CN105859298A - Microwave aftertreatment modifying method for polymer precursor-derived ceramics - Google Patents

Microwave aftertreatment modifying method for polymer precursor-derived ceramics Download PDF

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CN105859298A
CN105859298A CN201610188129.9A CN201610188129A CN105859298A CN 105859298 A CN105859298 A CN 105859298A CN 201610188129 A CN201610188129 A CN 201610188129A CN 105859298 A CN105859298 A CN 105859298A
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polymer precursor
microwave
modification method
precursor
temperature
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CN105859298B (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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    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

The invention discloses a microwave aftertreatment modifying method for polymer precursor-derived ceramics. The method comprises the following steps: (1) mixing a polysilazane precursor with a thermosetting agent under nitrogen protection; (2) carrying out thermosetting on the mixture at the temperature of 110 DEG C to 200 DEG C under vacuum conditions; (3) carrying out pyrolysis for 4 hours in a tube type furnace at the temperature of 1,000 DEG C under nitrogen protection; and (4) heating the pyrolysis product to the temperature of 1,000 DEG C by using microwaves under nitrogen protection, carrying out heat preservation for 30 minutes, and carrying out cooling, thereby obtaining modified polymer precursor-derived ceramics. In the prior art, a polymer precursor is modified through conventional heating, a relatively high temperature is usually required, and different degrees of crystallization of a matrix can be caused. The high-temperature thermal stability and electric properties of ceramic materials are greatly dependent on a ceramic amorphous matrix, and the performance of products is always affected by the crystallization of different degrees. Thus, the microwaves are used to carry out rapid low-temperature modification on PDC, and an amorphous state for the matrix is maintained while the performance of the material is greatly improved.

