CN107698271A - High-temperature-resistant high toughness nitrogenizes silicon substrate wave-penetrating composite material and preparation method - Google Patents

High-temperature-resistant high toughness nitrogenizes silicon substrate wave-penetrating composite material and preparation method Download PDF

Info

Publication number
CN107698271A
CN107698271A CN201710809871.1A CN201710809871A CN107698271A CN 107698271 A CN107698271 A CN 107698271A CN 201710809871 A CN201710809871 A CN 201710809871A CN 107698271 A CN107698271 A CN 107698271A
Authority
CN
China
Prior art keywords
whisker
matrix
temperature
preparation
composite material
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
Application number
CN201710809871.1A
Other languages
Chinese (zh)
Other versions
CN107698271B (en
Inventor
刘永胜
叶昉
陈乃齐
成来飞
李明星
张立同
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwestern Polytechnical University
Original Assignee
Northwestern Polytechnical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northwestern Polytechnical University filed Critical Northwestern Polytechnical University
Priority to CN201710809871.1A priority Critical patent/CN107698271B/en
Publication of CN107698271A publication Critical patent/CN107698271A/en
Application granted granted Critical
Publication of CN107698271B publication Critical patent/CN107698271B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C04B35/806—
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—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
    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • 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
    • C04B35/624—Sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/42—Housings not intimately mechanically associated with radiating elements, e.g. radome
    • H01Q1/422—Housings not intimately mechanically associated with radiating elements, e.g. radome comprising two or more layers of dielectric material

Abstract

The present invention relates to a kind of high-temperature-resistant high toughness nitridation silicon substrate wave-penetrating composite material and preparation method, first, porous Si is prepared using gel casting forming3N4Whisker biscuit, porous Si is received after drying dumping3N4Precast body, boron nitride (BN) interface is prepared in the whisker preform using chemical vapor infiltration technique (CVI), and multilayer alternating BN/Si is prepared using CVI techniques3N4Matrix.For high temperature wave transparent antenna cover structure and the design requirement of performance, realize that multilayer replaces BN/Si by CVI regulation and control3N4The regulation and control of each layer micro-structural of matrix, the number of plies and thickness, to realize the regulation and control of composite structure and performance and optimization, obtain the excellent Si of a kind of high temperature resistant, high-strength and high ductility, wideband wave transparent, thermophysical property3N4Base wave-penetrating composite material.

