method of near-net-shape silicon carbide reaction-sintered material | |
| CN111548182A (en) | Porous ceramic and preparation method thereof | |
| CN108178640A (en) | It is a kind of using graphite microspheres as aluminium carbon castable of carbon source and preparation method thereof | |
| CN107935576B (en) | Silicon nitride combined mullite-silicon carbide ceramic composite material and preparation method thereof | |
| CN116354729B (en) | SiC ceramic part and preparation method and application thereof | |
| CN108610088A (en) | A kind of alumina-mullite porous heat-insulating ceramics and preparation method thereof | |
| CN105924179A (en) | Silicon nitride ceramic heater protection tube, preparation method and applications thereof | |
| CN101671172B (en) | Composite binder for preparing sintered porous body of silicon carbide powder and using method thereof | |
| CN111072378B (en) | Slow-blocking type aeolian sand permeable brick with surface loaded with nano titanium dioxide and preparation method thereof | |
| CN112321310B (en) | Preparation method of nanoparticle toughened high-toughness SiC product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20181105 Address after: 317015 No. 1, 12 road, Beiyang Industrial Park, Shang pan Town, Taizhou, Zhejiang. Applicant after: ZHEJIANG DONGXIN NEW MATERIAL TECHNOLOGY CO.,LTD. Address before: 317015 12 road, Beiyang Industrial Park, upper plate Town, Lin Hai, Taizhou, Zhejiang Applicant before: TAIZHOU DONGXIN SEALS Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation of fine grain silicon carbide ceramics by reactive sintering Effective date of registration: 20210907 Granted publication date: 20190222 Pledgee: Zhejiang Linhai Rural Commercial Bank Co.,Ltd. Duqiao sub branch Pledgor: ZHEJIANG DONGXIN NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2021330001415 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230301 Granted publication date: 20190222 Pledgee: Zhejiang Linhai Rural Commercial Bank Co.,Ltd. Duqiao sub branch Pledgor: ZHEJIANG DONGXIN NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2021330001415 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |