CN104591741B - A kind of preparation method of SiNCB ceramic material - Google Patents
A kind of preparation method of SiNCB ceramic material Download PDFInfo
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Abstract
The preparation method of a kind of SiNCB ceramic material, relates to the preparation method of a kind of ceramic material.The present invention is to solve the easy crystallize of SiNCB ceramic material prepared by existing method, problem unstable under high temperature.Method: one, put in the reactor with inert gas shielding by nitrogen source, silicon source, acid binding agent and solvent, reacts under room temperature condition；Two, by product vacuum filtration, mix with borine oxolane, put in reactor and react；Three, in reactor, add boron chloride hexane solution, after reaction, be warming up to room temperature；Four, by product sucking filtration, rotary evaporation in vacuo, ceramic forerunner is obtained；Five, ceramic forerunner is put in tube furnace, pyrolysis, cool to room temperature with the furnace, i.e. obtain SiNCB ceramic material.There is at 1450 DEG C excellent non-oxidizability, can not decompose by life-time service, not crystallization.The present invention is applied to silicon-based ceramic material field.
Description
Technical field
The present invention relates to the preparation method of a kind of ceramic material.
Background technology
Silicon based ceramic has the performances such as higher heat stability, non-oxidizability and creep resistant and is widely used in state due to it
The fields such as anti-, chemistry, Aero-Space and medical science.Precursor polymer conversion method prepares high-tech silicon based ceramic, it is possible to
Less than 1400 DEG C do not crystallize, do not decompose, do not aoxidize, and have the most excellent high-temperature behavior so that ceramics there occurs
Important breakthrough.In recent years, achieved with some impressive progresses, as found the various functional characteristics relevant to PDC.Additionally,
It is deep into molecular level and is conducive to people's high chemical stability to PDC, high temperature resistant creep properties from the angle inquiring into its structure
Or various superior and unique performance studys such as characteristic of semiconductor.There are some researches show, improving suppression crystal of Boron contents
Formation serves pivotal role.But on the premise of keeping relatively low cost, the raising relative difficult of B content.Existing
The ceramic productivity of SiNCB pottery prepared of synthetic route relatively low, and less than 1400 DEG C start crystallize, is unfavorable for pottery
High-temperature stability and croop property.
Summary of the invention
The present invention is to solve the easy crystallize of SiNCB ceramic material prepared by existing method, problem unstable under high temperature,
The preparation method of a kind of SiNCB ceramic material is provided.
The preparation method of SiNCB ceramic material of the present invention, sequentially includes the following steps:
One, nitrogen source, silicon source, acid binding agent and solvent are put in the reactor with inert gas shielding, anti-under room temperature condition
Answering 16h, wherein the mol ratio in nitrogen source and silicon source is 1～2:1, and the mol ratio of silicon source and solvent is 1:1～5, silicon source and acid binding agent
Mol ratio be 2:1；
Two, the product of step one is carried out vacuum filtration, by the borine oxolane of the liquid after sucking filtration Yu 2mol/L
According to the mixed in molar ratio of 1:1, put in the reactor with inert gas shielding, under conditions of 0 DEG C, react 12h；
Three, in reactor, then add the boron chloride hexane solution of 1mol/L, the product in reactor and tri-chlorination
The mol ratio of boron hexane solution is 1:3, is warming up to room temperature after reacting 12h under conditions of 0 DEG C；
Four, product step 3 obtained carries out sucking filtration, and gained filtrate is carried out rotary evaporation in vacuo process, the thickness obtained
Shape liquid is SiNCB ceramic forerunner；
Five, SiNCB ceramic forerunner is put in tube furnace, is pyrolyzed under argon or nitrogen atmosphere, then with
Stove is cooled to room temperature, i.e. obtains SiNCB ceramic material.
The present invention has gone out SiCNB precursor polymer with organic boron and nitrogenous silane for Material synthesis, further will polymerization
Thing pyrolysis processing i.e. obtains SiCNB ceramic material, and reaction condition is gentle, and simple to operate, productivity is higher, pollutes few；This
The method of invention, with silazane for nitrogen source, with chlorosilane for silicon source, reduces the cost of raw material, improves Si in material system
Content, thus improve security performance and the stability of system, reduce thermal conductivity and the thermal coefficient of expansion of material；This
The ceramic material that bright method obtains is black solid material, has excellent non-oxidizability at 1450 DEG C, can life-time service
Do not decompose, not crystallization.Boron contents in the SiCNB ceramic material of the present invention is enhanced, the ceramic productivity of material and height
Temperature stability is also improved significantly.
Accompanying drawing explanation
Fig. 1 is the optics picture of the SiNCB ceramic material of embodiment 1 preparation；Fig. 2 is SiNCB ceramic forerunner warp
Cross the x-ray photoelectron power spectrum after heat treatment under different temperatures；Fig. 3 is that SiNCB ceramic forerunner polymer is through 1600 DEG C
X-ray powder diffracting spectrum after heat treatment；Fig. 4 is the DTG coupling differential scanning of SiNCB ceramic forerunner polymer
Calorimetry analysis chart (TG-DSC).
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes appointing between each detailed description of the invention
Meaning combination.
Detailed description of the invention one: the preparation method of present embodiment SiNCB ceramic material, sequentially includes the following steps:
One, nitrogen source, silicon source, acid binding agent and solvent are put in the reactor with inert gas shielding, anti-under room temperature condition
Answering 16h, wherein the mol ratio in nitrogen source and silicon source is 1～2:1, and the mol ratio of silicon source and solvent is 1:1～5, silicon source and acid binding agent
Mol ratio be 2:1；
Two, the product of step one is carried out vacuum filtration, by the borine oxolane of the liquid after sucking filtration Yu 2mol/L
According to the mixed in molar ratio of 1:1, put in the reactor with inert gas shielding, under conditions of 0 DEG C, react 12h；
Three, in reactor, then add the boron chloride hexane solution of 1mol/L, the product in reactor and tri-chlorination
The mol ratio of boron hexane solution is 1:3, is warming up to room temperature after reacting 12h under conditions of 0 DEG C；
Four, product step 3 obtained carries out sucking filtration, and gained filtrate is carried out rotary evaporation in vacuo process, the thickness obtained
Shape liquid is SiNCB ceramic forerunner；
Five, SiNCB ceramic forerunner is put in tube furnace, is pyrolyzed under argon or nitrogen atmosphere, then with
Stove is cooled to room temperature, i.e. obtains SiNCB ceramic material.
Noble gas described in present embodiment is nitrogen or argon.
Present embodiment method the most just can be carried out, and preparation cost is relatively low, and building-up process is simple, equipment requirements letter
List, processing ease, controllability are good, have good repeatability, have the organic ceramic of excellent high-temperature stability in preparation
There is on presoma the most real using value.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: in step one, nitrogen source is hexamethyl
Disilazane or ethylenediamine.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: in step one, silicon source is first
One or both in base ethylene silazane ylmethyl hydrogen silazane copolymer, methylvinyldichlorosilane are by arbitrarily than composition
Mixture.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is unlike detailed description of the invention three: ethylene methacrylic silazane ylmethyl
The preparation method of hydrogen silazane copolymer is: be raw material by methylhydrochlorosilane, ethylene methacrylic chlorosilane and ammonia, with toluene
It is prepared at 70 DEG C of backflow 6h for solvent.Other is identical with detailed description of the invention three.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: tie up acid in step one
Agent is triethylamine.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: solvent in step one
For one or more in hexamethylene, normal hexane, pyridine, oxolane, toluene, benzene and diethylene glycol dimethyl ether by arbitrarily
Mixture than composition.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment is unlike one of detailed description of the invention one to six: nitrogen source in step one
It is 1:1 with the mol ratio in silicon source.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment is unlike one of detailed description of the invention one to seven: silicon source and solvent
Mol ratio is 1:2.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention one to eight: rotate in step 4
The condition of evaporation: pressure is-0.5～-0.9 atmospheric pressure, and temperature is 60～80 DEG C.Other with detailed description of the invention one to eight it
One is identical.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention one to nine: be pyrolyzed in step 5
Heating-up temperature be 800～1100 DEG C, temperature retention time is 4～6h.Other is identical with one of detailed description of the invention one to nine.
