CN104591741A - Method for preparing SiNCB ceramic material - Google Patents
Method for preparing SiNCB ceramic material Download PDFInfo
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- CN104591741A CN104591741A CN201510086371.0A CN201510086371A CN104591741A CN 104591741 A CN104591741 A CN 104591741A CN 201510086371 A CN201510086371 A CN 201510086371A CN 104591741 A CN104591741 A CN 104591741A
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Abstract
The invention discloses a method for preparing a SiNCB ceramic material, relates to a method for preparing a ceramic material, and aims to solve the problems that a SiNCB ceramic material prepared by using a conventional method has high possibility of crystallization and instable at high temperature. The method comprises the following steps: I, putting a nitrogen source, a silicon source, an acid-binding agent and a solvent into a reactor to react at the room temperature under the protection of an inert gas; II, performing vacuum extraction filtration on the reaction product, mixing with borane tetrahydrofuran, and putting into a reactor to react; III, adding a boron trichloride n-hexane into the reactor to react, and heating to be the room temperature; IV, performing extraction filtration on the product, and performing vacuum rotary evaporation to obtain a ceramic precursor; V, putting the ceramic precursor into a tubular furnace, performing pyrolysis, and cooling to be the room temperature along the furnace to obtain the SiNCB ceramic material. The SiNCB ceramic material is excellent in oxidation resistance at 1450 DEG C and is not decomposed or crystallized when being used for a long time. The method can be applied to the field of silicon-based ceramic materials.
Description
Technical field
The present invention relates to a kind of preparation method of stupalith.
Background technology
Silicon based ceramic has the performances such as higher thermostability, oxidation-resistance and creep resistance and is widely used in the fields such as national defence, chemistry, aerospace and medical science due to it.Precursor polymer conversion method prepares hi-tech silicon based ceramic, can non-crystallizable below 1400 DEG C, do not decompose, be not oxidized, there is very excellent high-temperature behavior, make ceramics there occurs important breakthrough.In recent years, some impressive progresses are obtained, as found the various functional performance relevant to PDC.In addition, be deep into molecular level and be conducive to the high chemical stability of people to PDC, various superior and unique performance studies such as high temperature resistant creep properties or characteristic of semiconductor from the angle inquiring into its structure.There are some researches show, the raising of Boron contents serves keying action to suppressing the formation of crystal.But under keeping the prerequisite of relatively low cost, the raising relative difficult of B content.The ceramic productive rate of SiNCB pottery prepared by existing synthetic route is lower, and less than 1400 DEG C start crystallization, is unfavorable for high-temperature stability and the creep property of pottery.
Summary of the invention
The present invention will solve the easy crystallization of SiNCB stupalith prepared by existing method, and problem unstable under high temperature, provides a kind of preparation method of SiNCB stupalith.
The preparation method of SiNCB stupalith of the present invention, carries out according to the following steps:
One, nitrogenous source, silicon source, acid binding agent and solvent are put into the reactor with protection of inert gas, 16h is reacted under room temperature condition, wherein the mol ratio in nitrogenous source and silicon source is 1 ~ 2:1, and the mol ratio of silicon source and solvent is 1:1 ~ 5, and the mol ratio of silicon source and acid binding agent is 2:1;
Two, the reaction product of step one is carried out vacuum filtration, by the borine tetrahydrofuran (THF) of the liquid after suction filtration and 2mol/L according to the mixed in molar ratio of 1:1, put into the reactor with protection of inert gas, under the condition of 0 DEG C, react 12h;
Three, in reactor, then add the boron trichloride hexane solution of 1mol/L, the mol ratio of the product in reactor and boron trichloride hexane solution is 1:3, is warming up to room temperature after reacting 12h under the condition of 0 DEG C;
Four, product step 3 obtained carries out suction filtration, and gained filtrate is carried out rotary evaporation in vacuo process, and the viscous liquid obtained is SiNCB ceramic forerunner;
Five, SiNCB ceramic forerunner is put into tube furnace, under argon gas or nitrogen atmosphere, carry out pyrolysis, then cool to room temperature with the furnace, namely obtain SiNCB stupalith.
Namely Polymer-pyrolysis process for Material synthesis has gone out SiCNB precursor polymer, then is obtained SiCNB stupalith with organic boron and nitrogenous silane by the present invention further, and reaction conditions is gentle, and simple to operate, productive rate is higher, pollutes few; Method of the present invention is nitrogenous source with silazane, take chlorosilane as silicon source, reduces material cost, improves the content of Si in material system, thus improves security performance and the stability of system, reduces thermal conductivity and the thermal expansivity of material; The stupalith that the inventive method obtains is black solid material, at 1450 DEG C, have excellent oxidation-resistance, can not decompose by life-time service, not crystallization.Boron contents in SiCNB stupalith of the present invention is enhanced, and the ceramic productive rate of material and high-temperature stability are also improved significantly.
Accompanying drawing explanation
Fig. 1 is the optics picture of SiNCB stupalith prepared by embodiment 1; Fig. 2 is the x-ray photoelectron power spectrum of SiNCB ceramic forerunner after thermal treatment under differing temps; Fig. 3 is the X-ray powder diffracting spectrum of SiNCB ceramic forerunner polymkeric substance after 1600 DEG C of thermal treatment; Fig. 4 is thermogravimetry coupling dsc analysis chart (TG-DSC) of SiNCB ceramic forerunner polymkeric substance.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment SiNCB stupalith, carry out according to the following steps:
One, nitrogenous source, silicon source, acid binding agent and solvent are put into the reactor with protection of inert gas, 16h is reacted under room temperature condition, wherein the mol ratio in nitrogenous source and silicon source is 1 ~ 2:1, and the mol ratio of silicon source and solvent is 1:1 ~ 5, and the mol ratio of silicon source and acid binding agent is 2:1;
Two, the reaction product of step one is carried out vacuum filtration, by the borine tetrahydrofuran (THF) of the liquid after suction filtration and 2mol/L according to the mixed in molar ratio of 1:1, put into the reactor with protection of inert gas, under the condition of 0 DEG C, react 12h;
Three, in reactor, then add the boron trichloride hexane solution of 1mol/L, the mol ratio of the product in reactor and boron trichloride hexane solution is 1:3, is warming up to room temperature after reacting 12h under the condition of 0 DEG C;
Four, product step 3 obtained carries out suction filtration, and gained filtrate is carried out rotary evaporation in vacuo process, and the viscous liquid obtained is SiNCB ceramic forerunner;
Five, SiNCB ceramic forerunner is put into tube furnace, under argon gas or nitrogen atmosphere, carry out pyrolysis, then cool to room temperature with the furnace, namely obtain SiNCB stupalith.
Rare gas element described in present embodiment is nitrogen or argon gas.
Present embodiment method just can be carried out at normal temperatures, preparation cost is relatively low, and building-up process is simple, and equipment requirements is simple, processing ease, controllability are good, there is good circulation ratio, the organic ceramic presoma that preparation has an excellent high-temperature stability has very real using value.
Embodiment two: present embodiment and embodiment one unlike: in step one, nitrogenous source is hexamethyldisilazane or quadrol.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: in step one silicon source be one or both in ethylene methacrylic silazane ylmethyl hydrogen silazane multipolymer, methylvinyldichlorosilane by arbitrarily than the mixture formed.Other is identical with embodiment one or two.
Embodiment four: present embodiment and embodiment three unlike: the preparation method of ethylene methacrylic silazane ylmethyl hydrogen silazane multipolymer is: be raw material by methylhydrochlorosilane, ethylene methacrylic chlorosilane and ammonia, is that solvent obtains in 70 DEG C of backflow 6h preparation with toluene.Other is identical with embodiment three.
Embodiment five: one of present embodiment and embodiment one to four unlike: in step one, acid binding agent is triethylamine.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: in step one, solvent is that one or more in hexanaphthene, normal hexane, pyridine, tetrahydrofuran (THF), toluene, benzene and diethylene glycol dimethyl ether are by arbitrarily than the mixture formed.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in step one, the mol ratio in nitrogenous source and silicon source is 1:1.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the mol ratio of silicon source and solvent is 1:2.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight are unlike the condition of rotary evaporation in step 4: pressure is-0.5 ~-0.9 normal atmosphere, and temperature is 60 ~ 80 DEG C.Other is identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the Heating temperature of pyrolysis in step 5 is 800 ~ 1100 DEG C, and soaking time is 4 ~ 6h.Other is identical with one of embodiment one to nine.
Embodiment 1:
The preparation method of the present embodiment SiNCB ceramic forerunner, carries out according to the following steps:
One, by the 2:1:1 mixing in molar ratio of quadrol, methylvinyldichlorosilane and ethylene methacrylic silazane ylmethyl hydrogen silazane multipolymer, add toluene and triethylamine again, mixture puts into the reactor with protection of inert gas, reacts 16h under room temperature condition;
Two, the reaction product of step one is carried out vacuum filtration, by the liquid after suction filtration and borine tetrahydrofuran (THF) according to the mixed in molar ratio of 1:1, put into the reactor with protection of inert gas, under the condition of 0 DEG C, react 12h;
Three, then in reactor, add boron trichloride hexane solution, the mol ratio of the product in reactor and boron trichloride hexane solution is 1:3, is warming up to room temperature after reacting 12h under the condition of 0 DEG C;
Four, product step 3 obtained carries out suction filtration, and gained filtrate is carried out rotary evaporation in vacuo process, and the condition of rotary evaporation is: pressure-0.7 normal atmosphere, temperature 70 C, and the viscous liquid obtained is SiNCB ceramic forerunner;
Five, SiNCB ceramic forerunner is put into tube furnace, under argon gas or nitrogen atmosphere, carry out pyrolysis, the Heating temperature of pyrolysis is 1000 DEG C, and soaking time is 5h, then cools to room temperature with the furnace, namely obtains SiNCB stupalith.
The present embodiment prepare obtained SiNCB stupalith can under 1450 DEG C of conditions life-time service not crystallization, do not decompose, there is excellent high temperature stability performance.
The optics picture of SiNCB ceramic forerunner prepared by the present embodiment is as (left: by product in Fig. 1; Right: SiCNB ceramic forerunner).
The x-ray photoelectron power spectrum of SiNCB ceramic forerunner after thermal treatment under differing temps is as Fig. 2, and as shown in Figure 2, along with the rising of temperature, the content of Si-N reduces gradually, and the content of B-N and Si-C increases gradually, is conducive to the thermostability of material.
The X-ray powder diffracting spectrum of SiNCB ceramic forerunner polymkeric substance (PSB1 and PSB2) after 1600 DEG C of thermal treatment is as in Fig. 3, Fig. 3 ● represent that SiC, △ represent Si
3n
4.In Fig. 3, PSB1 represents that the product that step 2 prepares, PSB2 represent SiNCB stupalith prepared by the present embodiment, increasing as shown in Figure 3 along with Boron contents in product, and the crystallization temperature of product raises gradually, and the thermostability of product is improved.
After 90 DEG C of solidifications, thermogravimetry coupling dsc analysis chart (TG-DSC) of SiCNB ceramic forerunner polymkeric substance (PSB1 and PSB2) is as Fig. 4.In Fig. 4, PSB1 represents that the product (being obtained by a kind of boron source) that step 2 prepares, PSB2 represent SiNCB stupalith (being obtained by two kinds of boron sources) prepared by the present embodiment.Range of measuring temp is room temperature to 1500 DEG C; Temperature rise rate is 10 DEG C of min
-1; Protective atmosphere is argon gas.As shown in Figure 4, SiCNB presoma completes at 800 DEG C of ceramics, and ceramic productive rate is about 80%, embodies better high-temperature stability.
