CN112960982A - Preparation method of SiHfBCN wave-absorbing ceramic - Google Patents

Preparation method of SiHfBCN wave-absorbing ceramic Download PDF

Info

Publication number
CN112960982A
CN112960982A CN202110213436.9A CN202110213436A CN112960982A CN 112960982 A CN112960982 A CN 112960982A CN 202110213436 A CN202110213436 A CN 202110213436A CN 112960982 A CN112960982 A CN 112960982A
Authority
CN
China
Prior art keywords
ceramic
preparation
wave
sihfbcn
block
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202110213436.9A
Other languages
Chinese (zh)
Inventor
范晓孟
张敏
叶昉
薛继梅
成来飞
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 CN202110213436.9A priority Critical patent/CN112960982A/en
Publication of CN112960982A publication Critical patent/CN112960982A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—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
    • C04B35/58007—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 refractory metal nitrides
    • C04B35/58028—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 refractory metal nitrides based on zirconium or hafnium nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5622—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on zirconium or hafnium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/5805—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 borides
    • C04B35/58064—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 borides based on refractory borides
    • C04B35/58078—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 borides based on refractory borides based on zirconium or hafnium borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • C04B2235/3834—Beta silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to a preparation method of SiHfBCN wave-absorbing ceramic, which comprises the steps of mixing Polyborosilazane (PBSZ) and Poly Hafnocene (PHO) according to a certain volume ratio by adopting a precursor blending method, and then carrying out curing, cracking and high-temperature heat treatment to obtain the SiHfBCN ceramic. The wave absorbing performance can be adjusted and controlled by adjusting the blending ratio of the precursor and the high-temperature heat treatment temperature. HfC, HfN and HfB2The crystal grain reaches the nanometer level, the volume proportion is adjusted, and the response of the material to the electromagnetic wave from absorption to reflection can be realized. The invention can be applied to composite materials, and the generated ablation-resistant HfC, HfN and HfB2And the ablation resistance of the composite material in an ultrahigh-temperature environment can be effectively improved.

Description

Preparation method of SiHfBCN wave-absorbing ceramic
Technical Field
The invention belongs to a preparation method of an ultrahigh-temperature ceramic-based composite material, and relates to a preparation method of SiHfBCN wave-absorbing ceramic, in particular to a method for preparing hafnium-phase-rich ceramic by adopting a precursor blending process, and a method for preparing wave-absorbing and ablation integrated ceramic.
Background
The new generation of fighters puts forward new requirements of ablation resistance and wave absorption integration on materials. When the speed of the aircraft is higher than Mach 5, the surface of the aircraft can be severely rubbed, the temperature of the surface layer is rapidly increased, and a higher requirement is put on the ablation resistance of the thermal protection material. With the development of detection and guidance technologies in modern war, the survivability and penetration of aircraft are seriously threatened. Therefore, on the basis of the requirement of high ablation resistance on the thermal protection material, the requirement of high-temperature wave absorption is further provided so as to meet the design requirement of aircraft stealth.
SiBCN is a novel quaternary structure ceramic, and is widely concerned due to the specific organization structure and good thermal property at high temperature. But the SiBCN ceramic reacts with oxygen at high temperature to form B2O3And SiO2And the oxidation product has low melting point, so that the ablation resistance is poor under the condition of strong heat flow. Therefore, an anti-ablation unit needs to be introduced.
The hafnium phase ceramic material has the characteristics of high melting point, high modulus and high thermal conductivity, and can form a high melting point oxide HfO under ablation conditions2The inner material is protected from erosion, and the ablation resistance of the material is enhanced. It is thus understood that the introduction of the hafnium phase improves the ablation resistance of SiBCN.
The SiBCN ceramic has the amorphous microstructure characteristic and can be used as a matrix of a wave-absorbing ceramic composite material. The hafnium phase ceramic is introduced into SiBCN, so that the wave absorbing performance of the SiBCN can be obviously improved.
The current preparation methods of SiHfBCN ceramics are mainly divided into two types, namely' Aomefei2Research on thermal shock resistance and ablation resistance of/SiBCN complex phase ceramic [ D]The SiHfBCN amorphous ceramic is prepared by adopting a mechanical alloying method. The document "Yuan J, Hapis S, Breitzke H, et al, Single-Source-Presrosor Synthesis of Hafnium-Containing ultra-high-Temperature Ceramic Nanocomposites (UHTC-NCs) [ J]Inorganic Chemistry 2015,45(49): 10443-10455' preparation of beta-SiC, HfC, HfN and HfB containing compounds using single source precursor synthesis2Of four crystal phasesSiHfBCN ceramic. The SiHfBCN ceramic is prepared by the first method, so that the energy consumption is high, and the requirement on equipment is high; the SiHfBCN ceramic is prepared by the second method, the cost is high, the synthesis process needs to be carried out under the conditions of no water, no oxygen and low temperature, the requirements are difficult to meet in a common laboratory or an enterprise, and the product is unstable; both methods are not suitable for batch production, and the regulation and control of the wave-absorbing and ablation-resisting properties of the SiHfBCN ceramic are not researched so far.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of SiHfBCN wave-absorbing ceramic, and two precursors of Polyborosilazane (PBSZ) and hafnocene (PHO) are used, so that the method is feasible. The regulation and control of the wave absorbing and ablation resisting performances can be realized by regulating the blending ratio of the two precursors and the heat treatment temperature. The invention provides a preparation method of SiHfBCN wave-absorbing ceramic, which greatly reduces the energy consumption and cost of preparation, and simultaneously adjusts the blending ratio of precursors and the heat treatment temperature to realize the regulation and control of the wave-absorbing and ablation-resisting performance of the SiHfBCN ceramic.
Technical scheme
A preparation method of SiHfBCN wave-absorbing ceramic is characterized by comprising the following steps:
step 1, preparation of prepolymer: mixing polyborosilazane PBSZ and poly hafnoxane PHO, stirring and dissolving in dimethylbenzene, and then ultrasonically dispersing in an ultrasonic cleaner for 1-3h to uniformly mix the two precursors to obtain a prepolymer;
step 2, preparation of a cured product: curing the prepolymer in a drying oven at the temperature of 150 ℃ and 250 ℃ for 2-4h to obtain a massive cured substance;
step 3, preparation of cured powder: grinding the massive condensate in an agate mortar for 20-40 minutes, and then sieving the ground massive condensate under a screen to obtain condensate powder with micron scale;
step 4, preparation of a cured block: putting the solidified material powder into a mould, and briquetting under the pressure of 6-10MPa to obtain a solidified material block;
step 5, preparing the ceramic block: putting the cured block into a quartz crucible, transferring the quartz crucible into a tubular cracking furnace, and cracking for 2-4h at 900 ℃ in an argon atmosphere to obtain a ceramic block;
step 6, heat treatment of the ceramic block: and (3) putting the ceramic block into a quartz crucible, then transferring the quartz crucible into a kettle type cracking furnace, and carrying out heat treatment for 2-10h at the temperature of 1100-1700 ℃ in the argon atmosphere to obtain the ceramic block.
In the step 1, the polyborosilazane PBSZ and the poly-hafnoxane PHO are mixed at different volume ratios to obtain beta-SiC, HfC, HfN and HfB2The content of (A) is different.
The selection of the heat treatment temperature in the step 6 depends on the proportion requirement of the crystalline phase and the amorphous phase of the ceramic block, the SiHfBCN ceramic is mainly amorphous at the temperature of 1700 ℃, and the crystallization is started at the temperature of 1700 ℃.