Embodiment 1:
The preparation method of the present embodiment SiNCB ceramic forerunner, sequentially includes the following steps:
One, by ethylenediamine, methylvinyldichlorosilane and ethylene methacrylic silazane ylmethyl hydrogen silazane copolymer by mole
Mixing than 2:1:1, add toluene and triethylamine, mixture is put in the reactor with inert gas shielding, room temperature bar
16h is reacted under part；
Two, the product of step one is carried out vacuum filtration, by the liquid after sucking filtration with borine oxolane according to 1:1's
Mixed in molar ratio, puts in the reactor with inert gas shielding, reacts 12h under conditions of 0 DEG C；
Three, then adding boron chloride hexane solution in reactor, the product in reactor is molten with boron chloride normal hexane
The mol ratio of liquid is 1:3, is warming up to room temperature after reacting 12h under conditions of 0 DEG C；
Four, product step 3 obtained carries out sucking filtration, and gained filtrate is carried out rotary evaporation in vacuo process, rotary evaporation
Condition is :-0.7 atmospheric pressure of pressure, temperature 70 C, and the viscous liquid obtained is SiNCB ceramic forerunner；
Five, SiNCB ceramic forerunner is put in tube furnace, be pyrolyzed under argon or nitrogen atmosphere, pyrolysis
Heating-up temperature is 1000 DEG C, and temperature retention time is 5h, then cools to room temperature with the furnace, i.e. obtains SiNCB ceramic material.
The present embodiment preparation obtained by SiNCB ceramic material can under the conditions of 1450 DEG C life-time service not crystallization, regardless of
Solve, there is excellent high temperature stability performance.
Optics picture such as Fig. 1 of SiNCB ceramic forerunner prepared by the present embodiment is (left: by-product；Right: SiCNB makes pottery
Porcelain presoma).
SiNCB ceramic forerunner x-ray photoelectron power spectrum such as Fig. 2 after heat treatment under different temperatures, can by Fig. 2
Knowing, along with the rising of temperature, the content of Si-N is gradually lowered, and the content of B-N and Si-C is gradually increased, beneficially material
Heat stability.
SiNCB ceramic forerunner polymer (PSB1 and PSB2) X-ray powder diffracting spectrum after 1600 DEG C of heat treatments
Such as Fig. 3, in Fig. 3 ● represent that SiC, △ represent Si3N4.In Fig. 3, PSB1 represents the product that step 2 prepares, PSB2
Represent the SiNCB ceramic material prepared of the present embodiment, as shown in Figure 3 along with the increasing of Boron contents in product, the crystalline substance of product
Changing temperature to gradually rise, the heat stability of product is improved.
The DTG coupling differential scanning calorimetry of SiCNB ceramic forerunner polymer (PSB1 and PSB2) after 90 DEG C of solidifications
Analysis chart (TG-DSC) is such as Fig. 4.In Fig. 4, PSB1 represents the product (being prepared by a kind of boron source) that step 2 prepares,
PSB2 represents SiNCB ceramic material (being prepared by two kinds of boron source) prepared by the present embodiment.Range of measuring temp be room temperature extremely
1500℃；Heating rate is 10 DEG C of min-1；Protective atmosphere is argon.As shown in Figure 4, SiCNB presoma is at 800 DEG C
Ceramic completes, and ceramic productivity is about 80%, embodies preferable high-temperature stability.
