CN108752821A - Silicon carbide with microcosmic oriented structure/resin bionic composite material and preparation method thereof - Google Patents
Silicon carbide with microcosmic oriented structure/resin bionic composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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Abstract
The present invention relates to a kind of silicon carbide with microcosmic oriented structure/resin bionic composite materials and preparation method thereof.The silicon carbide and resin that the composite material is 10%~95% by volume fraction form, microcosmic upper with bionical oriented structure, show as silicon carbide and are aligned in resin matrix.The water-based slurry containing silicon carbide powder is prepared first, the green body with orienting stephanoporate structure is obtained by freezing casting and vacuum freeze drying again, compression processing is carried out to green body, organic matter and sintering is gone to obtain the orienting stephanoporate skeleton of silicon carbide, surface modification and liquid resin Monomer infiltration are carried out to skeleton, the silicon carbide with microcosmic oriented structure/resin bionic composite material is obtained after resin polymerization.The composite material of the present invention has the excellent properties such as lightweight, high-strength, wear-resisting, and its plasticity, toughness and shock resistance are obviously improved compared to silicon carbide, is expected to as structural material for fields such as armor facing, communications and transportation, electronic products.
Description
Technical field
The present invention relates to silicon carbide/resin composite materials field more particularly to a kind of carbonizations with microcosmic oriented structure
Silicon/resin bionic composite material and preparation method thereof.
Background technology
Silicon carbide is called moissanite, is commonly called as diamond dust, is a kind of extremely strong covalent key compound of covalency, lattice defect
It is few, and Si-C interatomic bonds are high by force, therefore there is high-melting-point, high rigidity and high creep resisting ability.Silicon carbide includes having high temperature
α-the SiC of stability and β-SiC with low-temperature stability, wherein α-SiC are applied than wide in the industry.α-SiC are six
Square crystal structure, density 3.217g/cm3, there is light weight, hardness using it as the thyrite prepared by raw material
High, wear-resistant, the corrosion-resistant, advantageous characteristics such as heat conductivility is good, thermal shock resistance is good, can be applicable to communications and transportation, plate armour
A variety of industries such as protection, aerospace, machinery, chemical industry.
However, strong covalent bond is but also silicon carbide ceramics shows significant brittleness, fracture toughness is very low, to defect and
Crackle is very sensitive, and although silicon carbide ceramics can bear the prodigious impact force of single, is hit i.e. broken, secondary anti-impact
Hit poor performance.For the above mechanical property disadvantage of silicon carbide, it is all by silicon carbide substrate that the prior art is most of
Second Phase Particle, whisker or fiber are added to carry out reinforcement to it, although these methods can weaken carbonization to a certain extent
The brittleness of silicon ceramics, but the raising of its fracture toughness is still limited, and the problem of secondary impact resistance difference could not also obtain
It solves, while the other problems such as silicon carbide and the second phase interface bonding strength are weak, thermal expansion mismatches can be introduced.
The Nature is exactly the source of human engineering technology and thought inspiration, many great discoveries of the mankind and hair since ancient times
It is bright to all originate from naturally, and with the development of science and technology the mankind are gradually deep into microcosmos to naturally recognizing, in nature
Natural biologic material can not only bring enlightenment on macro geometry to the innovation and creation of the mankind, but also multiple in its microcosmic upper exquisiteness
Miscellaneous institutional framework also can provide inspiration for the design of high-performance artificial material.As the natural bioceramic material in nature
Material, shell are that 95% calcium carbonate and 5% organic matter form by volume fraction.Although constituent element is simple, shell shows
Go out exquisite and complicated heterogeneous microstructure.Inorganic component and organic matter in shell is spaced with sheet form, and has
Have a microcosmic oriented structure, i.e., inorganic component in organic matter matrix according to certain orientation prioritization.It is different from shell, crab
Shell is mainly made of the chitin fiber of mineralising and protein matrices.Nevertheless, Carapax Eriocheir sinensis is shown and material as shell
Expect heterogeneous microstructure design concept, chitin fiber constituent element is also spaced in protein matrices with sheet form, and
And the orientation of fiber all concentrates in piece level.This microcosmic oriented structure contributes to material to realize optimization along specific direction
Mechanical property, while crackle is introduced in the material along the toughening mechanisms such as the deflection at interface and the bridging of crack surface, to realize material
The toughening of material.
A kind of imitative shell ceramic matric composite of Chinese patent (publication number CN107522475A) announcement and preparation method thereof,
Its composite material prepared has the lamellar structure that ceramics are alternateed with the second phase.However, in the composite material ceramic layer with
Two-phase layer has wavy curved shape, and microstructure lacks preferable directionality, simultaneously because ceramic layer structure is fine and close,
The patent cannot achieve being interconnected between the second phase.Also, since two-phase interface lacks effective design and strengthens, ceramics
Bond strength between the second phase is limited, easily causes material along ceramics or two-phase interface cracking.In addition, the patent is compound
Volume fraction in material shared by ceramic phase is no more than 75%, thus the intensity of material and hardness are by larger limitation, single layer pottery
Porcelain phase thickness is more than 5 μm, and heterogeneous microstructure is coarse, influences the plasticity and toughness of material.
Chinese patent (publication number CN103072363A) announces a kind of metal/ceramic multilayer materials of anti-high energy impact
Preparation method, it is more that refractory metal powder and high-temperature rigid ceramic powder through curtain coating, roll and hot pressed sintering are prepared into metal/ceramic
Layer composite material.Although the material has orientation lamellar structure, ceramics preparative body and metallic film prepared by casting technique
Green body thickness is larger, in millimeter magnitude, causes the institutional framework for the composite material that final hot pressed sintering obtains excessively coarse, mechanics
Therefore performance is also restricted.Meanwhile that there may be interface binding powers is weak between metal and ceramic phase, thermally expands to mismatch etc. and ask
Topic, and the preparation process is complicated for operation, long flow path, to equipment requirement height.
In addition, above-mentioned patent is only capable of realizing simple lamellar structure in the material, friendship common in shell cannot achieve
Pitch lamination and fiber spiral structure similar with Carapax Eriocheir sinensis.
Invention content
The purpose of the present invention is to provide a kind of silicon carbide with microcosmic oriented structure/resin bionic composite material and its
Preparation method retains the high-strength, high of silicon carbide ceramics by forming Composite design and microstructure Bionic Design in part
Firmly, under the premise of the advantages that wear-resisting, the fracture toughness and shock resistance of material are significantly improved, to obtain lightweight and resultant force
Learn the composite material haveing excellent performance.
To achieve the above object, the technical solution that the present invention is taken is as follows：
A kind of silicon carbide with microcosmic oriented structure/resin bionic composite material, the composite material is by silicon carbide
It is formed with resin, with volume percent, carborundum content is 10%~95%, remaining is resin；The composite material is micro-
There is bionical oriented structure in sight, show as silicon carbide and aligned in resin matrix；Wherein, bionical oriented structure includes carbon
SiClx and the spaced fiber spiral structure of resin intersect lamination or lamellar structure.
The resin is epoxy resin, polymethyl methacrylate, makrolon, acrylic acid modified resin, phenolic aldehyde tree
One or more kinds of compound resins of fat.
Silicon carbide and resin are spaced with sheet form in the composite material, and wherein silicon carbide lamella is by silicon carbide
Particle, whisker or both mixing are constituted, and lamellar spacing is 0.1~50 μm, and piece interlamellar spacing is 0.1~50 μm.
The compressive strength of the composite material is more than 80MPa, and compressive strain is more than 4%, and fracture toughness is more thanImpact flexibility is more than 5kJ/m2。
The preparation method of silicon carbide with the microcosmic oriented structure/resin bionic composite material, including following step
Suddenly：
(a) silicon carbide powder and additive are dispersed in water, the water base slurry containing silicon carbide powder is prepared
Material；
(b) so that silicon carbide powder therein is aligned using freezing casting process slurry, to the slurry of solidification into
Row demoulding and vacuum freeze drying processing remove its moisture contained, obtain the silicon carbide green body with orienting stephanoporate structure；
(c) to silicon carbide green body carry out compression processing, remove silicon carbide green body in organic matter, sintered silicon carbon green body,
Obtain the silicon carbide skeleton with orienting stephanoporate structure；
(d) surface modification is carried out to silicon carbide skeleton, infiltrates skeleton using resin monomer, polymerize through follow-up resin monomer
To the silicon carbide with microcosmic oriented structure/resin bionic composite material.
In step (a), the silicon carbide powder is the combination of silicon carbide whisker, particle or both；The additive
Including organic binder, dispersant and sintering aid, which is hydroxypropyl methyl cellulose, polyvinyl alcohol, poly- second
One or more in glycol, sucrose or guar gum, the dispersant be polyacrylic acid, Darvan CN, polyethyleneimine,
One or more in neopelex or lauryl sodium sulfate, the sintering aid be aluminium oxide, yttrium oxide,
One or more in silica, magnesia or zirconium oxide.
The technique that the silicon carbide powder and additive disperses in water is the combination of stirring, ball milling or both, wherein
Mixing speed is 10~500rpm, and mixing time is more than 0.5h, and ball milling speed is 30~500rpm, and Ball-milling Time is 4~100h,
The mass ratio of abrading-ball and slurry is more than 0.1.
