CN105884374B - A method of preparing super alpha-phase silicon nitride using nano-tube - Google Patents

A method of preparing super alpha-phase silicon nitride using nano-tube Download PDF

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CN105884374B
CN105884374B CN201610416082.7A CN201610416082A CN105884374B CN 105884374 B CN105884374 B CN 105884374B CN 201610416082 A CN201610416082 A CN 201610416082A CN 105884374 B CN105884374 B CN 105884374B
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silicon nitride
tube
nano
phase silicon
alpha
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CN105884374A (en
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赵立旸
戎华
李钦稿
杜英
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Zhejiang lichen New Material Technology Co.,Ltd.
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Hangzhou Guinuo Technology Co Ltd
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Abstract

The invention discloses a kind of methods preparing alpha-phase silicon nitride using nano-tube, include the following steps：S1, by outer diameter be 50-500nm, internal diameter 20-300nm, specific surface area 20-100m2The nano-tube of/g carries out high-temperature ammonolysis in nitrogen, and the temperature of the high-temperature ammonolysis is 1220~1370 DEG C, and soaking time is 12~28h, obtains product 1；S2, the product 1 after S1 is subjected to planetary milling, the rotating speed of the planetary milling is 1000r/min, time is 20-30h, preparation method of the invention is simple for process, performance is controllable, and it is with short production cycle, significantly reduce energy consumption, be particularly suitable for preparing super alpha-phase silicon nitride.