Claims (8)
1. the preparation method of a SiNCB ceramic material, it is characterised in that the method sequentially includes the following steps:
One, nitrogen source, silicon source, acid binding agent and solvent are put in the reactor with inert gas shielding, anti-under room temperature condition
Answering 16h, wherein the mol ratio in nitrogen source and silicon source is 1～2:1, and the mol ratio of silicon source and solvent is 1:1～5, silicon source and acid binding agent
Mol ratio be 2:1；
Two, the product of step one is carried out vacuum filtration, the borine oxolane of the liquid after sucking filtration with 2mol/L is pressed
According to the mixed in molar ratio of 1:1, put in the reactor with inert gas shielding, under conditions of 0 DEG C, react 12h；
Three, in reactor, then add the boron chloride hexane solution of 1mol/L, the product in reactor and boron chloride
The mol ratio of hexane solution is 1:3, is warming up to room temperature after reacting 12h under conditions of 0 DEG C；
Four, product step 3 obtained carries out sucking filtration, and gained filtrate is carried out rotary evaporation in vacuo process, the thickness obtained
Shape liquid is SiNCB ceramic forerunner；
Five, SiNCB ceramic forerunner is put in tube furnace, be pyrolyzed under argon or nitrogen atmosphere, then with stove
It is cooled to room temperature, i.e. obtains SiNCB ceramic material；
In step one, silicon source is ethylene methacrylic silazane ylmethyl hydrogen silazane copolymer, ethylene methacrylic silazane ylmethyl hydrogen silicon
The preparation method of azane copolymer is: be raw material by methylhydrochlorosilane, ethylene methacrylic chlorosilane and ammonia, is molten with toluene
Agent is prepared at 70 DEG C of backflow 6h.
The preparation method of a kind of SiNCB ceramic material the most according to claim 1, it is characterised in that nitrogen in step one
Source is hexamethyldisiloxane or ethylenediamine.
The preparation method of a kind of SiNCB ceramic material the most according to claim 1, it is characterised in that tie up in step one
Acid agent is triethylamine.
The preparation method of a kind of SiNCB ceramic material the most according to claim 3, it is characterised in that molten in step one
Agent is that one or more in hexamethylene, normal hexane, pyridine, oxolane, toluene, benzene and diethylene glycol dimethyl ether are by appointing
Meaning is than the mixture of composition.
The preparation method of a kind of SiNCB ceramic material the most according to claim 4, it is characterised in that nitrogen in step one
The mol ratio in source and silicon source is 1:1.
The preparation method of a kind of SiNCB ceramic material the most according to claim 5, it is characterised in that silicon source and solvent
Mol ratio be 1:2.
The preparation method of a kind of SiNCB ceramic material the most according to claim 6, it is characterised in that revolve in step 4
Turn the condition of evaporation: pressure is-0.5～-0.9 atmospheric pressure, and temperature is 60～80 DEG C.
The preparation method of a kind of SiNCB ceramic material the most according to claim 7, it is characterised in that heat in step 5
The heating-up temperature solved is 800～1100 DEG C, and temperature retention time is 4～6h.
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| CN107540399B (en) * | 2017-09-18 | 2020-01-17 | 中科院广州化学有限公司南雄材料生产基地 | Carbon nano tube toughened SiBCN (O) metal-based ceramic coating and preparation method thereof |
| CN107739207B (en) * | 2017-09-19 | 2021-05-11 | 东华大学 | Preparation method of amorphous silicon boron carbon nitrogen zirconium aluminum ceramic material |
| CN109369918A (en) * | 2018-10-29 | 2019-02-22 | 航天材料及工艺研究所 | A kind of high boron content Si-B-C-N presoma and preparation method thereof |
| CN109704778A (en) * | 2019-01-21 | 2019-05-03 | 武汉科技大学 | A kind of SiBCN ceramics and preparation method thereof |
| CN112707741B (en) * | 2020-12-29 | 2021-10-01 | 哈尔滨工业大学 | Preparation method of CSiNB-based multielement integrated fiber felt material |
| CN115340379B (en) * | 2021-05-14 | 2023-09-01 | 中国科学院化学研究所 | High-carbon-content silicon-boron-carbon-nitrogen ceramic fiber as well as preparation method and application thereof |
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| CN1293015C (en) * | 2004-04-14 | 2007-01-03 | 哈尔滨工业大学 | Process for preparing high temperature texture ceramic material SiBONC |
| CN101525234B (en) * | 2009-04-13 | 2011-08-10 | 哈尔滨工业大学 | Preparation method for SiBCN ceramic material |
| CN101700978A (en) * | 2009-11-11 | 2010-05-05 | 哈尔滨工业大学 | Method for preparing SiBCN(O) ceramic material |
| CN103881101A (en) * | 2014-03-18 | 2014-06-25 | 天津大学 | Polycarbosilazane precursor for silicon carbonitride ceramic and preparation method thereof |
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