Description

High-temperature-resistant high toughness nitrogenizes silicon substrate wave-penetrating composite material and preparation method
Technical field
The invention belongs to nitrogenize silicon substrate wave-penetrating composite material technology, it is related to a kind of high-temperature-resistant high toughness nitridation silicon substrate wave transparent Composite and preparation method.
Background technology
Antenna house is protection guided missile and other spacecrafts communicate in harsh environments, remote measurement, guidance, the system such as ignition Exempt from important feature part affected by environment, be used widely in the radio systems such as guided missile, radar and satellite.Modern army Thing is urgent to High Mach number (Ma >=8) guided missile and other aircraft demands, and harsher use is then proposed to antenna house will Ask.The performance of antenna house directly depends on selected materials, to realize the flight of the high Mach of aircraft and precise guidance, it is desirable to antenna Cover material allows for integrating heatproof, heat shock resistance, carrying, wideband wave transparent, anti-weathering etc. multi-functional.
Si3N4Material has the excellent properties such as relatively low density, high intensity, heat shock resistance, anti-weathering, and low Jie The excellent dielectric properties such as electrical loss, relatively low dielectric constant, it is preferable high temperature wave-transparent material.Solid sintering technology is (as reacted Sintering, hot pressed sintering, HIP sintering etc.) it is current preparation Si3N4The most frequently used method of base antenna house.Under normal circumstances, make pottery The sintering temperature of ceramic material is high, and sintering process control difficulty is big, and machining is more difficult, and production cost is higher.Using sintering Fine and close Si prepared by method3N4Though material is with higher intensity, toughness deficiency, and dielectric constant is higher, can not meet height The requirement of Mach number device.Such as Qi Gongjin is adopted in document " Progress of Preparation Process For Ceramic Matrix Composites Radomes " Fine and close Si is made with hot pressed sintering3N4Material, its density 3.2g/cm3, bending strength 391MPa, dielectric constant 7.9, mechanical property It is excellent, but dielectric constant is higher.By changing moulding process (such as compression molding or 3D printing are molded) or introducing pore creating material, use Porous Si prepared by sintering process3N4Material dielectric constant significantly reduces, but raising of the allied processes to material mechanical performance is not Profit.For example, open strong wait in " a kind of low-k, high intensity, porous silicon nitride nano wave-pervious ceramic preparation method " (CN200910150098.8) with Si in3N4Powder and metal oxide are raw material, using cold compression molding method, in nitrogen atmosphere Porous Si is made in lower sintering3N4Material, its porosity ＞ 40%, bending strength ＞ 71MPa, dielectric loss ＜ 6.5 × 10-3, it is situated between Electric constant ＜ 3.5, dielectric properties are excellent, but intensity has much room for improvement.In view of the above-mentioned problems, there is an urgent need to develop a kind of Si3N4Material The novel processing step of material, it must possess the features such as low preparation temperature, process control and processability are good, and can also realize Si3N4The structure of material optimizes with performance, makes Si3N4Material has high-strength tenacity and wideband wave concurrently, effectively solves current high temperature Wave transparent Si3N4The research puzzle of material.
Chemical vapor infiltration technology (CVI) is presently the most one of advanced ceramic matric composite technology of preparing.Using Ceramic matric composite purity prepared by the technique is high, compactness is good, good mechanical performance, and the technique preparation temperature it is low, Process control space is big, processing approach enriches, and suitable for preparing complex large-scale component, therefore can be used as high-performance Si3N4Material it is excellent Different candidate's technique.The controllable precast body of pore structure is that CVI methods prepare high-performance Si3N4The premise of material, current BN or Si3N4Big fiber development difficulty, ceramic fibre braiding difficulty be present, weave hole influence matrix deposition effect, be pre- in fiber preform The problems such as body structural anisotropy (such as two dimension, two dimension half or three-dimensional braided structure) processed；And BN or Si3N4Particle precast body is present The problems such as sintered particles connectivity is poor, mechanical property is insufficient, pore structure hardly possible regulates and controls, structural homogeneity is hard to keep.Therefore, need pair Precast body material and structure are reselected and optimization design, to meet that follow-up CVI methods prepare high-performance Si3N4Material is wanted Ask.
Gel-casting process be it is a kind of be suitable to prepare the moulding process of loose structure precast body, its can realize near net-shape into Type, made base substrate have some strength, and beneficial to roughing, and process control is good, the cycle is short, cost is low.Si3N4Whisker is A kind of reinforcement material with excellent mechanical performance, environmental performance and excellent dielectric performance, by its with ceramic matrix is compound can Significantly improve the obdurability of material.In view of above-mentioned technique and material advantages, the present invention proposes to prepare using gel injection-moulding method first Si3N4Whisker preform.In precast body, Si3N4Whisker is intersected, connected, and is uniformly distributed in three-dimensional network polymer, Skeleton function can be given full play to, the three-dimensional hole for making to be formed between whisker again is evenly distributed, is connective good, beneficial to following body Preparation and densification.As can be seen here, the Si that prepared by gel injection-moulding method3N4Whisker preform can realize isotropism, loose structure With Strengthening and Toughening target, meet high-performance Si3N4The precursor structure requirement of material.