In step (b), the freezing casting technical process is：Slurry is poured into mold, by mold one end into
Row cooling so that for the water in slurry along the bottom-up generation directional solidification of mold, the ice crystal along the growth of solidification direction will be in slurry
Silicon carbide powder and additive gradually exclusion is between ice sheet, to realize aligning for powder.
In step (b), the technique of the vacuum freeze drying is：After the slurry of solidification is demoulded, it is placed in cold-trap
For temperature less than under -30 DEG C, vacuum environment of the vacuum degree less than 10Pa, standing time is 12~120h.
In step (c), the technique that compression processing is carried out to silicon carbide green body include parallel hole to compression green body or
Vertical hole to compression green body；Wherein, parallel hole introduces bionical intersection lamination to compression green body in silicon carbide green body, handles
Method is：Using the solution infiltrating silicon carbide green body containing organic matter, one layer of organic matter is coated in the sheet surfaces of silicon carbide green body,
The solution containing organic matter is the acetone soln for the polymethyl methacrylate that mass fraction is 0.5~6%, then edge is parallel to piece
Green body is compressed in the direction of layer, and compression stress is 1MPa~2GPa；Vertical hole can control what is be finally prepared to answer to compression green body
The volume content of silicon carbide in condensation material, compression deformation are 0%~90%, and compression deformation is bigger, is finally prepared
The volume content of silicon carbide is higher in composite material.
In step (c), the technique of the organic matter in the removal silicon carbide green body is：In air to silicon carbide green body
Heating and thermal insulation processing is carried out, holding temperature is 300~600 DEG C, and soaking time is 1~5h.
In step (c), contain sometimes when the sintering aid in additive contains silica or zirconium oxide or both, it is described
The atmosphere of silicon carbide green body sintering is air, vacuum or protective atmosphere, and sintering temperature is 900~2100 DEG C；When in additive
Sintering aid not silicon oxide-containing and when zirconium oxide, the sintering atmosphere of the silicon carbide green body is vacuum or protective atmosphere, sintering
Temperature is 1500~2200 DEG C；Wherein, the protective atmosphere is nitrogen, argon gas, helium or combination thereof gas.
In step (d), steps are as follows for the technological operation to the progress surface modification of silicon carbide skeleton：(1) alcohol is prepared
With the mixed liquor of water, the wherein mass percent of alcohol is 70%~95%；(2) by the way that acid-conditioning solution pH is added into mixed liquor
To 1~7；(3) silane coupling agent that mass percent is 5%~35% is added into solution and stirs evenly；(4) by silicon carbide
Ceramic skeleton immerses in solution and stands 1h or more, dry after taking-up.
The present invention design philosophy be：
In the composite material of the present invention, silicon carbide is connected with each other in three dimensions, primarily serves the effect of reinforced phase, is assigned
The excellent intensity of composite material, hardness and wearability, and the preferable resin of plasticity is mutually as the matrix in composite material, Neng Gouwei
Composite material provides certain plasticity and toughness, and assigns its unique dynamic energy consumption characteristic, and the presence of microcosmic oriented structure
So that the mechanical property of composite material is optimized in particular directions.In particular, by Bionic Design, in composite material
Crackle tendency between relatively weak organic matter phase or two-phase interface extend, thus extensions path on three dimensions not
It is disconnected to deflect, while the silicon carbide on crack surface can be extracted from resin matrix, and prevent crackle by modes such as bridgings
The opening in face.The above toughening mechanisms are introduced into the extension that can significantly hinder crackle in composite material, to enhance composite material
Fracture toughness and shock resistance.
Compared with current material, technology, the present invention has the following advantages that and advantageous effect：
(A) since constituent element is silicon carbide and resin, composite material of the invention has the characteristics that lightweight, simultaneously because carbonization
Silicon reinforced phase is interconnected in three dimensions, strengthens effect and is given full play in the composite, especially along microcosmic knot
It is maximized on the direction of structure, therefore the composite material of the present invention has excellent intensity, hardness and wearability；
(B) compared to silicon carbide ceramics, plasticity, fracture toughness and shock resistance are shown composite material of the invention
It writes and is promoted, and there is dynamic energy consumption characteristic, therefore excellent combination property, there is considerable application prospect as structural material；
(C) preparation method of composite material of the invention can realize the bionical microcosmic fixed of diversified forms in the composite
Contain carbonization to structure, including fiber spiral structure, intersection lamination and lamellar structure, the raw material that ought especially use
When silicon wafer palpus, the resin in obtained composite material is mutually interconnected in three dimensions, plays better toughening effect；
(D) preparation method of composite material of the invention can by adjusting preparation process to the microstructure of composite material and
Performance control effectively, and the material prepared does not have size limitation, it is easy to accomplish industrialization.