Description

A kind of polymer precursor ceramic microwave after-treatment modification method
Technical field
The invention belongs to polymer precursor ceramic technology field, after being specifically related to a kind of polymer precursor ceramic microwave Process method of modifying.
Background technology
Polymer precursor method is a kind of method utilizing polymer precursor conversion to prepare ceramic material, accordingly pottery Material can be referred to as polymer precursor pottery (PDC).Can as the type of polymer of precursor have Polycarbosilane, polysilazane, Polysiloxanes, polyborazine etc..Polymer precursor pottery (PDC) is the refractory ceramics that a class is novel, and it is to pass through high-temperature hot Solve what (800～1000 DEG C) silicon-containing polymer precursor obtained, generally by Si-C-N (O) tetrahedral amorphous matrix and free carbon group Become.
The typical process of polymer precursor method includes the crosslinking of preceramic polymer, inorganization and crystallization process；Crosslinking Process makes polymeric preceramic precursor chain grow up or form network structure, to improve heat endurance, 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 slowly splits Solution is converted into amorphous state inorganic material, and it comprises chain fracture, low-molecular weight polymer and micro-molecular gas discharge etc.；Crystallization mistake Journey can improve the performances such as anti-oxidant, corrosion-resistant, makes that ceramic matrix is finer and close, mechanical performance is more preferable.
PDC pottery has the 26S Proteasome Structure and Function characteristic of a series of excellence.Functionally, PDC pottery has the temperature of excellence Degree-resistance characteristic, resistance can reduce along with the rising of temperature, and this characteristic can remain to 1300 DEG C, is significantly larger than SiC material (650 DEG C)；Structurally, being easily doped it, the PDC of B doping has prominent high high-temp stability, can With at 2000 DEG C of stable existences, without obvious degradation；Meanwhile, the PDC of Al doping has the high-temperature oxidation resistance and anticorrosive of excellence Property, oxidation rate is less 10 times than CVD-SiC, and this advantage along with test temperature rising more and more significant.PDC method can It is applicable to millimeter, micron and nano-sized ceramic parts, it is possible to use the polymer shaping works such as micro Process, micro-casting, photoetching Skill prepares the ceramic material of complicated shape, has preparation technology simple, the feature of low cost.
Tang Yun etc. (SCI, phase August 29 in 2008) utilize precursor pyrolysis and hot pressing to be prepared for a kind of Si-B- N-C ceramic fibre, it is with PVDF hollow fiber membrane as precursor, high temperature pyrolysis, sintering in melt spinning, cure treatment and nitrogen Obtain Si-B-N-C ceramic fibre.Fiber mainly has Si3N4, the phase composition such as BN and SiC, its room temperature tensile intensity is 2.1GPa, tool There are good amorphous stability and high-temperature oxidation resistance.
In prior art, general modifies to polymeric preceramic by conventional heating, generally require higher temperature, can lead Cause matrix to crystallize to some extent.And the high high-temp stability of ceramic material and electrical property, especially thermo-resistive effect are largely Depend on pottery noncrystal substrate, crystallization in various degree often leads to the performance of product and is affected.Thus we carry Go out to utilize microwave that PDC carries out fast low temperature speed modified, make material keep the amorphous of matrix while performance has the biggest lifting State.
Summary of the invention
It is an object of the invention to provide a kind of polymer precursor ceramic microwave after-treatment modification method, thus solve existing Conventional heating means deficiency in prepared by polymer precursor pottery.
In order to realize object above, the technical solution adopted in the present invention is:
A kind of polymer precursor ceramic microwave after-treatment modification method, comprises the following steps:
1) under nitrogen protection, polysilazane precursor is mixed with hot-setter, obtains mixture；
2) under vacuum, by step 1) gained mixture carries out heat cure at 110～200 DEG C, obtains solidfied material；
3) under nitrogen protection, by step 2) gained solidfied material in tube furnace at 1000 DEG C be pyrolyzed 4h, obtain forerunner Body pottery；
4) under nitrogen protection, by step 3) gained precursor ceramic utilizes microwave to be warming up to 1000 DEG C, is incubated 30min, Cooling, to obtain final product.
The polymer precursor ceramic microwave after-treatment modification method that the present invention provides, with polysilazane as precursor, logical Cross heat cure, pyrolysis step obtains ceramic inorganic thing, is obtained the PRECURSOR-DERIVED CERAMICS of excellent performance further by heating using microwave.First The performance driving body pottery has the biggest relation, by free carbon with Si-C-N (O) tetrahedral amorphous matrix in its structure and free carbon Heat endurance and the electric conductivity of material are had significant effect by structure and the form in the carbon district of composition；Traditional mode of heating together with Time noncrystal substrate and carbon district are acted on, the degree of crystallinity making material overall improves, and the difference of crystallization degree often leads to precursor pottery The performance of porcelain produces big deviation.Step 4) utilize amorphous Si district different to the responding ability of microwave with carbon district: carbon district is to microwave Responding ability be better than Si district, realize amorphous Si district and carbon district with heating using microwave and be heated to some extent, it is achieved to polymer The quick modification of precursor ceramic.
Step 1) and step 2) it is the crosslinking curing process of polysilazane, the molecule of preceramic polymer is made by this process Chain is grown up or cross-links, and to improve heat endurance, ceramic yield, reduces hole and crackle, improves compactness.
Preferably, step 1) in, described polysilazane precursor has a structure shown in formula 1:
In formula 1, x=2, y=8.Polysilazane precursor synthesize prior art, chlorosilane ammonolysis process can be passed through, urge Fluidized dehydrogenation coupling, ring-opening polymerisation or transistion metal compound catalytic dehydrogenation methods obtain the polysilazane precursor of said structure.
Described hot-setter is cumyl peroxide.Polysilazane precursor is 90～95:5 with the mass ratio of hot-setter ～10.Described being mixed into stirs mixing；Described stirring is carried out at 60～100 DEG C, and the time of stirring is 0.5～2h.Step 2) In, described thermal curing time is 2～5h.
In this invention, by step 2) gained solidfied material is molded by various means, available green compact.Preferably, by step 2) gained solidfied material carries out ball milling, compressing.The time of described ball milling is 20～120min.