Due to Si3N4Whisker is crystalline structure, using CVI methods in Si3N4The Si prepared in whisker preform3N4Matrix is usual For amorphous structure, to alleviate thermal expansion and the modulus mismatch between whisker and matrix, need to be introduced between whisker and matrix compared with The BN interfaces of low modulus and energy to failure, low-k and dielectric loss.Meanwhile for meet different antennae cover obdurability and electrically It can require, need to be in Si3N4Multilayer alternating BN/Si is prepared in whisker preform3N4Matrix, by CVI process controls realize BN and Si3N4Micro-structural, relative amount, the number of plies and the thickness regulation and control of matrix, improve the pore structure and performance of composite, meet day The excellent mechanics of irdome material, calorifics and dielectric properties integration requirement.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that a kind of high-temperature-resistant high toughness nitridation silicon substrate wave transparent is answered Condensation material and preparation method, solves existing Si3N4Base electromagnetic wave transparent material obdurability and wave deficiency, it can not meet that High Mach number flies A kind of the problems such as row device requirement, there is provided high-performance Si3N4Whisker reinforcement BN/Si3N4The gel injection-moulding of base wave-penetrating composite material Shaping combines CVI technology preparation methods.
Technical scheme
A kind of high-temperature-resistant high toughness nitrogenizes silicon substrate wave-penetrating composite material, it is characterised in that：Composite replaces for multilayer BN/Si3N4Matrix, innermost layer are BN matrixes, and intermediate layer is alternately BN/Si3N4Matrix, outermost layer Si3N4Matrix.
A kind of method for preparing the high-temperature-resistant high toughness nitridation silicon substrate wave-penetrating composite material, it is characterised in that step is such as Under：
Step 1, Si3N4The preparation of whisker biscuit：By the Si that volume fraction is 20~50%3N4Whisker and 1.5~ 2.5wt.% dispersant poly amic acid is dissolved in deionized water, adds pH value conditioning agent TMAH regulation slurry pH It is worth for 9~11；4~10wt.% monomeric acrylamide AM and 0.2~1.0wt.% crosslinking agent di-2-ethylhexylphosphine oxide third are added afterwards 24~36h of ball milling after acrylamide MBAM, froth in vacuum 10min；0.2~0.5wt.% initiator ammonium persulfate is added afterwards APS and 0.02~0.1wt.% catalyst tetramethylethylenediamine TEMED, is cast in mould after stirring, is molded and Si is made3N4 Whisker biscuit；
Step 2：By Si3N4Whisker biscuit is subsequently placed in 50~100 DEG C of baking ovens and dried in 12~36h of natural drying at room temperature It is dry；It is placed in again in muffle furnace, in 400~700 DEG C of empty burning 2~4h of dumping, obtains Si3N4Whisker preform；
Step 3, the preparation at interface：By Si3N4Whisker preform is placed in cvd furnace, and BN interfaces, boundary are prepared using CVI methods 0.8~1.5 μm of face thickness；Then can be by the Si at the interface containing BN3N4Whisker preform is placed in high temperature furnace and is heat-treated, processing 1300 DEG C of temperature, 2~6h of processing time；
The preparation of step 4, matrix：Step 3 is obtained into the Si at the interface containing BN3N4Whisker preform is placed in cvd furnace, is used CVI methods prepare multilayer alternating BN/Si3N4Matrix, innermost layer are BN matrixes, and intermediate layer is alternately BN/Si3N4Matrix, outermost layer are Si3N4Matrix.
The step 1Si3N4 whisker preforms use gel casting forming.
Beneficial effect
A kind of high-temperature-resistant high toughness nitridation silicon substrate wave-penetrating composite material proposed by the present invention and preparation method, first, are adopted Porous Si is prepared with gel casting forming3N4Whisker biscuit, porous Si is received after drying dumping3N4Precast body, using chemical gaseous phase Osmosis process (CVI) prepares boron nitride (BN) interface in the whisker preform, and prepares multilayer alternating BN/ using CVI techniques Si3N4Matrix.For high temperature wave transparent antenna cover structure and the design requirement of performance, realize that multilayer replaces BN/ by CVI regulation and control Si3N4The regulation and control of each layer micro-structural of matrix, the number of plies and thickness, to realize the regulation and control of composite structure and performance and optimization, obtain The excellent Si of a kind of high temperature resistant, high-strength and high ductility, wideband wave transparent, thermophysical property3N4Base wave-penetrating composite material.
Beneficial effect：
1st, the present invention is molded porous Si using Gel-casting process3N4Whisker preform, formed precision is high, process controllability By force, the near-net-shape of complicated shape antenna house can be achieved.Si after shaping3N4Whisker biscuit has some strength, can carry out Roughing, and then reduce processing cost, solve ceramic material difficulty processing problems after densification.Porous Si3N4It is brilliant in whisker preform Palpus micro-structural, volume fraction and precast body pore structure isogel molding process Parameter adjustable control, are advantageous to Si3N4Whisker is prefabricated The design and optimization of bulk microstructure and mechanics/wave transparent performance.