Description of the drawings
Fig. 1 be embodiment 1 be sintered obtain woven by silicon carbide whisker made of with orienting stephanoporate structure silicon carbide
The scanning electron micrographs of skeleton；In figure, the porosity of (a), (b) respectively may be about 75% and 30%.
Fig. 2 is the silicon carbide whisker by the fiber spiral structure with microcosmic orientation and poly- first that embodiment 1 is prepared
The scanning electron micrographs of the composite material of base methyl acrylate composition；In figure, the silicon carbide body fraction of (a), (b) are distinguished
For 25% and 70%, brilliant white is silicon carbide, and furvous is resin, and the hole in figure is since silicon carbide whisker is from resin matrix
Caused by middle extraction, and the defect of non-composite material itself.
Fig. 3 is silicon carbide whisker by the fiber spiral structure with microcosmic orientation and poly- methyl-prop prepared by embodiment 1
The composite material of e pioic acid methyl ester composition is along the room temperature compressive stress strain curve for being parallel and perpendicular to lamella direction；In figure, (a),
(b) silicon carbide body fraction is respectively 25% and 70%.
Fig. 4 is the scanning with the silicon carbide/epoxy resin composite material for intersecting lamination that embodiment 2 is prepared
Electron microscopic picture, brilliant white is silicon carbide in figure, and furvous is resin, and what white dashed line indicated is a typical silicon carbide
The microcosmic intersection lamination of lamella is orientated.
Fig. 5 is silicon carbide/epoxy resin composite material with intersection lamination of the preparation of embodiment 2 along parallel and vertical
Directly in the room temperature compressive stress strain curve in lamella direction.
Specific implementation mode
In specific implementation process, composite material of the present invention by volume fraction be 10%~95% (preferably 30%~
90%) the resin composition of silicon carbide and surplus, it is microcosmic upper with bionical oriented structure, silicon carbide is shown as in resin matrix
It aligns.The preparation method of the composite material is：The water-based slurry containing silicon carbide powder is prepared first, then is cast by freezing
It makes and obtains the green body with orienting stephanoporate structure with vacuum freeze drying, compression processing is carried out to green body, removes organic matter and sintering
The orienting stephanoporate skeleton of silicon carbide is obtained, surface modification and liquid resin Monomer infiltration are carried out to skeleton, obtained after resin polymerization
Silicon carbide with microcosmic oriented structure/resin bionic composite material.
Present invention is further elaborated in following combination specific embodiment, and following embodiment is only limited the use of in illustrating the present invention,
Rather than it limits the scope of the invention.
Embodiment 1：
In the present embodiment, silicon carbide whisker/composite material of polymethyl methacrylate with microcosmic oriented structure is prepared.
Raw material used mainly have silicon carbide whisker (2.5 μm of average diameter, 50~200 μm of length), silica powder (average grain diameter
20nm), deionized water, polyvinyl alcohol, hydroxypropyl methyl cellulose powder (180 μm of average grain diameter), polyacrylic acid and methyl
Methyl acrylate, specific preparation process are as follows：
(A) slurry is prepared
720g deionized waters are added in the plastic jar of 1000mL, 100g silicon carbide whiskers are sequentially added into bottle
Palpus, 4g silica powders, 35g polyvinyl alcohol and 2g polyacrylic acid, with the speed stirring of 60rpm until solid powder is dispersed in
In water.Wide-mouth bottle is placed in 70 DEG C of constant water bath box, keeps the temperature 30min, 14g hydroxypropyl methyl fibers are slowly added into bottle
Plain powder, stirring is until powder is dispersed in slurry.Wide-mouth bottle is taken out from water bath, after slurry cooling, to slurry
Middle each 12 of the zirconium oxide balls that a diameter of 3mm, 6mm and 10mm is added, and instill 6 drop (about 0.4mL) antifoaming agent, the antifoaming agent
It is positioned over by lid for jar upper bottle cover and after sealing for the XPM-120 type antifoaming agent of antifoaming agent Co., Ltd of Nanjing Huaxing production
Ball milling, ball milling speed 100rpm, Ball-milling Time 50h are carried out on tumbling ball mill.