Claims (10)
1. a preparation method for SiNCB stupalith, is characterized in that the method is carried out according to the following steps:
One, nitrogenous source, silicon source, acid binding agent and solvent are put into the reactor with protection of inert gas, 16h is reacted under room temperature condition, wherein the mol ratio in nitrogenous source and silicon source is 1 ~ 2:1, and the mol ratio of silicon source and solvent is 1:1 ~ 5, and the mol ratio of silicon source and acid binding agent is 2:1;
Two, the reaction product of step one is carried out vacuum filtration, by the borine tetrahydrofuran (THF) of the liquid after suction filtration and 2mol/L according to the mixed in molar ratio of 1:1, put into the reactor with protection of inert gas, under the condition of 0 DEG C, react 12h;
Three, in reactor, then add the boron trichloride hexane solution of 1mol/L, the mol ratio of the product in reactor and boron trichloride hexane solution is 1:3, is warming up to room temperature after reacting 12h under the condition of 0 DEG C;
Four, product step 3 obtained carries out suction filtration, and gained filtrate is carried out rotary evaporation in vacuo process, and the viscous liquid obtained is SiNCB ceramic forerunner;
Five, SiNCB ceramic forerunner is put into tube furnace, under argon gas or nitrogen atmosphere, carry out pyrolysis, then cool to room temperature with the furnace, namely obtain SiNCB stupalith.
2. the preparation method of a kind of SiNCB stupalith according to claim 1, is characterized in that in step one, nitrogenous source is hexamethyldisilazane or quadrol.
3. the preparation method of a kind of SiNCB stupalith according to claim 1 and 2, is characterized in that silicon source in step one is that one or both in ethylene methacrylic silazane ylmethyl hydrogen silazane multipolymer, methylvinyldichlorosilane are by arbitrarily than the mixture formed.
4. the preparation method of a kind of SiNCB stupalith according to claim 3, it is characterized in that the preparation method of ethylene methacrylic silazane ylmethyl hydrogen silazane multipolymer is: be raw material by methylhydrochlorosilane, ethylene methacrylic chlorosilane and ammonia, is that solvent obtains in 70 DEG C of backflow 6h preparation with toluene.
5. the preparation method of a kind of SiNCB stupalith according to claim 4, is characterized in that in step one, acid binding agent is triethylamine.
6. the preparation method of a kind of SiNCB stupalith according to claim 5, is characterized in that solvent in step one is that one or more in hexanaphthene, normal hexane, pyridine, tetrahydrofuran (THF), toluene, benzene and diethylene glycol dimethyl ether are by arbitrarily than the mixture formed.
7. the preparation method of a kind of SiNCB stupalith according to claim 6, is characterized in that the mol ratio in nitrogenous source and silicon source in step one is 1:1.
8. the preparation method of a kind of SiNCB stupalith according to claim 7, is characterized in that the mol ratio of silicon source and solvent is 1:2.
9. the preparation method of a kind of SiNCB stupalith according to claim 8, is characterized in that the condition of rotary evaporation in step 4: pressure is-0.5 ~-0.9 normal atmosphere, and temperature is 60 ~ 80 DEG C.
10. the preparation method of a kind of SiNCB stupalith according to claim 9, it is characterized in that the Heating temperature of pyrolysis in step 5 is 800 ~ 1100 DEG C, soaking time is 4 ~ 6h.
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| CN107540399A (en) * | 2017-09-18 | 2018-01-05 | 中科院广州化学有限公司南雄材料生产基地 | CNT toughness reinforcing SiBCN (O) metal matrix ceramic composite coatings and its preparation method |
| CN107739207A (en) * | 2017-09-19 | 2018-02-27 | 东华大学 | A kind of preparation method of amorphous Si-B-C-N zirconium aluminium 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 |
| CN112707741A (en) * | 2020-12-29 | 2021-04-27 | 哈尔滨工业大学 | Preparation method of CSiNB-based multielement integrated fiber felt material |
| CN115340379A (en) * | 2021-05-14 | 2022-11-15 | 中国科学院化学研究所 | High-carbon-content silicon-boron-carbon-nitrogen ceramic fiber and preparation method and application thereof |
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| CN112707741A (en) * | 2020-12-29 | 2021-04-27 | 哈尔滨工业大学 | Preparation method of CSiNB-based multielement integrated fiber felt material |
| 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 |
| CN115340379A (en) * | 2021-05-14 | 2022-11-15 | 中国科学院化学研究所 | High-carbon-content silicon-boron-carbon-nitrogen ceramic fiber and preparation method and application thereof |
| 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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