2nd, the present invention relates to a kind of Si of low temperature preparation high temperature application3N4Base wave-penetrating composite material, low temperature preparation can not only Effectively enough reduction enhancings mutually damage, and composite is obtained excellent mechanical property, and can also reduce technology difficulty, improve work Skill stability.
3rd, multilayer alternating BN/Si of the present invention3N4Matrix passes through innermost layer BN, outermost layer Si3N4, middle BN/Si3N4 The structure design thinking of alternating deposit, had both realized the matched well of substrates multilayer and BN interfaces, and and can meets that composite resists The environment requirements such as oxidation, anti-weathering, and each layer micro-structural, thickness, the number of plies designability of substrates multilayer are strong, are advantageous to Improve and optimize composite property, antenna house high-strength tenacity, the Si of wideband wave transparent are obtained to be final3N4Based composites are established Fixed basis.
Brief description of the drawings
Fig. 1 is porous Si prepared by the embodiment of the present invention 13N4Whisker preform micro-structural SEM photograph.
Fig. 2 is Si prepared by the embodiment of the present invention 13N4Based composites micro-structural SEM photograph.
Embodiment
In conjunction with embodiment, accompanying drawing, the invention will be further described：
The present invention uses following technical scheme：
Step 1.Si3N4The preparation of whisker biscuit：By the Si that volume fraction is 20~50%3N4Whisker and 1.5~ 2.5wt.% dispersant poly amic acid is dissolved in deionized water, adds pH value conditioning agent TMAH regulation slurry PH value is 9~11；4~10wt.% monomeric acrylamide (AM) and 0.2~1.0wt.% crosslinking agent methylene are added afterwards Bisacrylamide (MBAM), by 24~36h of slurry ball milling, uniformly rear froth in vacuum 10min to be mixed；Addition 0.2 afterwards~ 0.5wt.% initiator ammonium persulfate and 0.02~0.1wt.% catalyst tetramethylethylenediamine (TEMED), stir After be cast in mould, be molded be made Si3N4Whisker biscuit.
Step 2.Si3N4The drying of whisker biscuit：By Si in step 13N4Whisker biscuit in 12~36h of natural drying at room temperature, It is subsequently placed in 50~100 DEG C of baking ovens and dries.
Step 3.Si3N4The dumping of whisker biscuit：By Si in step 23N4Whisker biscuit is placed in muffle furnace, 400~ 700 DEG C of empty burning 2~4h of dumping, obtain Si3N4Whisker preform.
The preparation at step 4. interface：By Si in step 33N4Whisker preform is placed in cvd furnace, and BN is prepared using CVI methods Interface, 0.8~1.5 μm of interfacial thickness.Then can be by the Si at the interface containing BN3N4Whisker preform, which is placed in high temperature furnace, carries out hot place Reason, 1300 DEG C for the treatment of temperature, 2~6h of processing time.
The preparation of step 5. matrix：According to structure and performance design demand, by the Si at the interface containing BN in step 43N4Whisker is pre- Body processed is placed in cvd furnace, and multilayer alternating BN/Si is prepared using CVI methods3N4Matrix.Wherein, innermost layer matrix is BN, realize with The matched well at BN interfaces；Outermost layer matrix is Si3N4, meet the environment requirements such as anti-oxidant, anti-weathering.By regulating and controlling BN And Si3N4The technological parameters such as the preparation temperature of matrix, heat treatment condition, sedimentation time, change multilayer alternating BN/Si3N4In matrix Each phase micro-structural and relative amount and Rotating fields, optimize composite property.
Embodiment 1
Step 1.Si3N4The preparation of whisker biscuit：By the Si that volume fraction is 30%3N4The dispersant of whisker, 1.5wt.% Poly amic acid is dissolved in deionized water, and PH conditioning agents are TMAH, pH value 11, then adds 5wt.% list Body AM, 0.25wt.% crosslinking agent MBAM ball millings disperse 24h, after slurry is well mixed after froth in vacuum 10min, add 0.4wt.% initiator A PS, 0.02wt.% catalyst TEMED, pour into a mould in a mold after stirring, are obtained after shaping Si3N4Whisker biscuit；
Step 2.Si3N4The drying of whisker biscuit：By the whisker biscuit of step 1 in natural drying at room temperature 36h, it is subsequently placed in Dried in 80 DEG C of baking oven；
Step 3.Si3N4The dumping of whisker biscuit：Biscuit after drying is placed in muffle furnace, it is empty at 500 DEG C to burn Dumping 3h, obtains Si3N4Whisker preform；
The preparation at step 4.BN interfaces：Using CVI techniques in Si3N4Deposition BN interfaces in whisker preform.The elder generation at BN interfaces Purging body is by BCl3、NH3、H2Formed with Ar, technological parameter is：Reaction gas ratio [BCl3]/[NH3]=1/3, system pressure 1KPa, 1100 DEG C, sedimentation time 2h of depositing temperature, it is 800nm that BN interfacial thicknesses, which are made, and to the Si at the interface containing BN3N4Whisker Precast body is placed in high temperature furnace and is heat-treated, 1300 DEG C for the treatment of temperature, processing time 2h.
The preparation of step 5. substrates multilayer：Using Si of the CVI techniques at the interface containing BN3N4Alternating deposit in whisker preform Multilayer BN/Si3N4Matrix.BN matrix deposition process is similar to BN interfaces depositing operation in the present embodiment step 4, and difference exists Sedimentation time is 4.5h.CVI prepares Si3N4Matrix, precursor is by SiCl4、NH3, Ar and H2Composition, technological parameter are：Reaction gas Ratio [SiCl4]/[NH3]=1/2, system pressure 1KPa, reaction temperature are 800 DEG C, sedimentation time 5h.Multilayer replaces BN/ Si3N4Rotating fields parameter：Innermost layer is BN, outermost layer Si3N4, every layer of BN and Si3N4Matrix is all 2 μm, and the number of plies is all 5 layers, most The obtained composite porosity is 24vol.% eventually
