CN105859298B - A kind of polymer precursor ceramic microwave after-treatment modification method - Google Patents

A kind of polymer precursor ceramic microwave after-treatment modification method Download PDF

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CN105859298B
CN105859298B CN201610188129.9A CN201610188129A CN105859298B CN 105859298 B CN105859298 B CN 105859298B CN 201610188129 A CN201610188129 A CN 201610188129A CN 105859298 B CN105859298 B CN 105859298B
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microwave
precursor
polymer precursor
nitrogen protection
under nitrogen
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CN105859298A (en
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邵刚
彭文峰
赵婉瑜
王海龙
陈德良
张锐
安立楠
范冰冰
卢红霞
许红亮
郭静霞
马超
彭星淋
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Zhengzhou University
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    • 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
    • C04B35/589—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 obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—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
    • C04B2235/667—Sintering using wave energy, e.g. microwave sintering

Abstract

The invention discloses a kind of polymer precursor ceramic microwave after-treatment modification methods.This approach includes the following steps：1) under nitrogen protection, polysilazane precursor is mixed with hot-setter；2) under vacuum, mixture is carried out to heat cure at 110~200 DEG C；3) under nitrogen protection, 4h is pyrolyzed in 1000 DEG C in tube furnace；4) 1000 DEG C under nitrogen protection, are warming up to using microwave, keeps the temperature 30min, it is cooling to get.In the prior art, modifies to polymeric preceramic by conventional heating, higher temperature is generally required, matrix can be caused to crystallize to some extent.And the high high-temp stability and electrical property of ceramic material, the noncrystal substrate of ceramics is depended heavily on, the performance that different degrees of crystallization often leads to product is affected.Thus it is proposed that being modified using microwave to carry out fast low temperature speed to PDC, material is made to keep the amorphous state of matrix while performance has very big promotion.