Description

A method of preparing super alpha-phase silicon nitride using nano-tube
Technical field
The present invention relates to the preparation fields of silicon nitride more particularly to a kind of utilization nano-tube to prepare super alpha-phase silicon nitride Method.
Background technology
Silicon nitride is a kind of widely used special ceramic material.Its with high temperature resistant, proportion is small, intensity is high, hardness is big, The advantages that wear-resistant, is widely used in the industries such as automobile, military project, metallurgy, medical treatment.
The silicon nitride ceramics of high intensity, high rigidity in order to obtain, often using the silicon nitride powder of high α phases as raw material.This is Since in silicon nitride high-temperature sintering process, α phases can be changed into rodlike or acicular β phases, this to have certain length-width ratio β phases will contribute to the raising of silicon nitride ceramics intensity, hardness as toughened fiber.Therefore, the high nitrogen of α phase contents is prepared SiClx powder has actual significance of scientific research and application value.
But α phases are a kind of metastable state phases of silicon nitride, and silicon powder nitride reaction is a kind of strong exothermal reaction, so, During the high-temperature ammonolysis of silicon, the heat that reaction heat is released is easy to that reaction system is made to overheat so that α phase transition is equilibrium transport-β Phase.It is industrial generally to solve the problems, such as that this method is that a large amount of silicon nitride is added in reaction raw materials-silica flour as dispersant, with Reaction heat is evacuated, sintering is inhibited.But cost will be significantly greatly increased in this way, reduce production efficiency.And effect is limited, can not Obtain the silicon nitride of superelevation α.
In order to solve silica flour very exothermic in nitridation reaction reaction system is overheated so that the α phases content of generation is not High problem, expert both domestic and external have done a large amount of research.
Wherein, Fukuhira et al. is disclosed in the american documentation literature of Publication No. US5441694A a kind of preparing height The method of α phase silicon nitrides adds the compound of Cu or Cu as catalyst so that reaction temperature that is, in silicon powder nitride system It reduces, the reaction time shortens.In addition, the good capacity of heat transmission of Cu can help system more smoothly by heat derives, to drop The possibility of low system overheat, improves the content of α phases.But it since the density difference of Cu and Si are very big, is difficult to before reaction by two Person is uniformly mixed, and Cu is remained in silicon nitride as impurity after reaction, will influence the performance of silicon nitride sintering.
James.P et al. is in the United States Patent (USP) of Publication No. US25519124 it is also proposed that a kind of preceding processing of silicon powder nitride Technique first carries out silica flour advance heat treatment that is, before high-temperature ammonolysis at certain temperature and hydrogen atmosphere, wherein temperature Degree is 200~800 DEG C, and hydrogen content is 25~100% (V%) in atmosphere.This is because hydrogen can be by silicon face under low temperature Oxide layer reduction removal, contribute to the progress of subsequent nitridation reaction.Although this scheme can effectively shorten the reaction time, It is the use of the higher gaseous mixture of density of hydrogen to be to have certain dangerous under 200~800 DEG C of high temperature, do not meet industrialized The requirement of safety in production.
It is proposed in the Chinese patent of Publication No. CN102173396A and prepares doing for alpha-phase silicon nitride using revolving burner Method.During silicon powder nitride reacts, boiler tube is rotated so that reactant is overturn in boiler tube, this is conducive to silica flour and nitrogen is abundant Contact, and the heat dissipation of advantageous system can effectively improve the content of α phases in product.But the boiler tube rotated under high temperature is very It is easily deformed and is broken, this does not meet the production requirement for stablizing safety yet.
In addition, the scheme using two-step method silicon powder nitride is proposed in the Chinese patent of Publication No. CN102245503A, In this scheme, the first partial nitridation in 1150~1250 DEG C of cylindrical rotary furnace of warm area of silica flour, it is then transferred into 1250~ It is nitrogenized completely in 1350 DEG C of warm area.Although this scheme can also improve the content of α phases to a certain extent, equipment is wanted Ask very high, and operating process is complicated, the degree of first step nitridation is difficult to control, less reproducible, is also not suitable for industrial metaplasia Production.
Invention content
The present invention provides a kind of method preparing alpha-phase silicon nitride using nano-tube, method is simple and efficient, especially It is the silicon nitride that can obtain superelevation α phases.
A method of super alpha-phase silicon nitride being prepared using nano-tube, steps are as follows：
S1, by outer diameter be 50-500nm, internal diameter 20-300nm, specific surface area 20-100m2The nano-tube of/g is in nitrogen High-temperature ammonolysis is carried out in gas, the temperature of the high-temperature ammonolysis is 1220~1370 DEG C, and soaking time is 12~28h, obtains product 1；
S2, the product 1 after S1 is carried out to planetary milling, the rotating speed of the planetary milling is 1000r/ Min, time 20-30h, finished product.
Further preferably, the outer diameter of the nano-tube is 50-200nm, internal diameter 20-100nm, specific surface area 50- 100m2/g.Most preferably, the outer diameter of the nano-tube is 50-100nm, internal diameter 20-80nm, specific surface area 70-100m2/ g.Using it as raw material, α phases content highest in the silicon nitride being prepared.
Preferably, the temperature of the high-temperature ammonolysis is 1220~1370 DEG C, soaking time is 12~28h.
Preferably, the rotating speed of the planetary type ball-milling is 1000r/min, time 20-30h.
The present invention is using nano-tube as raw material, and first, specific surface area can reach 100m2/g, specific surface big in this way Product can increase considerably the contact area of nitrogen and silicon, improve reaction rate, shorten the time needed for reaction；Secondly, this hair The nano-tube structure of bright use is special, it has been investigated that, when silicon is reacted with nitrogen, a large amount of heat of release can To be dredged and be scattered and disappeared well by the pipe passage of its own, the effective temperature for controlling reaction system inhibits silica flour From be sintered, and then obtain superelevation α phase contents silicon nitride.
Description of the drawings
Fig. 1 be the present invention the embodiment of the method 1 that super alpha-phase silicon nitride is prepared using nano-tube in prepare product XRD spectrum；
Fig. 2 be the present invention the embodiment of the method 2 that super alpha-phase silicon nitride is prepared using nano-tube in prepare product XRD spectrum；
Fig. 3 be the present invention the embodiment of the method 3 that super alpha-phase silicon nitride is prepared using nano-tube in prepare product XRD spectrum.
Specific implementation mode
Below by specific embodiment, the invention will be further described, but protection scope of the present invention be not limited to it is following Embodiment.
Embodiment 1：
It is raw material, outer diameter 400nm, internal diameter 250nm, specific surface area 24m2/g to take nano-tube.In nitrogen Under atmosphere, 25h is kept the temperature in 1350 DEG C, you can obtain loose alpha-phase silicon nitride；Planetary ball mill is reused to obtained nitrogen SiClx carries out planetary milling.Its rotational speed of ball-mill is 1000r/min, time 30h, you can obtain even particle size distribution Super alpha-phase silicon nitride.
Product manufactured in the present embodiment is subjected to X-ray energy spectrum analysis (XRD), the results are shown in Figure 1, and α phase contents are 94.8%.
Embodiment 2：
It is raw material, outer diameter 150nm, internal diameter 85nm, specific surface area 75m2/g to take nano-tube.In nitrogen gas Under atmosphere, 22h is kept the temperature in 1300 DEG C, you can obtain loose alpha-phase silicon nitride；Reuse nitridation of the planetary ball mill to obtaining Silicon carries out planetary milling.Its rotational speed of ball-mill is 1000r/min, time 26h, you can obtains the super of even particle size distribution Alpha-phase silicon nitride.
Product manufactured in the present embodiment is subjected to X-ray energy spectrum analysis (XRD), the results are shown in Figure 2, and α phase contents are 97.9%.
Embodiment 3：
It is raw material, outer diameter 75nm, internal diameter 30nm, specific surface area 90m2/g to take nano-tube.In nitrogen gas Under atmosphere, 20h is kept the temperature in 1250 DEG C, you can obtain loose alpha-phase silicon nitride；Reuse nitridation of the planetary ball mill to obtaining Silicon carries out planetary milling.Its rotational speed of ball-mill is 1000r/min, time 22h, you can obtains the super of even particle size distribution Alpha-phase silicon nitride.
Product manufactured in the present embodiment is subjected to X-ray energy spectrum analysis (XRD), the results are shown in Figure 3, and α phase contents are 99.1%.
In the description of this specification, reference term " one embodiment ", " in one embodiment or example.In this explanation In book, a schematic expression of the above terms does not necessarily refer to the same embodiment or example.Moreover, the specific spy of description Sign, structure, material or feature can a little embodiments ", the description of " example ", " specific example " or " some examples " etc. means Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example be contained in the present invention at least at any one Or it can be combined in any suitable manner in multiple embodiments or example.In addition, without conflicting with each other, those skilled in the art Member can be combined by different embodiments described in this specification or with the feature of example and different embodiments or examples and Combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changes, replacing and modification.