Embodiment 2
Step 1.Si3N4The preparation of whisker biscuit：By the Si that volume fraction is 35%3N4The dispersant of whisker, 1.5wt.% Poly amic acid is dissolved in deionized water, and PH conditioning agents are TMAH, pH value 11, then adds 5wt.% list Body AM, 0.25wt.% crosslinking agent MBAM ball millings disperse 28h, after slurry is well mixed after froth in vacuum 10min, add 0.35wt.% initiator A PS, 0.02wt.% catalyst TEMED, pour into a mould in a mold after stirring, are obtained after shaping Si3N4Whisker biscuit；
Step 2.Si3N4The drying of whisker biscuit：By the whisker biscuit of step 1 in natural drying at room temperature 36h, it is subsequently placed in Dried in 80 DEG C of baking oven；
Step 3.Si3N4The dumping of whisker biscuit：Biscuit after drying is placed in muffle furnace, it is empty at 500 DEG C to burn Dumping 3h, obtains Si3N4Whisker preform；
The preparation at step 4.BN interfaces：Using CVI techniques in Si3N4Deposition BN interfaces in whisker preform.Depositing operation with The step 4 of embodiment 1 is similar, but difference is 2.5h in sedimentation time, be made BN interfacial thicknesses be 1000nm, and to containing The Si at BN interfaces3N4Whisker preform is placed in high temperature furnace and is heat-treated, 1300 DEG C for the treatment of temperature, processing time 4h.
The preparation of step 5. substrates multilayer：Using CVI techniques in the Si containing interface3N4Alternating deposit is more in whisker preform Layer BN/Si3N4Matrix.BN and Si3N4Matrix deposition process is similar to depositing operation in the step 5 of embodiment 1, difference BN The matrix deposition time is 6h, Si3N4The matrix deposition time is 7h.Multilayer replaces BN/Si3N4Rotating fields parameter：Innermost layer is BN, Outermost layer Si3N4, every layer of BN and Si3N4Matrix is all 2.5 μm, and the number of plies is all 4 layers, and finally the obtained composite porosity is 18vol.%.
Embodiment 3
Step 1.Si3N4The preparation of whisker biscuit：By the Si that volume fraction is 40%3N4The dispersant of whisker, 1.5wt.% Poly amic acid is dissolved in deionized water, and PH conditioning agents are TMAH, pH value 11, then adds 4wt.% list Body AM, 0.2wt.% crosslinking agent MBAM ball millings disperse 32h, after slurry is well mixed after froth in vacuum 10min, add 0.35wt.% initiator A PS, 0.02wt.% catalyst TEMED, pour into a mould in a mold after stirring, are obtained after shaping Si3N4Whisker biscuit；
Step 2.Si3N4The drying of whisker biscuit：By the whisker biscuit of step 1 in natural drying at room temperature 32h, it is subsequently placed in Dried in 80 DEG C of baking oven；
Step 3.Si3N4The dumping of whisker biscuit：Biscuit after drying is placed in muffle furnace, it is empty at 600 DEG C to burn Dumping 3h, obtains Si3N4Whisker preform；
The preparation at step 4.BN interfaces：Using CVI techniques in Si3N4Deposition BN interfaces in whisker preform.Depositing operation with The step 4 of Examples 1 and 2 is similar, but difference is 3h in sedimentation time, and it is 1200nm that BN interfacial thicknesses, which are made,.
The preparation of step 5. substrates multilayer：Using CVI techniques in the Si containing interface3N4Alternating deposit is more in whisker preform Layer BN/Si3N4Matrix.BN and Si3N4Matrix deposition process is similar to depositing operation in Examples 1 and 2 step 5, and difference is The BN matrix deposition times are 3.5h, Si3N4The matrix deposition time is 7h.Multilayer replaces BN/Si3N4Rotating fields parameter：Innermost layer is BN, outermost layer Si3N4, every layer of BN thickness and Si3N4Matrix is respectively 1.5 μm and 2.5 μm, and the number of plies is all 5 layers.Multilayer is prepared to hand over For BN/Si3N4Composite is heat-treated after matrix, heat treatment temperature is 1300 DEG C, heat treatment time 2h, final system It is 16vol.% to obtain the composite porosity.
Embodiment 4
Step 1.Si3N4The preparation of whisker biscuit：By the Si that volume fraction is 45%3N4The dispersant of whisker, 1.5wt.% Poly amic acid is dissolved in deionized water, and PH conditioning agents are TMAH, and pH value adjustable range is 11, is then added 4wt.% monomer AM, 0.2wt.% crosslinking agent MBAM ball millings disperse 36h, after slurry is well mixed after froth in vacuum 10min, 0.25wt.% initiator A PS, 0.02wt.% catalyst TEMED are added, is poured into a mould after stirring in a mold, after shaping Obtain Si3N4Whisker biscuit；
Step 2.Si3N4The drying of whisker biscuit：By the whisker biscuit of step 1 in natural drying at room temperature 36h, it is subsequently placed in Dried in 80 DEG C of baking oven；
Step 3.Si3N4The dumping of whisker biscuit：Biscuit after drying is placed in muffle furnace, it is empty at 500 DEG C to burn Dumping 3h, obtains Si3N4Whisker preform；
The preparation at step 4.BN interfaces：Using CVI techniques in Si3N4Deposition BN interfaces in whisker preform.Heavy technique and reality It is similar to apply the step 4 of example 1,2 and 3, but difference is 3.5h in sedimentation time, and it is 1500nm that BN interfacial thicknesses, which are made,.
The preparation of step 5. substrates multilayer：Using CVI techniques in the Si containing interface3N4Alternating deposit is more in whisker preform Layer BN/Si3N4Matrix.BN and Si3N4Matrix deposition process and embodiment 1,2 are similar with depositing operation in 3 steps 5, difference It is 6h, Si in the BN matrix deposition times3N4The matrix deposition time is 3h.Multilayer replaces BN/Si3N4Rotating fields parameter：Innermost layer is BN, outermost layer Si3N4, every layer of BN thickness and Si3N4Matrix is respectively 2.5 μm and 1.5 μm, and the number of plies is all 4 layers.Multilayer is prepared to hand over For BN/Si3N4Composite is heat-treated after matrix, heat treatment temperature is 1300 DEG C, heat treatment time 2h, final system It is 18vol.% to obtain the composite porosity.