The SiHfBCN ceramic has a crystalline phase accounting for 60-85% of the molar fraction of the hafnium phase and a beta-SiC molar fraction of 15-40%.
And the drying box in the step 2 is an electrothermal blowing drying box.
Advantageous effects
The invention provides a preparation method of SiHfBCN wave-absorbing ceramic, which is characterized in that Polyborosilazane (PBSZ) and Poly Hafnoxane (PHO) are mixed according to a certain volume ratio by adopting a precursor blending method, and then the SiHfBCN ceramic is obtained through solidification, cracking and high-temperature heat treatment. The wave absorbing performance can be adjusted and controlled by adjusting the blending ratio of the precursor and the high-temperature heat treatment temperature. HfC, HfN and HfB2The crystal grain reaches the nanometer level, the volume proportion is adjusted, and the response of the material to the electromagnetic wave from absorption to reflection can be realized. The invention can be applied to composite materials, and the generated ablation-resistant HfC, HfN and HfB2And the ablation resistance of the composite material in an ultrahigh-temperature environment can be effectively improved.
The preparation method of the invention adjusts the crystal phase, the amorphous phase and the proportion of each crystal phase by changing the blending proportion and the heat treatment temperature of the two precursors, thereby realizing the regulation and control of the wave absorption performance. The molar fraction of the hafnium compound phase in the obtained material reaches 60-85 percent, and the molar fraction of beta-SiC is 15-40 percent. And generateHfC, HfN and HfB of2The size of the silicon nitride is less than 500nm, so that the ablation resistance is effectively improved. The SiHfBCN ceramic has an open porosity of 30-65% and a density of 3.5-3.9g/cm3。
The invention can be applied to composite materials and can produce HfC, HfN and HfB2The molar fraction of the hafnium compound phase in the matrix is effectively increased, and the ablation resistance of the hafnium compound phase in the ultrahigh-temperature environment is improved.
Drawings
FIG. 1: the surface XRD pattern of the SiHfBCN wave-absorbing ceramic prepared by the invention,
the volume mixing ratio of Polyborosilazane (PBSZ) to Poly Hafnoxane (PHO) is 1:0.25, and the XRD pattern of the SiHfBCN wave-absorbing ceramic is obtained;
FIG. 2: the SiHfBCN wave-absorbing ceramic scanning electron microscope picture prepared by the invention,
SEM atlas of SiHfBCN ceramic obtained from 1:1 volume mixing ratio of Polyborosilazane (PBSZ) and poly-hafnoxane (PHO)
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1: SiHfBCN wave-absorbing ceramic is prepared by adopting Polyborosilazane (PBSZ) and Poly Hafnane (PHO) in a volume mixing ratio of 1:0.25
The preparation method comprises the following specific steps:
step 1, preparation of prepolymer: putting 20ml of Polyborosilazane (PBSZ) and 5ml of hafnocene (PHO) into a 250ml beaker, adding a certain amount of dimethylbenzene, fully stirring, and ultrasonically dispersing in an ultrasonic cleaner for 1-3 hours to uniformly mix the two precursors to obtain a prepolymer;
step 2, preparation of a cured product: putting the prepolymer obtained in the step 1 into an electric heating forced air drying oven for curing at the temperature of 200 ℃ for 2 hours to obtain a massive cured substance;
step 3, preparation of cured powder: putting the massive condensate obtained in the step 2 into an agate mortar for grinding for 30 minutes, and then sieving the crushed massive condensate under a screen to obtain micron-scale condensate powder;
step 4, preparation of a cured block: dividing the solidified material powder obtained in the step 3 into 5 parts according to the mass average, respectively putting the 5 parts into a die with a certain size, and briquetting the 5 parts under the pressure of 6-10MPa to obtain a solidified material block;
step 5, preparing the ceramic block: putting the cured material block obtained in the step (4) into a quartz crucible, transferring the quartz crucible into a tubular cracking furnace, and cracking for 2-10h at 900 ℃ in an argon atmosphere to obtain a ceramic block;
step 6, heat treatment of the ceramic block: taking 4 ceramic blocks obtained in the step 5, respectively placing the ceramic blocks into 4 quartz crucibles, then transferring the quartz crucibles into a kettle type cracking furnace, and respectively carrying out heat treatment for 2-10h at 1100-1700 ℃ under the argon atmosphere to obtain ceramic blocks subjected to heat treatment at different temperatures;
step 7, wave-absorbing performance testing: and (4) placing the ceramic block obtained in the step (6) into a vector network analyzer, and testing the absorption performance of the ceramic block on electromagnetic waves. Tests show that in an X wave band (8.2-12.4GHz), the wave-absorbing performance is optimal as follows: the effective absorption bandwidth is 4.1GHz, the minimum thickness is 2.50mm, and the minimum value of the reflection coefficient is-23 dB.
Example 2: SiHfBCN wave-absorbing ceramic is prepared by adopting Polyborosilazane (PBSZ) and Poly Hafnane (PHO) in a volume mixing ratio of 1:0.5
The preparation method comprises the following specific steps:
step 1, preparation of prepolymer: putting 20ml of Polyborosilazane (PBSZ) and 10ml of hafnocene (PHO) into a 250ml beaker, adding a certain amount of dimethylbenzene, fully stirring, and ultrasonically dispersing in an ultrasonic cleaner for 1-3 hours to uniformly mix the two precursors to obtain a prepolymer;
step 2, preparation of a cured product: putting the prepolymer obtained in the step 1 into an electric heating forced air drying oven for curing at the temperature of 200 ℃ for 2 hours to obtain a massive cured substance;
step 3, preparation of cured powder: putting the massive condensate obtained in the step 2 into an agate mortar for grinding for 30 minutes, and then sieving the crushed massive condensate under a screen to obtain micron-scale condensate powder;