(B) porous body is prepared
Slurry after ball milling is poured into the cuboid polymethyl methacrylate that interior chamber size is 20mm × 20mm × 60mm
In mold, mold lower end is sealed with the dimethyl silicone polymer pedestal that inclination angle is 25 °, and it is 60mm, thickness that mold, which is positioned over the length of side,
On the rectangular copper coin of 5mm, copper coin to be connected with the copper rod that one end is immersed in liquid nitrogen (or dry ice), passes through the cooling of copper coin
Make water in slurry along the bottom-up generation directional solidification of mold, the ice crystal along the growth of solidification direction is by the silicon carbide whisker in slurry
Must and additive gradually exclusion is between ice sheet, to realize aligning for powder.After slurry solidification completely, by solidification
Slurry is removed from the molds, and is put into vacuum freeze drier and is dried, and setting condenser temperature is -60 DEG C, and vacuum degree is
1Pa takes out after handling 84h, obtains having orienting stephanoporate structure by what the lamella that silicon carbide whisker and additive form was constituted
Green body, the thickness in the average hole of green body is about 110 μm, and porosity is about 89%.
(C) green body compression processing
Green body after freeze-drying is positioned in steel die, using thermal pressure machine in 100 DEG C of lower edges perpendicular to carbonization
Silicon wafer must the direction of lamella compress green body, compression deformation is respectively 20% and 80%, pressurize 10min, is unloaded after cooling and will
Green body is removed from the molds.
(D) organic matter and sintering are removed
Compressed green body is positioned in heat-treatment furnace, under air conditions, with the rate of 3 DEG C/min from room temperature
To 500 DEG C, 2h is kept the temperature, then room temperature is cooled to the rate of 10 DEG C/min, remove the organic matter in green body.After organic matter being removed
Green body be positioned in batch-type furnace, under air conditions, with the rate of 5 DEG C/min from room temperature to 1000 DEG C, then with 2 DEG C/
The rate of min is warming up to 1100 DEG C, keeps the temperature 1.5h, is then cooled to 1000 DEG C with the rate of 2 DEG C/min, then with 5 DEG C/min's
Rate is cooled to room temperature, is conducive to shorten sintering time using above-mentioned stage heating and cooling, improves sintering efficiency, and reduce
Internal stress obtains having the silicon carbide whisker skeleton of the fiber spiral structure of microcosmic orientation, sees Fig. 1 through sintering.It can be seen by Fig. 1
Go out, the silicon carbide whisker in the skeleton is woven into preferentially according to certain orientations in parallel lamella in piece level
It is netted, and whisker is interconnected in three dimensions, and compression deformation is respectively 20% and 80% base in corresponding step (C)
The porosity of body, the skeleton respectively may be about 75% and 30%.
(E) skeleton surface is modified
It is 9 to prepare mass ratio:1 methanol and the mixed solution 200g of deionized water, under agitation into solution by
Drop instills glacial acetic acid and adjusts the pH value of solution to 4.γ-methacryloxypropyl trimethoxy of 50g is added into solution
Silane, it is uniform to solution with magnetic stirrer.The silicon carbide whisker skeleton obtained in (D) is slowly immersed in the solution
In, standing takes out skeleton afterwards for 24 hours, and it is placed for 24 hours under the conditions of atmosphere at room temperature, makes it dry.Silicon is adjusted using glacial acetic acid
The pH value of alkane coupling agent alcohol water mixed solution, utilizes the acidity of γ-methacryloxypropyl trimethoxy silane of hydrolysis
Solution impregnates silicon carbide whisker skeleton, and carrying out the effect of surface modification and effect to skeleton is：In acid condition, the silicon of hydrolysis
Alkane coupling agent reacts with silicon carbide whisker skeleton, between the polymethyl methacrylate in silicon carbide whisker and subsequently infiltrated
Transitional bonding layer is formed, to enhance the interface bond strength between silicon carbide whisker and polymethyl methacrylate.
(F) polymethyl methacrylate Monomer infiltration with polymerize
At room temperature, 1g azodiisobutyronitrile initiators are added in 200g methyl methacrylate monomers, are stirred with magnetic force
Device is mixed to stir to being completely dissolved.Silicon carbide whisker skeleton by surface modification and drying under the vacuum condition of 1Pa is slowly immersed in
It in the liquid monomer, after monomer is sealed, is positioned in 30 DEG C of insulating box, standing 60h makes polymethyl methacrylate monomer
Solid is aggregated into, then keeping the temperature 2h processing at 90 DEG C keeps its polymerization complete, then furnace cooling.