Claims (3)

1. a kind of high-temperature-resistant high toughness nitrogenizes silicon substrate wave-penetrating composite material, it is characterised in that：Composite is that multilayer replaces BN/ Si3N4Matrix, innermost layer are BN matrixes, and intermediate layer is alternately BN/Si3N4Matrix, outermost layer Si3N4Matrix.
2. a kind of method for preparing high-temperature-resistant high toughness nitridation silicon substrate wave-penetrating composite material described in claim 1, its feature exist It is as follows in step：
Step 1, Si3N4The preparation of whisker biscuit：By the Si that volume fraction is 20~50%3N4Whisker and 1.5~2.5wt.%'s Dispersant poly amic acid is dissolved in deionized water, and it is 9~11 to add pH value conditioning agent TMAH regulation slurry pH value； 4~10wt.% monomeric acrylamide AM and 0.2~1.0wt.% crosslinking agent methylene-bisacrylamide MBAM are added afterwards 24~36h of ball milling afterwards, froth in vacuum 10min；Afterwards add 0.2~0.5wt.% initiator ammonium persulfate APS and 0.02~ 0.1wt.% catalyst tetramethylethylenediamine TEMED, is cast in mould after stirring, is molded and Si is made3N4Whisker biscuit；
Step 2：By Si3N4Whisker biscuit is subsequently placed in 50~100 DEG C of baking ovens and dried in 12~36h of natural drying at room temperature；Again It is placed in muffle furnace, in 400~700 DEG C of empty burning 2~4h of dumping, obtains Si3N4Whisker preform；
Step 3, the preparation at interface：By Si3N4Whisker preform is placed in cvd furnace, prepares BN interfaces using CVI methods, interface is thick 0.8~1.5 μm of degree；Then can be by the Si at the interface containing BN3N4Whisker preform is placed in high temperature furnace and is heat-treated, treatment temperature 1300 DEG C, 2~6h of processing time；
The preparation of step 4, matrix：Step 3 is obtained into the Si at the interface containing BN3N4Whisker preform is placed in cvd furnace, using CVI Method prepares multilayer alternating BN/Si3N4Matrix, innermost layer are BN matrixes, and intermediate layer is alternately BN/Si3N4Matrix, outermost layer are Si3N4Matrix.
3. the method for high-temperature-resistant high toughness nitridation silicon substrate wave-penetrating composite material according to claim 1, it is characterised in that：Institute State step 1Si3N4 whisker preforms and use gel casting forming.
CN201710809871.1A 2017-09-11 2017-09-11 High-temperature-resistant high-strength and high-toughness silicon nitride-based wave-transparent composite material and preparation method thereof Active CN107698271B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710809871.1A CN107698271B (en) 2017-09-11 2017-09-11 High-temperature-resistant high-strength and high-toughness silicon nitride-based wave-transparent composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710809871.1A CN107698271B (en) 2017-09-11 2017-09-11 High-temperature-resistant high-strength and high-toughness silicon nitride-based wave-transparent composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107698271A true CN107698271A (en) 2018-02-16
CN107698271B CN107698271B (en) 2020-11-06