step 4, preparation of a cured block: dividing the solidified material powder obtained in the step 3 into 5 parts according to the mass average, respectively putting the 5 parts into a die with a certain size, and briquetting the 5 parts under the pressure of 6-10MPa to obtain a solidified material block;
step 5, preparing the ceramic block: putting the cured material block obtained in the step (4) into a quartz crucible, transferring the quartz crucible into a tubular cracking furnace, and cracking for 2-10h at 900 ℃ in an argon atmosphere to obtain a ceramic block;
step 6, heat treatment of the ceramic block: taking 4 ceramic blocks obtained in the step 5, respectively placing the ceramic blocks into 4 quartz crucibles, then transferring the quartz crucibles into a kettle type cracking furnace, and respectively carrying out heat treatment for 2-10h at 1100-1700 ℃ under the argon atmosphere to obtain ceramic blocks subjected to heat treatment at different temperatures;
step 7, wave-absorbing performance testing: and (4) placing the ceramic block obtained in the step (6) into a vector network analyzer, and testing the absorption performance of the ceramic block on electromagnetic waves. Tests show that in an X wave band (8.2-12.4GHz), the wave-absorbing performance is optimal as follows: the effective absorption bandwidth is 4.0GHz, the minimum thickness is 2.32mm, and the minimum value of the reflection coefficient is-20 dB.
Example 3: SiHfBCN wave-absorbing ceramic prepared by adopting Polyborosilazane (PBSZ) and Poly Hafnane (PHO) in a volume mixing ratio of 1:0.75
The preparation method comprises the following specific steps:
step 1, preparation of prepolymer: putting 20ml of Polyborosilazane (PBSZ) and 15ml of hafnocene (PHO) into a 250ml beaker, adding a certain amount of dimethylbenzene, fully stirring, and ultrasonically dispersing in an ultrasonic cleaner for 1-3 hours to uniformly mix the two precursors to obtain a prepolymer;
step 2, preparation of a cured product: putting the prepolymer obtained in the step 1 into an electric heating forced air drying oven for curing at the temperature of 200 ℃ for 2 hours to obtain a massive cured substance;
step 3, preparation of cured powder: putting the massive condensate obtained in the step 2 into an agate mortar for grinding for 30 minutes, and then sieving the crushed massive condensate under a screen to obtain micron-scale condensate powder;
step 4, preparation of a cured block: dividing the solidified material powder obtained in the step 3 into 5 parts according to the mass average, respectively putting the 5 parts into a die with a certain size, and briquetting the 5 parts under the pressure of 6-10MPa to obtain a solidified material block;
step 5, preparing the ceramic block: putting the cured material block obtained in the step (4) into a quartz crucible, transferring the quartz crucible into a tubular cracking furnace, and cracking for 2-10h at 900 ℃ in an argon atmosphere to obtain a ceramic block;
step 6, heat treatment of the ceramic block: taking 4 ceramic blocks obtained in the step 5, respectively placing the ceramic blocks into 4 quartz crucibles, then transferring the quartz crucibles into a kettle type cracking furnace, and respectively carrying out heat treatment for 2-10h at 1100-1700 ℃ under the argon atmosphere to obtain ceramic blocks subjected to heat treatment at different temperatures;
step 7, wave-absorbing performance testing: and (4) placing the ceramic block obtained in the step (6) into a vector network analyzer, and testing the absorption performance of the ceramic block on electromagnetic waves. Tests show that in an X wave band (8.2-12.4GHz), the wave-absorbing performance is optimal as follows: the effective absorption bandwidth is 3.8GHz, the minimum thickness is 2.10mm, and the minimum value of the reflection coefficient is-15 dB.
Example 4: SiHfBCN wave-absorbing ceramic is prepared by adopting Polyborosilazane (PBSZ) and Poly Hafnane (PHO) in a volume mixing ratio of 1:0.5
The preparation method comprises the following specific steps:
step 1, preparation of prepolymer: putting 20ml of Polyborosilazane (PBSZ) and 20ml of hafnocene (PHO) into a 250ml beaker, adding a certain amount of dimethylbenzene, fully stirring, and ultrasonically dispersing in an ultrasonic cleaner for 1-3 hours to uniformly mix the two precursors to obtain a prepolymer;
step 2, preparation of a cured product: putting the prepolymer obtained in the step 1 into an electric heating forced air drying oven for curing at the temperature of 200 ℃ for 2 hours to obtain a massive cured substance;
step 3, preparation of cured powder: putting the massive condensate obtained in the step 2 into an agate mortar for grinding for 30 minutes, and then sieving the crushed massive condensate under a screen to obtain micron-scale condensate powder;
step 4, preparation of a cured block: dividing the solidified material powder obtained in the step 3 into 5 parts according to the mass average, respectively putting the 5 parts into a die with a certain size, and briquetting the 5 parts under the pressure of 6-10MPa to obtain a solidified material block;
step 5, preparing the ceramic block: putting the cured material block obtained in the step (4) into a quartz crucible, transferring the quartz crucible into a tubular cracking furnace, and cracking for 2-10h at 900 ℃ in an argon atmosphere to obtain a ceramic block;
step 6, heat treatment of the ceramic block: taking 4 ceramic blocks obtained in the step 5, respectively placing the ceramic blocks into 4 quartz crucibles, then transferring the quartz crucibles into a kettle type cracking furnace, and respectively carrying out heat treatment for 2-10h at 1100-1700 ℃ under the argon atmosphere to obtain ceramic blocks subjected to heat treatment at different temperatures;
step 7, wave-absorbing performance testing: and (4) placing the ceramic block obtained in the step (6) into a vector network analyzer, and testing the absorption performance of the ceramic block on electromagnetic waves. Tests show that in an X wave band (8.2-12.4GHz), the wave-absorbing performance is optimal as follows: the effective absorption bandwidth is 3.5GHz, the minimum thickness is 2.00mm, and the minimum value of the reflection coefficient is-14 dB.