The silicon carbide whisker of the fiber spiral structure with microcosmic orientation can be prepared through above-mentioned technique enhances poly- methyl
Acid propyl methyl esters based composites, microstructure are shown in Fig. 2.Wherein, the volume fraction of silicon carbide is respectively in (a) and (b)
25% and 70%.After tested, when the volume fraction of SiC reinforcement phase is about 25% in the composite material, it is parallel to lamella direction
Compressive strength be 245MPa, the compressive strength perpendicular to lamella direction is 220MPa, SiC reinforcement phase in the composite material
Volume fraction be 70% when, be parallel to lamella direction compressive strength be 320MPa, the compressive strength perpendicular to lamella direction
For 295MPa, which sees Fig. 3 along the room temperature compressive stress strain curve for being parallel and perpendicular to lamella direction.
Embodiment 2：
In the present embodiment, silicon carbide/epoxy resin composite material of the intersection lamination with microcosmic orientation is prepared.Institute
Mainly there are nano silicon carbide powder (average grain diameter 100nm), nano yttrium oxide powder (average grain diameter 30nm), nanometer with raw material
Alumina powder (average grain diameter 20nm), deionized water, polyvinyl alcohol, hydroxypropyl methyl cellulose powder (180 μ of average grain diameter
M), polyacrylic acid, epoxy resin and curing agent, specific preparation process are as follows：
(A) slurry is prepared
185g deionized waters are added in the plastic jar of 500mL, 45g nano carborundum powders are sequentially added into bottle
Body, 2.853g nano yttrium oxide powders, 2.147g are nano alumina powder jointed, 8g polyvinyl alcohol and 1g polyacrylic acid, with 100rpm
Speed stirring until solid powder be dispersed in water.Wide-mouth bottle is placed in 70 DEG C of constant water bath box, keeps the temperature 30min,
2.96g hydroxypropyl methyl cellulose powder is slowly added into bottle, stirring is until powder is dispersed in slurry.From water bath
Each 6 of the zirconium oxide balls of a diameter of 3mm, 6mm and 10mm are added into slurry after slurry cooling for middle taking-up wide-mouth bottle, and
3 drop (about 0.2mL) antifoaming agent are instilled, which is the XPM-120 type antifoaming agent of antifoaming agent Co., Ltd of Nanjing Huaxing production,
After lid for jar upper bottle cover is sealed, it is positioned on tumbling ball mill, with the ball milling speed of 500rpm, ball milling 12h.
(B) porous body is prepared
Step operation is identical as step (B) in embodiment 1.
(C) parallel compression green body
5g polymethyl methacrylate powders are scattered in 145g acetone, being stirred continuously makes powder dissolve, and obtains quality
The acetone soln for the polymethyl methacrylate that score is 3.33% will obtain in step (B) with orienting stephanoporate structure
Green body is slowly immersed in the acetone soln, and green body is taken out after standing 30min, places it in dry 3h in draught cupboard.By green body
It is placed in steel die, be parallel to the direction of silicon carbide synusia in 110 DEG C of lower edges using thermal pressure machine is compressed with the pressure of 10MPa
Green body, pressurize 30s are unloaded after cooling and are removed from the molds green body, obtain with the green body for intersecting lamination.
(D) organic matter, sintering and surface is gone to be modified
Organic matter is carried out according to the identical operation of (D) step in embodiment 1 to parallel compressed green body to handle.Then
By remove organic matter after green body be positioned in sintering furnace, under the conditions of argon gas, with the rate of 5 DEG C/min from room temperature to
1500 DEG C, then 1600 DEG C are warming up to the rate of 2 DEG C/min, 2h is kept the temperature, is then cooled to 1500 DEG C with the rate of 2 DEG C/min,
Room temperature is cooled to the rate of 5 DEG C/min again.Be conducive to shorten sintering time using above-mentioned stage heating and cooling, improve and burn
Junction efficiency, and internal stress is reduced, obtain the intersection with microcosmic orientation being made of the lamella that silicon-carbide particle is constituted through sintering
The porosity of the silicon carbide skeleton of lamination, the skeleton is about 13%.According to the identical operation pair of (E) step in embodiment 1
It is sintered obtained skeleton and carries out surface modification treatment.
(E) epoxy resin infiltrates and polymerize
At room temperature, the cold solidification inlayed in resin suit of the MC003 types that Shanghai Chuan He industry developments Co., Ltd produces is taken
Agent 50g is added in 100g epoxy resin, so that the two is uniformly mixed with the speed stirring 15min of 100rpm.In the vacuum item of 1Pa
The modified silicon carbide skeleton in surface is slowly immersed in the solution under part, standing 3h makes epoxy resin fully cure.
Silicon carbide/epoxy resin composite wood of the intersection lamination with microcosmic orientation can be prepared through above-mentioned technique
Material, microstructure are shown in Fig. 4.As seen from Figure 4, the volume fraction of silicon carbide is about 87% in the composite material, silicon carbide
Lamellar spacing is about 10 μm, and lamella is spaced about 2 μm.After tested, in the composite material, it is parallel to the compressive strength in lamella direction
For 860MPa, the compressive strength perpendicular to lamella direction is 485MPa, and composite material edge is parallel and perpendicular to lamella direction
Room temperature compressive stress strain curve is shown in Fig. 5.