Family

ID=61172392

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710809871.1A Active CN107698271B (en) 2017-09-11 2017-09-11 High-temperature-resistant high-strength and high-toughness silicon nitride-based wave-transparent composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107698271B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108706978A (en) * 2018-06-08 2018-10-26 西北工业大学 The method that mist projection granulating combination 3DP and CVI prepare carbon/silicon carbide ceramic matrix composite
CN109231996A (en) * 2018-10-17 2019-01-18 中国人民解放军国防科技大学 Boron nitride-silicon nitride interlayer broadband wave-transmitting material and preparation method thereof
CN109320276A (en) * 2018-10-15 2019-02-12 西北工业大学 Silicon nitride crystal whisker and beta-silicon nitride nanowire enhancing nitridation silicon substrate wave transparent ceramic preparation
CN109761613A (en) * 2019-02-28 2019-05-17 西安交通大学 The short carbon fiber toughened ceramic composite forming method of gel injection-moulding based on 3D printing
CN110156484A (en) * 2019-05-13 2019-08-23 西北工业大学 A kind of BN/Si3N4Whisker preform and the preparation method for using gel casting forming
CN111099919A (en) * 2020-01-14 2020-05-05 中国人民解放军国防科技大学 Silicon nitride ceramic with hierarchical pore structure and preparation method thereof
CN111960838A (en) * 2020-08-31 2020-11-20 武汉科技大学 Silicon nitride framework reinforced quartz-based ceramic for photovoltaic silicon smelting and preparation method thereof
CN112898038A (en) * 2021-03-22 2021-06-04 河海大学 Preparation method of silicon nitride-based fiber monolithic ceramic wave-transmitting material
CN113200765A (en) * 2021-05-13 2021-08-03 湖南世鑫新材料有限公司 Si-containing alloy3N4Carbon-ceramic composite material crucible with BN composite coating and preparation method thereof
CN113248263A (en) * 2021-05-25 2021-08-13 西北工业大学 Si3N4wSi preform and preparation of Si using the same3N4w/Si3N4Method for compounding materials

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0499004A1 (en) * 1991-02-15 1992-08-19 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for manufacturing fiber reinforced ceramic materials by chemical vapor infiltration
CN103804006A (en) * 2014-02-24 2014-05-21 西北工业大学 Preparation method of wave-transparent Si3N4 fiber toughened Si3N4 ceramic based composite
CN105198472A (en) * 2015-09-25 2015-12-30 西北工业大学 Method for preparing silicon nitride layered ceramics reinforced by silicon nitride whiskers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0499004A1 (en) * 1991-02-15 1992-08-19 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for manufacturing fiber reinforced ceramic materials by chemical vapor infiltration
CN103804006A (en) * 2014-02-24 2014-05-21 西北工业大学 Preparation method of wave-transparent Si3N4 fiber toughened Si3N4 ceramic based composite
CN105198472A (en) * 2015-09-25 2015-12-30 西北工业大学 Method for preparing silicon nitride layered ceramics reinforced by silicon nitride whiskers