Step 3) it is thermal cracking processes, make organic polymer be cracked into the inorganic material of amorphous state by this process；Should Process is the Cross-linked presoma transfer process to amorphous covalency pottery, and by organic and inorganic conversion process, net high-polymer enters Row restructuring in situ, forms new key, and volume and density with whole material change simultaneously.In this invention, after pyrolysis, become The shrinkage factor of type green compact (disk) is 25～30%.
Step 4) in, the speed of described intensification is 25～45 DEG C/min.It is described that to be cooled to stove cold.Preferably, microwave treatment Precursor ceramic is placed in attemperator by process, together puts into microwave cavity and processes.Use above-mentioned processing mode, The carrying out that microwave mass transport process is uniform, stable can be made.
The polymer precursor ceramic microwave after-treatment modification method that the present invention provides, pyrolysis and microwave heating process are at nitrogen Carry out under gas shielded, material Zhong Tan district can be avoided to aoxidize in preparation process；Heating using microwave has can realize volume heating, choosing The heating of selecting property, pollution are less, energy consumption is low, promote the advantages such as mass transfer, by Si-C-N (O) tetrahedral amorphous matrix and the choosing in carbon district Selecting property heats, and can prepare heat endurance and the PRECURSOR-DERIVED CERAMICS of electrical properties in high temperatures excellence；The method technique is simple, operation side Just, the stability of gained pottery is good.
Accompanying drawing explanation
Fig. 1 is the I-V curve figure of embodiment gained PRECURSOR-DERIVED CERAMICS；
Fig. 2 is the XRD of embodiment gained PRECURSOR-DERIVED CERAMICS；
Fig. 3 is the Raman figure of embodiment gained PRECURSOR-DERIVED CERAMICS；
Fig. 4 is the XPS figure of embodiment gained PRECURSOR-DERIVED CERAMICS；
Fig. 5 is the I-V curve figure of comparative example gained PRECURSOR-DERIVED CERAMICS；
Fig. 6 is the XRD of comparative example gained PRECURSOR-DERIVED CERAMICS；
Fig. 7 is the Raman figure of comparative example gained PRECURSOR-DERIVED CERAMICS；
Fig. 8 is the XPS figure of comparative example gained PRECURSOR-DERIVED CERAMICS.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment
A kind of polymer precursor ceramic microwave after-treatment modification method of the present embodiment, comprises the following steps:
1) at N2Under protection, polysilazane is mixed with the mass ratio of 95:5 with hot-setter, stir 1h at 80 DEG C, mixed Compound；The structure of polysilazane is as shown in Equation 1；Hot-setter is cumyl peroxide；
2) under vacuum, by step 1) gained mixture in scintillation vial at 140 DEG C solidify 3h, solidified Thing；By solidfied material with after high-energy ball milling ball milling 30min, being pressed into diameter 20mm, thickness is about the disk of 2.4mm；
3) under nitrogen protection, disk is placed in tube furnace and is pyrolyzed 4h in 1000 DEG C, obtain precursor ceramic；
4) under nitrogen protection, precursor ceramic is placed in attemperator, together puts into microwave cavity and carry out micro- Ripple processes, and controlling heating rate is 35 DEG C/min, after being warming up to 1000 DEG C, is incubated 30min, and stove is cold, to obtain final product.
Comparative example
The preparation method of the polymer precursor pottery of comparative example, comprises the following steps:
1) at N2Under protection, polysilazane is mixed with the mass ratio of 95:5 with hot-setter, stir 1h at 80 DEG C, mixed Compound；
2) under vacuum, by step 1) gained mixture in scintillation vial at 140 DEG C solidify 3h, solidified Thing；By solidfied material with after high-energy ball milling ball milling 30min, being pressed into diameter 20mm, thickness is about the disk of 2.4mm；
3) under nitrogen protection, disk is placed in tube furnace in 1000 DEG C of pyrolysis 4h；
4) under nitrogen protection, being placed in tube furnace by disk and process 30min in 1000 DEG C of reheating, controlling heating rate is 35 DEG C/min, to obtain final product.
Test example
Detect each embodiment and the I-V performance of comparative example gained PRECURSOR-DERIVED CERAMICS, detect polishing material surface before resistivity, And coat silver slurry as electrode.Size calculation resistivity according to disk, its result is as shown in table 1.
Table 1 embodiment and the resistivity of comparative example gained PRECURSOR-DERIVED CERAMICS
Project Resistivity, Ω cm
Embodiment 1 5.95×106
Comparative example 1 2.41×108
Fig. 1, Fig. 5 respectively embodiment, comparative example gained PRECURSOR-DERIVED CERAMICS carry out the I-V curve figure of resistivity measurement；Knot The result of the test closing table 1 understands, and under the pyrolysis temperature of 1000 DEG C, the resistivity through microwave treatment gained PDC pottery reduces More than 2 orders of magnitude, i.e. electric conductivity is greatly improved.Illustrate that the method is particularly suited for changing of low temperature PDC pottery Property, thus on the premise of low energy consumption, fast and effeciently the performance of PDC pottery is improved.
The basal body structure of embodiment, comparative example gained PRECURSOR-DERIVED CERAMICS is detected by this test example, XRD such as Fig. 2, figure Shown in 6.As seen from the figure, microwaved before and after, Si-C-N (O) tetrahedron matrix is amorphous state.It is illustrated in 1000 DEG C to carry out Microwave treatment matrix still keeps amorphous state.
Fig. 3, Fig. 7 are respectively embodiment, the Raman figure of comparative example gained PRECURSOR-DERIVED CERAMICS, the D peak in figure, G peak exist Understand, product all contains the carbon of free state；And the increase from the D peak of Raman figure and the reduction of G peak width and G peak position is all After microwave treatment is described, the degree of crystallinity of free state carbon is significantly improved.
Fig. 4, Fig. 8 are respectively the XPS figure of embodiment, comparative example gained PRECURSOR-DERIVED CERAMICS, and the carbon spectrum of sample is carried out C1s plan After conjunction, formed key is C-Si, C=C and C-C/H, and result is as shown in table 2 below.The carbon of C-Si key and C=C key belongs to SP2Hydridization Carbon, C-C/H key is SP3The carbon of hydridization.As seen from the results in Table 2: the carbon in sample after microwave treatment there occurs SP3 Hydridization is to SP2Hydridization converts, SP2The C=C key carbon of hydridization can improve electric conductivity, and this improves with electrical conductivity above is corresponding , thus we can show that microwave can promote SP at about 1000 DEG C3The carbon of hydridization is to SP2Hydridization converts, and then the most real The now quick modification to PDC.
The fitting result of the XPS figure of table 2 embodiment and comparative example gained PRECURSOR-DERIVED CERAMICS
Project C-Si C=C C-C/H
Embodiment 27.89% 41.54% 30.57%
Comparative example 27.90% 24.73% 47.37%