Embodiment 3：
In the present embodiment, silicon carbide/epoxy resin composite material of the lamellar structure with microcosmic orientation is prepared.Used
Raw material are same as Example 2, and specific preparation process is as follows：
(A) it prepares slurry, prepare porous body
According to obtain being made of silicon carbide powder and additive with 2 step of embodiment (A), (B) identical operation preparation
The green body with orienting stephanoporate structure that lamella is constituted.
(B) green body compression processing
Green body after freeze-drying is positioned in steel die, using thermal pressure machine in 100 DEG C of lower edges perpendicular to carbonization
Green body, compression deformation 50% are compressed in the direction of silicon layer piece, and pressurize 10min is unloaded after cooling and taken green body from mold
Go out.
(C) organic matter and sintering are removed
Organic matter and sintering are carried out to green body according to the identical operation with step (D) in embodiment 1.It is obtained after sintering
In skeleton, silicon carbide is interconnected according to certain orientations, and between lamella with sheet form, the porosity of the skeleton
About 45%.
(D) skeleton surface is modified, resin impregnated and polymerize
Surface modification treatment and epoxy resin are carried out to skeleton according to 2 step of embodiment (D), (E) identical operation
It infiltrates and polymerize.
Silicon carbide/epoxy resin composite material of the lamellar structure with microcosmic orientation can be prepared through above-mentioned technique,
The volume fraction of silicon carbide is 55% in composite material.After tested, the composite material is along the compressive strength for being parallel to lamella direction
For 280MPa, the compressive strength perpendicular to lamella direction is 265MPa.
Embodiment the result shows that, the ingehious design of natural biologic material, can from bionical angle be overcome silicon carbide ceramics
Brittleness beneficial enlightenment is provided.The present invention introduces toughened resin phase, while root using composition Composite design in silicon carbide
According to the optimization of material design concept of shell and Carapax Eriocheir sinensis, keep ceramics in material and resin specific direction of handing down spaced,
Show bionical microcosmic oriented structure.The composite material of the present invention has the excellent properties such as lightweight, high-strength, wear-resisting, and it is moulded
Property, toughness and shock resistance be obviously improved compared to silicon carbide ceramics, be expected to as structural material for armor facing,
The fields such as communications and transportation, electronic product.
Claims (13)
1. a kind of silicon carbide with microcosmic oriented structure/resin bionic composite material, which is characterized in that the composite material
It is made of silicon carbide and resin, with volume percent, carborundum content is 10%~95%, remaining is resin；Described answers
Condensation material is microcosmic upper with bionical oriented structure, shows as silicon carbide and is aligned in resin matrix；Wherein, bionical orientation knot
Structure includes silicon carbide and the spaced fiber spiral structure of resin, intersects lamination or lamellar structure.
2. the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 1, feature exist
In, the resin be epoxy resin, polymethyl methacrylate, makrolon, acrylic acid modified resin, phenolic resin one
Kind or more than one compound resin.
3. the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 1, feature exist
In, silicon carbide and resin are spaced with sheet form in the composite material, wherein silicon carbide lamella by silicon-carbide particle,
Whisker or both mixing is constituted, and lamellar spacing is 0.1~50 μm, and piece interlamellar spacing is 0.1~50 μm.
4. the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 1, feature exist
In the compressive strength of the composite material is more than 80MPa, and compressive strain is more than 4%, and fracture toughness is more than
Impact flexibility is more than 5kJ/m2。
5. the system of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to one of Claims 1-4
Preparation Method, which is characterized in that include the following steps：
(a) silicon carbide powder and additive are dispersed in water, the water-based slurry containing silicon carbide powder is prepared；
(b) so that silicon carbide powder therein is aligned using freezing casting process slurry, the slurry of solidification is taken off
Mould and vacuum freeze drying processing remove its moisture contained, obtain the silicon carbide green body with orienting stephanoporate structure；
(c) compression processing is carried out to silicon carbide green body, removes the organic matter in silicon carbide green body, sintered silicon carbon green body obtains
Silicon carbide skeleton with orienting stephanoporate structure；
(d) surface modification is carried out to silicon carbide skeleton, infiltrates skeleton using resin monomer, polymerize through follow-up resin monomer and had
There is silicon carbide/resin bionic composite material of microcosmic oriented structure.