Description

A kind of polymer precursor ceramic microwave after-treatment modification method
Technical field
The invention belongs to polymer precursor ceramic technology fields, and in particular to after a kind of polymer precursor ceramic microwave Handle method of modifying.
Background technology
Polymer precursor method is a kind of method preparing ceramic material using polymer precursor conversion, corresponding ceramics It is ceramic (PDC) that material can be referred to as polymer precursor.Can be used as precursor type of polymer have Polycarbosilane, polysilazane, Polysiloxanes, polyborazine etc..Polymer precursor ceramics (PDC) are a kind of novel refractory ceramics, it is warmed by height Solve what (800~1000 DEG C) silicon-containing polymer precursor obtained, usually by Si-C-N (O) tetrahedral amorphous matrixes and free carbon group At.
The typical process of polymer precursor method includes being crosslinked of preceramic polymer, inorganization and crystallization process；Crosslinking Process makes polymeric preceramic precursor chain grow up or be formed reticular structure, to improve thermal stability, ceramic yield and compactness, accordingly Cross-linking method has heat cross-linking, high-power electron beam/ray crosslinking, chemical crosslinking etc.；Inorganization process refers to that macromolecular chain is slowly split Solution is converted into amorphous state inorganic material, and it includes chain fracture, low-molecular weight polymer and micro-molecular gas discharges etc.；Crystallization mistake The performances such as anti-oxidant, corrosion-resistant can be improved in journey, make that ceramic matrix is finer and close, mechanical performance is more preferable.
PDC ceramics have a series of excellent structural and functional characteristics.Functionally, PDC ceramics have excellent temperature Degree-resistance characteristic, resistance can be reduced with the raising of temperature, and the characteristic can remain to 1300 DEG C, significantly larger than SiC material (650 DEG C)；In structure, easily it is doped, the PDC of B doping has high high-temp stability outstanding, can To be stabilized at 2000 DEG C, no obvious degradation；Meanwhile the PDC of Al doping has excellent high-temperature oxidation resistance and anticorrosive Property, oxidation rate ratio CVD-SiC is 10 times small, and this advantage is more and more significant with the raising of test temperature.PDC methods can Suitable for millimeter, micron and nano-sized ceramic component, the polymer shapings works such as micro Process, micro- casting, photoetching can be utilized Skill prepares the ceramic material of complicated shape, with simple, the at low cost feature of preparation process.
Tang Yun etc. (Chemical Journal of Chinese Universities, 29 phase of August in 2008) is prepared for a kind of Si-B- using precursor pyrolysis and hot pressing N-C ceramic fibres, using PVDF hollow fiber membrane as precursor, through the pyrolysis of melt spinning, cure treatment and nitrogen high temperature, sintering Obtain Si-B-N-C ceramic fibres.Fiber mainly has Si3N4, the phase compositions such as BN and SiC, room temperature tensile intensity is 2.1GPa, tool There are good amorphous stability and high-temperature oxidation resistance.
In the prior art, generally modifies to polymeric preceramic by conventional heating, higher temperature is generally required, can be led Matrix is caused to crystallize to some extent.And the high high-temp stability and electrical property of ceramic material, especially thermo-resistive effect are largely Noncrystal substrate of the ground dependent on ceramics, the performance that different degrees of crystallization often leads to product are affected.Thus we carry Go out and be modified using microwave to carry out fast low temperature speed to PDC, material is made to keep the amorphous of matrix while performance has very big promotion State.
Invention content
It is existing to solve the object of the present invention is to provide a kind of polymer precursor ceramic microwave after-treatment modification method Deficiency of the conventional heating means in polymer precursor ceramic system is standby.
In order to achieve the goal above, the technical solution adopted in the present invention is：
A kind of polymer precursor ceramic microwave after-treatment modification method, includes the following steps：
1) polysilazane precursor is mixed with hot-setter under nitrogen protection, obtains mixture；
2) mixture obtained by step 1) under vacuum, is subjected to heat cure at 110~200 DEG C, obtains solidfied material；
3) under nitrogen protection, solidfied material obtained by step 2) is pyrolyzed 4h in tube furnace at 1000 DEG C, obtains forerunner Body ceramics；
4) precursor ceramic obtained by step 3) under nitrogen protection, is warming up to 1000 DEG C using microwave, keeps the temperature 30min, It is cooling to get.
Polymer precursor ceramic microwave after-treatment modification method provided by the invention is led to using polysilazane as precursor Cross heat cure, pyrolysis step obtains ceramic inorganic object, the PRECURSOR-DERIVED CERAMICS further being had excellent performance by microwave heating.First The performance and Si-C-N (O) tetrahedral amorphous matrixes in its structure and free carbon for driving body ceramics have prodigious relationship, by free carbon The structure and form in the carbon area of composition have significant effect the thermal stability and electric conductivity of material；Traditional mode of heating can be same When noncrystal substrate and carbon area are acted on, so that the crystallinity of material entirety is improved, the difference of crystallization degree often leads to precursor and makes pottery The performance of porcelain generates big deviation.Step 4) is different to the responding ability of microwave using the areas amorphous Si and carbon area：Carbon area is to microwave Responding ability be better than the areas Si, realize that the areas amorphous Si and carbon area are heated to some extent with microwave heating, realize to polymer The quick modification of precursor ceramic.
Step 1) and the crosslinking curing process that step 2) is polysilazane, the molecule of preceramic polymer is made by the process Chain is grown up or is crosslinked, and to improve thermal stability, ceramic yield, reduces hole and crackle, improves compactness.
Preferably, in step 1), the polysilazane precursor has structure shown in formula 1：
In formula 1, x=2, y=8.Polysilazane precursor synthesizes the prior art, can by chlorosilane ammonolysis process, urge Fluidized dehydrogenation coupling, ring-opening polymerisation or transistion metal compound catalytic dehydrogenation methods obtain the polysilazane precursor of above structure.
The hot-setter is cumyl peroxide.The mass ratio of polysilazane precursor and hot-setter is 90~95:5 ~10.Described be mixed into is stirred；The stirring carries out at 60~100 DEG C, and the time of stirring is 0.5~2h.Step 2) In, the thermal curing time is 2~5h.
In the invention, solidfied material obtained by step 2) is molded by various means, green compact can be obtained.Preferably, by step 2) gained solidfied material carries out ball milling, compression moulding.The time of the ball milling is 20~120min.
Step 3) is thermal cracking processes, so that organic polymer is cracked into the inorganic material of amorphous state by the process；It should Process is Cross-linked presoma to the transfer process of the covalent ceramics of amorphous, by organic and inorganic conversion process, net high-polymer into Row in-situ restructuring forms new keys, while changing with the volume and density of entire material.In the invention, after pyrolysis, at The shrinking percentage of type green compact (disk) is 25~30%.
In step 4), the rate of the heating is 25~45 DEG C/min.It is described to be cooled to furnace cooling.Preferably, microwave treatment Precursor ceramic is placed in attemperator by process, is put into microwave resonance intracavitary together and is handled.Using above-mentioned processing mode, It can make the progress of microwave mass transport process uniformly, stable.
Polymer precursor ceramic microwave after-treatment modification method provided by the invention, pyrolysis and microwave heating process are in nitrogen It is carried out under gas shielded, can avoid the areas material Zhong Tan and aoxidized in preparation process；Microwave heating have can realize volume heating, choosing The heating of selecting property, pollution are less, low energy consumption, promote the advantages that mass transfer, pass through the choosing to Si-C-N (O) tetrahedral amorphous matrix and carbon area Selecting property heats, and can prepare thermal stability and the excellent PRECURSOR-DERIVED CERAMICS of electrical properties in high temperatures；This method is simple for process, operation side Just, the stability of gained ceramics is good.
Description of the drawings
Fig. 1 is the I-V curve figure of PRECURSOR-DERIVED CERAMICS obtained by embodiment；
Fig. 2 is the XRD diagram of PRECURSOR-DERIVED CERAMICS obtained by embodiment；
Fig. 3 is the Raman figure of PRECURSOR-DERIVED CERAMICS obtained by embodiment；
Fig. 4 is the XPS figures of PRECURSOR-DERIVED CERAMICS obtained by embodiment；
Fig. 5 is the I-V curve figure of PRECURSOR-DERIVED CERAMICS obtained by comparative example；
Fig. 6 is the XRD diagram of PRECURSOR-DERIVED CERAMICS obtained by comparative example；
Fig. 7 is the Raman figure of PRECURSOR-DERIVED CERAMICS obtained by comparative example；
Fig. 8 is the XPS figures of PRECURSOR-DERIVED CERAMICS obtained by comparative example.
Specific implementation mode
The present invention is further explained in the light of specific embodiments.
Embodiment
A kind of polymer precursor ceramic microwave after-treatment modification method of the present embodiment, includes the following steps：
1) in N2Under protection, by polysilazane and hot-setter with 95:5 mass ratio mixing, 1h is stirred at 80 DEG C, is mixed Close object；The structure of polysilazane is as shown in Equation 1；Hot-setter is cumyl peroxide；
2) mixture obtained by step 1) under vacuum, is cured into 3h at 140 DEG C in scintillation vial, is cured Object；By solidfied material with after high-energy ball milling ball milling 30min, it is pressed into diameter 20mm, the disk that thickness is about 2.4mm；
3) under nitrogen protection, disk is placed in tube furnace and is pyrolyzed 4h in 1000 DEG C, obtains precursor ceramic；
4) under nitrogen protection, precursor ceramic is placed in attemperator, it is micro- to be put into the progress of microwave resonance intracavitary together Wave processing, control heating rate be 35 DEG C/min, after being warming up to 1000 DEG C, heat preservation 30min, furnace cooling to get.
Comparative example
The preparation method of the polymer precursor ceramics of comparative example, includes the following steps：
1) in N2Under protection, by polysilazane and hot-setter with 95:5 mass ratio mixing, 1h is stirred at 80 DEG C, is mixed Close object；
2) mixture obtained by step 1) under vacuum, is cured into 3h at 140 DEG C in scintillation vial, is cured Object；By solidfied material with after high-energy ball milling ball milling 30min, it is pressed into diameter 20mm, the disk that thickness is about 2.4mm；
3) under nitrogen protection, disk is placed in tube furnace and is pyrolyzed 4h in 1000 DEG C；
4) under nitrogen protection, disk is placed in tube furnace and handles 30min in 1000 DEG C of reheating, control heating rate is 35 DEG C/min to get.
Test example
Detect the I-V performances of PRECURSOR-DERIVED CERAMICS obtained by each embodiment and comparative example, polishing material surface before detection resistance rate, And silver paste is coated as electrode.Resistivity is calculated according to the size of disk, the results are shown in Table 1.
The resistivity of PRECURSOR-DERIVED CERAMICS obtained by 1 embodiment and comparative example of table
Project Resistivity, Ω cm
Embodiment 1 5.95×106
Comparative example 1 2.41×108
Fig. 1, Fig. 5 are respectively embodiment, PRECURSOR-DERIVED CERAMICS obtained by comparative example carries out the I-V curve figure of resistivity measurement；Knot The test result of table 1 is closed it is found that under 1000 DEG C of pyrolysis temperature, is reduced by the resistivity of PDC ceramics obtained by microwave treatment More than 2 orders of magnitude, i.e., electric conductivity is greatly improved.Illustrate that this method is particularly suitable for changing for low temperature PDC ceramics Property, under the premise of low energy consumption, be fast and effeciently improved to the performance of PDC ceramics.
This test example is detected the basal body structure of PRECURSOR-DERIVED CERAMICS obtained by embodiment, comparative example, XRD diagram such as Fig. 2, figure Shown in 6.As seen from the figure, microwaved front and back, Si-C-N (O) tetrahedron matrix is amorphous state.It is illustrated in 1000 DEG C of progress Microwave treatment matrix still keeps amorphous state.
Fig. 3, Fig. 7 be respectively embodiment, the Raman figure of PRECURSOR-DERIVED CERAMICS obtained by comparative example, is existed by the peaks D, the peaks G in figure It is found that the equal carbon containing free state in product；And all from the reduction of the peaks D of Raman figure and G peak widths and the increase of the peak positions G Illustrate that the crystallinity of free state carbon after microwave treatment is significantly improved.
Fig. 4, Fig. 8 be respectively embodiment, the XPS of PRECURSOR-DERIVED CERAMICS obtained by comparative example figures, and it is quasi- to carry out C1s to the carbon spectrum of sample After conjunction formed key be C-Si, C=C and C-C/H, as a result as shown in table 2 below.The carbon of C-Si keys and C=C keys belongs to SP2Hydridization Carbon, C-C/H keys be SP3The carbon of hydridization.As seen from the results in Table 2：SP has had occurred in the carbon in sample after microwave treatment3 Hydridization is to SP2Hydridization converts, SP2The C=C keys carbon of hydridization can improve electric conductivity, this is corresponding with the raising of the conductivity of front , thus we can show that microwave can promote SP at 1000 DEG C or so3The carbon of hydridization is to SP2Hydridization converts, and then can be real Now to the quick modification of PDC.
The fitting result of the XPS figures of PRECURSOR-DERIVED CERAMICS obtained by 2 embodiment and comparative example of table
Project C-Si C=C C-C/H
Embodiment 27.89% 41.54% 30.57%
Comparative example 27.90% 24.73% 47.37%