Claims (4)

1. A preparation method of SiHfBCN wave-absorbing ceramic is characterized by comprising the following steps:
step 1, preparation of prepolymer: mixing polyborosilazane PBSZ and poly hafnoxane PHO, stirring and dissolving in dimethylbenzene, and then ultrasonically dispersing in an ultrasonic cleaner for 1-3h to uniformly mix the two precursors to obtain a prepolymer;
step 2, preparation of a cured product: curing the prepolymer in a drying oven at the temperature of 150 ℃ and 250 ℃ for 2-4h to obtain a massive cured substance;
step 3, preparation of cured powder: grinding the massive condensate in an agate mortar for 20-40 minutes, and then sieving the ground massive condensate under a screen to obtain condensate powder with micron scale;
step 4, preparation of a cured block: putting the solidified material powder into a mould, and briquetting under the pressure of 6-10MPa to obtain a solidified material block;
step 5, preparing the ceramic block: putting the cured block into a quartz crucible, transferring the quartz crucible into a tubular cracking furnace, and cracking for 2-4h at 900 ℃ in an argon atmosphere to obtain a ceramic block;
step 6, heat treatment of the ceramic block: and (3) putting the ceramic block into a quartz crucible, then transferring the quartz crucible into a kettle type cracking furnace, and carrying out heat treatment for 2-10h at the temperature of 1100-1700 ℃ in the argon atmosphere to obtain the ceramic block.
2. The preparation method of SiHfBCN wave-absorbing ceramic according to claim 1, characterized in that: in the step 1, the polyborosilazane PBSZ and the poly-hafnoxane PHO are mixed at different volume ratios to obtain beta-SiC, HfC, HfN and HfB2The content of (A) is different.
3. The preparation method of SiHfBCN wave-absorbing ceramic according to claim 1, characterized in that: the selection of the heat treatment temperature in the step 6 depends on the proportion requirement of the crystalline phase and the amorphous phase of the ceramic block, the SiHfBCN ceramic is mainly amorphous at the temperature of 1700 ℃, and the crystallization is started at the temperature of 1700 ℃.
4. The preparation method of SiHfBCN wave-absorbing ceramic according to claim 1, characterized in that: and the drying box in the step 2 is an electrothermal blowing drying box.
CN202110213436.9A 2021-02-25 2021-02-25 Preparation method of SiHfBCN wave-absorbing ceramic Withdrawn CN112960982A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110213436.9A CN112960982A (en) 2021-02-25 2021-02-25 Preparation method of SiHfBCN wave-absorbing ceramic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110213436.9A CN112960982A (en) 2021-02-25 2021-02-25 Preparation method of SiHfBCN wave-absorbing ceramic

Publications (1)

Publication Number Publication Date
CN112960982A true CN112960982A (en) 2021-06-15

Family

ID=76286176

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110213436.9A Withdrawn CN112960982A (en) 2021-02-25 2021-02-25 Preparation method of SiHfBCN wave-absorbing ceramic

Country Status (1)

Country Link
CN (1) CN112960982A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113604195A (en) * 2021-07-29 2021-11-05 西北工业大学 X-waveband full-frequency wave-absorbing porous bentonite composite material and preparation method thereof
CN114276149A (en) * 2022-01-17 2022-04-05 西北工业大学 Hafnium-containing silicon-boron-carbon-nitrogen high-temperature wave-absorbing ceramic and preparation method and application thereof
WO2022174624A1 (en) * 2021-11-02 2022-08-25 航天材料及工艺研究所 High-temperature-resistant and oxidation-resistant light-weight heat-insulation foam material and preparation method therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113604195A (en) * 2021-07-29 2021-11-05 西北工业大学 X-waveband full-frequency wave-absorbing porous bentonite composite material and preparation method thereof
CN113604195B (en) * 2021-07-29 2024-01-30 西北工业大学 Porous bentonite composite material with X-band full-frequency wave absorption function and preparation method thereof
WO2022174624A1 (en) * 2021-11-02 2022-08-25 航天材料及工艺研究所 High-temperature-resistant and oxidation-resistant light-weight heat-insulation foam material and preparation method therefor
CN114276149A (en) * 2022-01-17 2022-04-05 西北工业大学 Hafnium-containing silicon-boron-carbon-nitrogen high-temperature wave-absorbing ceramic and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN112960982A (en) Preparation method of SiHfBCN wave-absorbing ceramic
Yang et al. Rapid sintering method for highly conductive Li7La3Zr2O12 ceramic electrolyte
CN105418071B (en) The synthetic method of high pure and ultra-fine ZrC SiC composite granules
KR101916712B1 (en) Negative electrode active material for nonaqueous electrolyte secondary battery and preparing method thereof
CN104891495B (en) Method for synthesizing boron carbide powder in high yield at low temperature
CN101570651B (en) Corrosion-resistance coating of polysilicon ingot furnace, high temperature resistance protective layer and preparation method thereof
Zhang et al. Microwave absorbing property of gelcasting SiC-Si3N4 ceramics with hierarchical pore structures
Liu et al. Effect of Y2O3 on the oxidation properties of ZrSi2/SiC coating prepared by SAPS on the carbon-carbon composites
CN114394827B (en) Low-dielectric-constant silicate microwave dielectric ceramic and preparation method thereof
CN114957897B (en) High-performance graphene film and preparation method thereof
Xing et al. 3D printing of liquid‐metal‐in‐ceramic metamaterials for high‐efficient microwave absorption
US20070062719A1 (en) Electrically conducting-inorganic substance-containing silicon carbide-based fine particles, electromagnetic wave absorbing material and electromagnetic wave absorber
CN107955998A (en) A kind of high soft mullite of lightweight is ultra-fine/nano ceramic fibers and preparation method thereof
CN112176719A (en) Preparation method of C/SiC shell-core structure composite fiber and composite fiber
CN114988716B (en) Tungsten carbide/graphene composite material and preparation method thereof
CN107740205B (en) A kind of compound organic precursor method preparation BN-Si3N4The method of complex phase ceramic continuous fiber
JP2004296161A (en) Conductive material-coated silicon and its manufacturing method and electrode material for non-aqueous electrolyte secondary battery
CN114204006B (en) Battery negative electrode active material, preparation method thereof, battery negative electrode and secondary battery
CN101082090B (en) Preparation method of Mo/AIN multi-phase microwave absorbing material
CN115196951A (en) Modified carbon fiber-mullite ceramic wave-absorbing material with multilayer structure and preparation method thereof
CN107759249A (en) A kind of oxide carbide composite coating containing chromium and preparation method thereof
CN113149656B (en) Rich in Si 3 N 4 SiHfBCN ceramic of nanowire and preparation method
CN105859280B (en) A kind of microwave-medium ceramics and preparation method thereof
CN107651852A (en) The seal glass and its preparation and application mixed outside a kind of cobalt sesquioxide nickel oxide
CN115433008B (en) Bismuth calcium niobate piezoelectric ceramic with high-voltage electrical property and high-temperature resistivity regulated and controlled by self components and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20210615