6. the preparation method of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5,
It is characterized in that, in step (a), the silicon carbide powder is the combination of silicon carbide whisker, particle or both；The addition
Agent includes organic binder, dispersant and sintering aid, which is hydroxypropyl methyl cellulose, polyvinyl alcohol, gathers
One or more in ethylene glycol, sucrose or guar gum, the dispersant are polyacrylic acid, Darvan CN, polyethyleneimine
One or more in amine, neopelex or lauryl sodium sulfate, the sintering aid are aluminium oxide, oxidation
One or more in yttrium, silica, magnesia or zirconium oxide.
7. the preparation side of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5 or 6
Method, which is characterized in that the technique that the silicon carbide powder and additive disperses in water is the group of stirring, ball milling or both
It closes, wherein mixing speed is 10~500rpm, and mixing time is more than 0.5h, and ball milling speed is 30~500rpm, Ball-milling Time 4
The mass ratio of~100h, abrading-ball and slurry is more than 0.1.
8. the preparation method of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5,
It is characterized in that, in step (b), the freezing casting technical process is：Slurry is poured into mold, by mold one end
It is cooled down so that water in slurry is along the bottom-up generation directional solidification of mold, and the ice crystal along the growth of solidification direction is by slurry
In silicon carbide powder and additive gradually exclusion is between ice sheet, to realize aligning for powder.
9. the preparation method of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5,
It is characterized in that, in step (b), the technique of the vacuum freeze drying is：After the slurry of solidification is demoulded, it is placed in cold
For trap temperature less than under -30 DEG C, vacuum environment of the vacuum degree less than 10Pa, standing time is 12~120h.
10. the preparation side of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5
Method, which is characterized in that in step (c), the technique that compression processing is carried out to silicon carbide green body includes parallel hole to compression
Green body or vertical hole are to compression green body；Wherein, parallel hole introduces bionical intersection lamination knot to compression green body in silicon carbide green body
Structure, processing method are：Using the solution infiltrating silicon carbide green body containing organic matter, one layer is coated in the sheet surfaces of silicon carbide green body
Organic matter, the solution for containing organic matter are the acetone soln for the polymethyl methacrylate that mass fraction is 0.5~6%, then edge
It is parallel to the direction compression green body of lamella, compression stress is 1MPa~2GPa；Vertical hole is finally prepared to compression green body is controllable
The volume content of silicon carbide in obtained composite material, compression deformation are 0%~90%, and compression deformation is bigger, final to make
The volume content of silicon carbide is higher in standby obtained composite material.
11. the preparation side of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5
Method, which is characterized in that in step (c), the technique of the organic matter in the removal silicon carbide green body is：Exist to silicon carbide green body
Heating and thermal insulation processing is carried out in air, holding temperature is 300~600 DEG C, and soaking time is 1~5h.
12. the preparation side of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5
Method, which is characterized in that in step (c), contain sometimes when the sintering aid in additive contains silica or zirconium oxide or both,
The atmosphere of the silicon carbide green body sintering is air, vacuum or protective atmosphere, and sintering temperature is 900~2100 DEG C；Work as addition
Sintering aid in agent not silicon oxide-containing and when zirconium oxide, the sintering atmosphere of the silicon carbide green body is vacuum or protection gas
Atmosphere, sintering temperature are 1500~2200 DEG C；Wherein, the protective atmosphere is nitrogen, argon gas, helium or combination thereof gas
Body.
13. the preparation side of the silicon carbide with microcosmic oriented structure/resin bionic composite material according to claim 5
Method, which is characterized in that in step (d), steps are as follows for the technological operation to the progress surface modification of silicon carbide skeleton：(1)
The mixed liquor of alcohol and water is prepared, the wherein mass percent of alcohol is 70%~95%；(2) it is adjusted by the way that acid is added into mixed liquor
PH value of solution is to 1~7；(3) silane coupling agent that mass percent is 5%~35% is added into solution and stirs evenly；(4) will
Silicon carbide ceramics skeleton immerses in solution and stands 1h or more, dry after taking-up.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021785A (en) * | 2017-04-11 | 2017-08-08 | 中国石油大学(北京) | A kind of ultra-toughness layered polymer ceramic composite and preparation method thereof |
-
2018
- 2018-06-14 CN CN201810610396.XA patent/CN108752821B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021785A (en) * | 2017-04-11 | 2017-08-08 | 中国石油大学(北京) | A kind of ultra-toughness layered polymer ceramic composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| VALENTINA NAGLIERI, BERND GLUDOVATZ, ANTONI P. TOMSIA, ROBERT O.: "Developing strength and toughness in bio-inspired silicon carbide hybrid materials containing a compliant phase", 《ACTA MATERIALIA》 * |
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