Claims (1)

1. a kind of method preparing super alpha-phase silicon nitride using nano-tube, which is characterized in that include the following steps：
It is raw material, outer diameter 75nm, internal diameter 30nm, specific surface area 90m to take nano-tube2/g.In a nitrogen atmosphere, 20h is kept the temperature in 1250 DEG C, you can obtains loose alpha-phase silicon nitride；Reuse planetary ball mill to obtained silicon nitride into Planetary high-energy ball milling, rotational speed of ball-mill 1000r/min, time 22h, you can obtain the superelevation α of even particle size distribution The α phase contents of phase silicon nitride, the super alpha-phase silicon nitride are 99.1%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102173396A (en) * 2011-01-25 2011-09-07 巩义市宏泰氮化硅材料有限公司 Production method of high-content alpha-crystal form silicon nitride powders
CN104291829A (en) * 2014-04-30 2015-01-21 浙江大学 Preparation method for high alpha-phase silicon nitride
CN104495765A (en) * 2014-12-09 2015-04-08 浙江大学 Method for preparing high alpha-phase silicon nitride by utilizing porous silicon

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102173396A (en) * 2011-01-25 2011-09-07 巩义市宏泰氮化硅材料有限公司 Production method of high-content alpha-crystal form silicon nitride powders
CN104291829A (en) * 2014-04-30 2015-01-21 浙江大学 Preparation method for high alpha-phase silicon nitride
CN104495765A (en) * 2014-12-09 2015-04-08 浙江大学 Method for preparing high alpha-phase silicon nitride by utilizing porous silicon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
硅纳米管的制备及应用前景;唐元洪等;《新材料产业》;20051203(第3期);全文 *

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