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GUIFANG HAN等: "Fabrication and characteristic of non-oxide fiber tow reinforced silicon nitride matrix composites by low temperature CVI process", 《CERAMICS INTERNATIONAL》 *
尹邦跃: "《陶瓷核燃料工艺》", 31 January 2016, 哈尔滨工程大学出版社 *
张立同等: "陶瓷基复合材料的界面设计", 《第十三届全国复合材料学术会议》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108706978B (en) * 2018-06-08 2020-11-06 西北工业大学 Method for preparing silicon carbide ceramic matrix composite by combining spray granulation with 3DP and CVI
CN108706978A (en) * 2018-06-08 2018-10-26 西北工业大学 The method that mist projection granulating combination 3DP and CVI prepare carbon/silicon carbide ceramic matrix composite
CN109320276A (en) * 2018-10-15 2019-02-12 西北工业大学 Silicon nitride crystal whisker and beta-silicon nitride nanowire enhancing nitridation silicon substrate wave transparent ceramic preparation
CN109231996A (en) * 2018-10-17 2019-01-18 中国人民解放军国防科技大学 Boron nitride-silicon nitride interlayer broadband wave-transmitting material and preparation method thereof
CN109761613A (en) * 2019-02-28 2019-05-17 西安交通大学 The short carbon fiber toughened ceramic composite forming method of gel injection-moulding based on 3D printing
CN110156484A (en) * 2019-05-13 2019-08-23 西北工业大学 A kind of BN/Si3N4Whisker preform and the preparation method for using gel casting forming
CN110156484B (en) * 2019-05-13 2021-10-22 西北工业大学 BN/Si3N4Whisker preform and preparation method adopting gel injection molding
CN111099919A (en) * 2020-01-14 2020-05-05 中国人民解放军国防科技大学 Silicon nitride ceramic with hierarchical pore structure and preparation method thereof
CN111960838A (en) * 2020-08-31 2020-11-20 武汉科技大学 Silicon nitride framework reinforced quartz-based ceramic for photovoltaic silicon smelting and preparation method thereof
CN111960838B (en) * 2020-08-31 2022-01-14 武汉科技大学 Silicon nitride framework reinforced quartz-based ceramic for photovoltaic silicon smelting and preparation method thereof
CN112898038A (en) * 2021-03-22 2021-06-04 河海大学 Preparation method of silicon nitride-based fiber monolithic ceramic wave-transmitting material
CN113200765A (en) * 2021-05-13 2021-08-03 湖南世鑫新材料有限公司 Si-containing alloy3N4Carbon-ceramic composite material crucible with BN composite coating and preparation method thereof
CN113248263A (en) * 2021-05-25 2021-08-13 西北工业大学 Si3N4wSi preform and preparation of Si using the same3N4w/Si3N4Method for compounding materials

Also Published As

Publication number Publication date
CN107698271B (en) 2020-11-06

Similar Documents

Publication Publication Date Title
CN107698271A (en) High-temperature-resistant high toughness nitrogenizes silicon substrate wave-penetrating composite material and preparation method
Chen et al. Preparation of broadband transparent Si3N4-SiO2 ceramics by digital light processing (DLP) 3D printing technology
CN103086731B (en) Micro-region in-situ reaction preparation method for high strength fiber-reinforced ceramic matrix composite material
CN107686366A (en) A kind of preparation method of nano wire and whisker coordination plasticizing ceramic matric composite
RU2744543C1 (en) Method for producing ceramic composite material based on silicon carbide, reinforced with silicon carbide fibers
CN107188596B (en) Porous gradient silicon nitride-silicon carbide composite ceramic and preparation method and application thereof
CN104261850A (en) High-temperature-resistant wave-transparent silicon nitride fiber-reinforced composite material and preparation method thereof
CN106007758A (en) Toughened silicon nitride combined silicon carbide ceramic composite material and preparation method thereof
CN105198475A (en) Method for producing complex-shaped porous silicon nitride ceramic product
Dong et al. Additive manufacturing of silicon nitride ceramics: A review of advances and perspectives
CN109320276A (en) Silicon nitride crystal whisker and beta-silicon nitride nanowire enhancing nitridation silicon substrate wave transparent ceramic preparation
CN109851362B (en) SiC prepared by 3D formingfMethod for preparing/SiC ceramic composite material
CN114315394B (en) By using Ti 3 SiC 2 Preparation method of three-dimensional network porous prefabricated body reinforced SiC ceramic matrix composite material
CN110304924B (en) Silicon carbide composite material with layered structure and preparation method thereof
CN113735590B (en) Preparation method and product of high-temperature-resistant electromagnetic wave-absorbing ceramic matrix composite material
CN102049514B (en) Powder for aluminum oxide ceramics nano metallized paste and preparation method thereof
Chen et al. Microstructure and properties of SiCw/SiC composites prepared by gel-casting combined with precursor infiltration and pyrolysis
CN103242044B (en) Gel-casting preparation method of BN/Si3N4 composite ceramics
CN115894041A (en) Preparation method of powder extrusion 3D printing molding reaction sintering silicon carbide ceramic
CN109761622A (en) A kind of silicon nitride base gradient composite material and preparation method thereof based on outfield ancillary technique
CN112453410B (en) Annular metal-ceramic gradient material and preparation method thereof
CN109320250A (en) A kind of porous B based on agarose macromolecules gel casting forming4C ceramics preparative body
JPH09268072A (en) Production of silicon nitride sintered compact
CN111747748A (en) Ultrahigh-temperature heat-insulation integrated ZrC/Zr2C complex phase material and preparation method thereof
CN109095932A (en) A kind of crystal whisker toughening silicon nitride foamed material and its pressureless sintering preparation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant