CN105884374A - Method for preparing ultrahigh alpha-phase silicon nitride by means of silicon nanotubes - Google Patents
Method for preparing ultrahigh alpha-phase silicon nitride by means of silicon nanotubes Download PDFInfo
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- CN105884374A CN105884374A CN201610416082.7A CN201610416082A CN105884374A CN 105884374 A CN105884374 A CN 105884374A CN 201610416082 A CN201610416082 A CN 201610416082A CN 105884374 A CN105884374 A CN 105884374A
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Abstract
The invention discloses a method for preparing ultrahigh alpha-phase silicon nitride by means of silicon nanotubes. The method comprises the following steps that 1, silicon nanotubes of which the outer diameters range from 50 nm to 500 nm, the inner diameter ranges from 20 nm to 300 nm, and the specific surface area ranges from 20 m<2>/g to 100 m<2>/g are subjected to high-temperature nitridation in nitrogen at the temperature of 1,220 DEG C to 1,370 DEG C, and a first product is obtained, wherein the heat preservation temperature ranges from 12 h to 28 h; 2, the first product obtained in the first step is subjected to planetary high-energy ball milling, wherein the rotating speed of planetary high-energy ball milling is 1,000 r/min, and the time ranges from 20 h to 30 h. According to the method for preparing ultrahigh alpha-phase silicon nitride by means of the silicon nanotubes, the process is simple, the performance is controllable, the production cycle is short, the production energy consumption is greatly reduced, and the method is specially suitable for preparing ultrahigh alpha-phase silicon nitride.
Description
Technical field
The present invention relates to the preparation field of silicon nitride, particularly relate to one and utilize nano-tube to prepare superelevation
The method of α phase silicon nitride.
Background technology
Silicon nitride is a kind of widely used special ceramic material.It has high temperature resistant, proportion is little, strong
The advantages such as degree is high, hardness is big, wear-resistant, are widely used in the row such as automobile, military project, metallurgy, medical treatment
Industry.
In order to obtain the silicon nitride ceramics of high intensity, high rigidity, often make with the silicon nitride powder of high α phase
For raw material.This is owing to, in silicon nitride high-temperature sintering process, α phase can be changed into bar-shaped or pin
The β phase of shape, this β phase with certain length-width ratio will contribute to nitridation as toughened fiber
Silicon ceramics strength, the raising of hardness.Therefore, prepare α phase content height beta-silicon nitride powder and there is reality
Significance of scientific research and using value.
But, α phase is a kind of metastable state phase of silicon nitride, and silicon powder nitride reaction is a kind of strongly exothermic
Reaction, so, during the high-temperature ammonolysis of silicon, reaction heat liberated heat is easy to make reactant
It is overheated so that α phase in version is equilibrium transport-β phase.The way of industrial general this problem of solution is
Substantial amounts of silicon nitride is added as dispersant in reaction raw materials-silica flour, to evacuate reaction heat, suppression
Sintering.But, cost so will be significantly greatly increased, reduce production efficiency.And effect is limited, not
The silicon nitride of superelevation α can be obtained.
Make reaction system overheated to solve silica flour very exothermic when nitridation reaction so that generation
The problem that α phase content is the highest, expert both domestic and external has done substantial amounts of research.
Wherein, Fukuhira et al. is disclosed in the american documentation literature of Publication No. US5441694A
A kind of method preparing alpha-phase silicon nitride, i.e. adds Cu's or Cu in silicon powder nitride system
Compound is as catalyst so that reaction temperature reduces, and the response time shortens.Additionally, Cu is good
The capacity of heat transmission system can be helped to be derived by heat more smoothly, thus reduce the possibility that system is overheated
Property, improve the content of α phase.But, owing to the density difference of Cu and Si is very big, it is difficult to before reaction
Mix homogeneously both will, and after reacting, impact as impurities left in silicon nitride, is nitrogenized by Cu
The performance of silicon sintering.
James.P et al. in the United States Patent (USP) of Publication No. US25519124 it is also proposed that a kind of silica flour
The pre-treating technology of nitridation, i.e. before high-temperature ammonolysis, first to silicon at certain temperature and hydrogen atmosphere
Powder carries out heat treatment in advance, and wherein, temperature is 200～800 DEG C, and in atmosphere, hydrogen content is
25～100% (V%).This is owing under low temperature, the oxide layer reduction of silicon face can be removed by hydrogen,
Contribute to the carrying out of follow-up nitridation reaction.Although this scheme can effectively shorten the response time, but,
Using the gaseous mixture that density of hydrogen is higher under 200～800 DEG C of high temperature is to have certain danger, is not inconsistent
Close the requirement of industrialized safety in production.
The Chinese patent of Publication No. CN102173396A proposes use revolving burner and prepares high α phase
The way of silicon nitride.During silicon powder nitride reacts, rotate boiler tube so that reactant turns in boiler tube
Turning, this is conducive to silica flour sufficiently to contact with nitrogen, and the heat radiation of favourable system, can effectively carry
The content of α phase in high product.But, the boiler tube rotated under high temperature is easily deformed and ruptures, and this is also
Do not meet stable safe production requirement.
Additionally, the Chinese patent of Publication No. CN102245503A proposes use two-step method silica flour
The scheme of nitridation, in this scheme, silica flour is first in the warm area of 1150～1250 DEG C of cylindrical rotary furnace
Partial nitridation, is then transferred in the warm area of 1250～1350 DEG C nitrogenizing completely.Although this scheme also may be used
To improve the content of α phase to a certain extent, but the highest to equipment requirements, and also operating process is multiple
Miscellaneous, the degree of first step nitridation is difficult to control to, and repeatability is poor, is also not suitable for industrialized production.
Summary of the invention
The invention provides a kind of method utilizing nano-tube to prepare alpha-phase silicon nitride, its method letter
Single efficient, particularly can obtain the silicon nitride of superelevation α phase.
A kind of method utilizing nano-tube to prepare super alpha-phase silicon nitride, step is as follows:
S1, being 50-500nm by external diameter, internal diameter is 20-300nm, and specific surface area is 20-100m2/g
Nano-tube in nitrogen, carry out high-temperature ammonolysis, the temperature of described high-temperature ammonolysis is 1220～1370 DEG C,
Temperature retention time is 12～28h, obtains product 1；
S2, the product 1 after S1 is carried out planetary milling, turning of described planetary milling
Speed is 1000r/min, and the time is 20-30h, finished product.
Further preferably, the external diameter of described nano-tube is 50-200nm, and internal diameter is 20-100nm, than
Surface area is 50-100m2/g.Most preferably, the external diameter of described nano-tube is 50-100nm, and internal diameter is
20-80nm, specific surface area is 70-100m2/g.With it as raw material, α phase in the silicon nitride prepared
Content is the highest.
As preferably, the temperature of described high-temperature ammonolysis is 1220～1370 DEG C, and temperature retention time is 12～28h.
As preferably, the rotating speed of described planetary type ball-milling is 1000r/min, and the time is 20-30h.
The present invention is with nano-tube as raw material, and first, its specific surface area can reach 100m2/g, this
The specific surface area that sample is big can increase considerably the contact area of nitrogen and silicon, improves reaction rate, contracting
Time needed for short reaction；Secondly, the nano-tube structure that the present invention uses is special, it has been investigated that,
Silicon reacts with nitrogen when, the substantial amounts of heat of its release can be by the pipe passage of himself
Well dredged and scattered and disappeared, the effective temperature controlling reaction system, the sintering certainly of suppression silica flour,
And then obtain the silicon nitride of superelevation α phase content.
Accompanying drawing explanation
Fig. 1 is that the nano-tube that utilizes of the present invention is prepared in the embodiment of the method 1 of super alpha-phase silicon nitride
Prepare the XRD figure spectrum of product；
Fig. 2 is that the nano-tube that utilizes of the present invention is prepared in the embodiment of the method 2 of super alpha-phase silicon nitride
Prepare the XRD figure spectrum of product；
Fig. 3 is that the nano-tube that utilizes of the present invention is prepared in the embodiment of the method 3 of super alpha-phase silicon nitride
Prepare the XRD figure spectrum of product.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not
It is confined to following example.
Embodiment 1:
Taking nano-tube is raw material, and its external diameter is 400nm, and internal diameter is 250nm, and specific surface area is
24m2/g.In a nitrogen atmosphere, being incubated 25h in 1350 DEG C, the high α phase that i.e. can obtain loosening nitrogenizes
Silicon；Re-use the planetary ball mill silicon nitride to obtaining and carry out planetary milling.Its ball milling turns
Speed is 1000r/min, and the time is 30h, i.e. can get the super alpha-phase silicon nitride of even particle size distribution.
The product prepared by the present embodiment carries out X-ray energy spectrum analysis (XRD), result such as Fig. 1 institute
Showing, α phase content is 94.8%.
Embodiment 2:
Taking nano-tube is raw material, and its external diameter is 150nm, and internal diameter is 85nm, and specific surface area is
75m2/g.In a nitrogen atmosphere, being incubated 22h in 1300 DEG C, the high α phase that i.e. can obtain loosening nitrogenizes
Silicon；Re-use the planetary ball mill silicon nitride to obtaining and carry out planetary milling.Its ball milling turns
Speed is 1000r/min, and the time is 26h, i.e. can get the super alpha-phase silicon nitride of even particle size distribution.
The product prepared by the present embodiment carries out X-ray energy spectrum analysis (XRD), result such as Fig. 2 institute
Showing, α phase content is 97.9%.
Embodiment 3:
Taking nano-tube is raw material, and its external diameter is 75nm, and internal diameter is 30nm, and specific surface area is
90m2/g.In a nitrogen atmosphere, being incubated 20h in 1250 DEG C, the high α phase that i.e. can obtain loosening nitrogenizes
Silicon；Re-use the planetary ball mill silicon nitride to obtaining and carry out planetary milling.Its ball milling turns
Speed is 1000r/min, and the time is 22h, i.e. can get the super alpha-phase silicon nitride of even particle size distribution.
The product prepared by the present embodiment carries out X-ray energy spectrum analysis (XRD), result such as Fig. 3 institute
Showing, α phase content is 99.1%.
In the description of this specification, reference term " embodiment ", " embodiment or example
In.In this manual, the schematic representation of above-mentioned term is necessarily directed to identical enforcement
Example or example.And, the specific features of description, structure, material or feature can embodiments a bit ",
The description of " example ", " concrete example " or " some examples " etc. means combine this embodiment or show
Example describe specific features, structure, material or feature be contained in the present invention at least any one or
Multiple embodiments or example combine in an appropriate manner.Additionally, in the case of the most conflicting,
Those skilled in the art can be by the different embodiments described in this specification or with example and difference
The feature of embodiment or example is combined and combines.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-mentioned reality
It is exemplary for executing example, it is impossible to be interpreted as that limitation of the present invention, those of ordinary skill in the art exist
Above-described embodiment can be changed in the scope of the present invention, revise, replace and modification.
Claims (3)
1. one kind utilizes the method that nano-tube prepares super alpha-phase silicon nitride, it is characterised in that include
Following steps:
S1, being 50-500nm by external diameter, internal diameter is 20-300nm, and specific surface area is 20-100m2/g
Nano-tube in nitrogen, carry out high-temperature ammonolysis, the temperature of described high-temperature ammonolysis is 1220～1370 DEG C,
Temperature retention time is 12～28h, obtains product 1；
S2, the product 1 after S1 is carried out planetary milling, turning of described planetary milling
Speed is 1000r/min, and the time is 20-30h, finished product.
Nano-tube the most according to claim 1 prepares the method for super alpha-phase silicon nitride, and it is special
Levying and be, the external diameter of described nano-tube is 50-200nm, and internal diameter is 20-100nm, and specific surface area is
50-100m2/g。
Nano-tube the most according to claim 2 prepares the method for alpha-phase silicon nitride, its feature
Being, the external diameter of described nano-tube is 50-100nm, and internal diameter is 20-80nm, and specific surface area is
70-100m2/g。
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Citations (3)
| 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 |
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Patent Citations (3)
| 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)
| Title |
|---|
| 唐元洪等: "硅纳米管的制备及应用前景", 《新材料产业》 * |
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