Claims (5)

1. a kind of polymer precursor ceramic microwave after-treatment modification method, which is characterized in that include the following steps：
1) polysilazane precursor is mixed with hot-setter under nitrogen protection, obtains mixture；The polysilazane pioneer Body has structure shown in formula 1：
In formula 1, x=2, y=8；
The hot-setter is cumyl peroxide；The mass ratio of polysilazane precursor and hot-setter is 90~95:5~ 10；
2) mixture obtained by step 1) under vacuum, is subjected to heat cure at 110~200 DEG C, obtains solidfied material；
3) solidfied material obtained by step 2) under nitrogen protection, is pyrolyzed 4h in 1000 DEG C in tube furnace, obtains precursor ceramic；
4) precursor ceramic obtained by step 3) under nitrogen protection, is warming up to 1000 DEG C using microwave, keeps the temperature 30min, it is cooling, To obtain the final product；The rate of the heating is 25~45 DEG C/min.
2. polymer precursor ceramic microwave after-treatment modification method as described in claim 1, which is characterized in that step 1) In, described be mixed into is stirred；Stirring carries out at 60~100 DEG C, and the time of stirring is 0.5~2h.
3. polymer precursor ceramic microwave after-treatment modification method as described in claim 1, which is characterized in that step 2) In, the thermal curing time is 2~5h.
4. polymer precursor ceramic microwave after-treatment modification method as described in claim 1, which is characterized in that step 2) In, gained solidfied material is subjected to ball milling, compression moulding.
5. polymer precursor ceramic microwave after-treatment modification method as described in claim 1, which is characterized in that step 4) In, it is described to be cooled to furnace cooling.
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CN108341674B (en) * 2018-02-05 2020-07-31 郑州大学 Polymer precursor ceramic composite aerogel and microwave synthesis method thereof
CN109456062B (en) * 2018-12-10 2021-06-25 郑州大学 PcBN cutter and preparation method thereof
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5698485A (en) * 1993-05-14 1997-12-16 Hoechst Aktiengesellschaft Process for producing ceramic microstructures from polymeric precursors
CN1800098A (en) * 2005-01-05 2006-07-12 中国科学院长春光学精密机械与物理研究所 Preparation method of Si-B-C-N amorphous ceramic material for high temperature sensing device
CN104328478A (en) * 2014-08-14 2015-02-04 郑州航空工业管理学院 Preparation method of SiC crystal whisker

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5698485A (en) * 1993-05-14 1997-12-16 Hoechst Aktiengesellschaft Process for producing ceramic microstructures from polymeric precursors
CN1800098A (en) * 2005-01-05 2006-07-12 中国科学院长春光学精密机械与物理研究所 Preparation method of Si-B-C-N amorphous ceramic material for high temperature sensing device
CN104328478A (en) * 2014-08-14 2015-02-04 郑州航空工业管理学院 Preparation method of SiC crystal whisker

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Comparison of microwave hybrid and conventional heating of preceramic polymers to form silicon carbide and silicon oxycarbide ceramics;Gene A. Danko*等;《J. Am. Ceram. Soc.》;20001231;第83卷(第7期);第1617-1625页 *

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