Claims (9)

1. a polymer precursor ceramic microwave after-treatment modification method, it is characterised in that comprise the following steps:
1) under nitrogen protection, polysilazane precursor is mixed with hot-setter, obtains mixture；
2) under vacuum, by step 1) gained mixture carries out heat cure at 110～200 DEG C, obtains solidfied material；
3) under nitrogen protection, by step 2) gained solidfied material in tube furnace in 1000 DEG C be pyrolyzed 4h, obtain precursor ceramic；
4) under nitrogen protection, by step 3) gained precursor ceramic utilizes microwave to be warming up to 1000 DEG C, is incubated 30min, cooling, Obtain.
2. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 1) In, described polysilazane precursor has a structure shown in formula 1:
In formula 1, x=2, y=8.
3. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 1) In, described hot-setter is cumyl peroxide.
4. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 1) In, polysilazane precursor is 90～95:5～10 with the mass ratio of hot-setter.
5. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 1) In, described in be mixed into stirring mixing；Stirring is carried out at 60～100 DEG C, and the time of stirring is 0.5～2h.
6. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 2) In, described thermal curing time is 2～5h.
7. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 2) In, gained solidfied material is carried out ball milling, compressing.
8. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 4) In, the speed of described intensification is 25～45 DEG C/min.
9. polymer precursor ceramic microwave after-treatment modification method as claimed in claim 1, it is characterised in that step 4) In, described in be cooled to stove cold.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108341674A (en) * 2018-02-05 2018-07-31 郑州大学 A kind of polymer precursor Ceramic Composite aeroge and its microwave synthesis method
CN109456062A (en) * 2018-12-10 2019-03-12 郑州大学 A kind of PcBN cutter and preparation method thereof
CN111660211A (en) * 2019-12-31 2020-09-15 河南联合精密材料股份有限公司 Polycrystalline diamond-like abrasive and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108341674A (en) * 2018-02-05 2018-07-31 郑州大学 A kind of polymer precursor Ceramic Composite aeroge and its microwave synthesis method
CN108341674B (en) * 2018-02-05 2020-07-31 郑州大学 Polymer precursor ceramic composite aerogel and microwave synthesis method thereof
CN109456062A (en) * 2018-12-10 2019-03-12 郑州大学 A kind of PcBN cutter and preparation method thereof
CN111660211A (en) * 2019-12-31 2020-09-15 河南联合精密材料股份有限公司 Polycrystalline diamond-like abrasive and preparation method thereof

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