CN102173396A - Production method of high-content alpha-crystal form silicon nitride powders - Google Patents
Production method of high-content alpha-crystal form silicon nitride powders Download PDFInfo
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Abstract
The invention discloses a production method of silicon nitride powders, in particular relates to a novel production method of silicon nitride powders with high content of alpha-Si3N4, and belongs to the technical field of inorganic chemistry. The method comprises the following steps: firstly pre-treating powdery raw materials by mechanical activation, and feeding a mixed diluting agent of alpha-Si3N4 and non-crystalline Si3N4 during the direct nitridation of silicon powders at a high temperature under normal pressure. By controlling the addition ratio of the diluting agent and the nitridation time and temperature, the silicon nitride powders with high content of alpha-Si3N4 are synthesized. The process improves the activity of solid-phase reactants, promotes the reaction between Si and N2, does not need high-temperature and high-pressure conditions, is easy to operate, adopts easily-available raw materials, increases the purity of products, has a low coat and a high efficiency, and is environment-friendly and energy-saving. The process is economical and highly-efficient and suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of production method of alpha-silicon nitride powders, relate in particular to a kind of α-Si
3N
4The new process for producing that content is higher belongs to technical field of inorganic.
Background technology
Silicon nitride (Si
3N
4) be a kind of important structured material, have the title of " all-round champion " in the stupalith.It is a kind of superhard material, is the excellent high-temperature structured material, is again new-type functional material.Itself has oilness, and wear-resistant, except that hydrofluoric acid, it not with other inorganic acid reaction, resistance to corrosion is strong, and is anti-oxidant during high temperature, and it can also resist thermal shock, be heated in air more than 1000 ℃, sharply cooling sharply heating can be not cracked more yet.Specific to the physicals aspect, silicon nitride material have the hardness height, wear-resistant, Young's modulus is big, intensity is high, high temperature resistant, characteristics such as thermal expansivity is little, thermal conductivity is big, good thermal shock, density is low, skin friction coefficient is little, electrical insulation capability is good.Silicon nitride ceramics is suitable for the structured material as various special purposes, Application Areas relates to industries such as machinery, chemical industry, electronics, military project, had very wide application prospect in fields such as automobile, machinery, metallurgy and chemical engineerings, and be penetrated into space technology gradually, a plurality of stratospheres such as ocean exploitation, electronic technology, health care, nondestructive testing, control automatically, broadcast television.21 century, silicon nitride ceramics continued as same metal, organic polymer material the bigger effect of progress, development of science and technology performance of human society.
Nano-silicon nitride has two kinds of crystal formations: metastable low temperature is six side α-Si mutually
3N
4With stable high temperature six side β-Si mutually
3N
4, α-Si
3N
4Hardness is greater than β-Si
3N
4, and β-Si
3N
4Toughness is greater than α-Si
3N
4The particle diameter of beta-silicon nitride powder, α, β phase content and foreign matter content have determined the quality of its quality, and directly influence the quality of ceramic, to such an extent as to if very thin nano level or the submicron order of reaching of the particle of beta-silicon nitride powder, or the reinforcement item that wherein adds is nano level or submicron order, so Tao Ci toughness will increase considerably, thereby adapts to the needs of various occasions.Preparation high-performance ceramic goods are very high to the requirement of beta-silicon nitride powder.And the beta-silicon nitride powder quality depends on its preparation method, preparation method commonly used at present has: silica flour direct nitridation method, carbothermic method, silicon halide ammonolysis process, preparation precursor process, chemical double decomposition, in-situ synthesis, silicon alloy ammonolysis process etc., the following deficiency of ubiquity: by macrobead silicon nitride, the preparation of heterogeneous powder sintering, fragility is big, lack of homogeneity, reliability are low, toughness and intensity difference, makes its application be subjected to bigger restriction.And the silica flour direct nitridation method prepares enough height of beta-silicon nitride powder requirement nitrogen pressure, to realize Si and N
2Abundant contact.The synthetic Si of general burning
3N
4The nitrogen pressure lower bound be 3MPa, but sometimes up to more than the 100MPa.Adopt the high pressure synthesis technique not only high but also increased production cost, also brought potential safety hazard simultaneously to production because of facility investment.Really it seems the Si that the most representative domestic enterprise produces from the index test and the examination sintering of domestic and international beta-silicon nitride powder
3N
4Average grain is about 3 microns, and metals content impurity is higher, be difficult to reach the qualified product requirement, and the powder of import is below 0.7 micron.Therefore, for meeting the need of market, suitability for industrialized production ultra micro, high-quality alpha-silicon nitride powders are the problem that needs to be resolved hurrily in the domestic silicon nitride industry development, and be very urgent.Key is its synthesis technique is improved.
Summary of the invention
At the prior art situation, the object of the invention is existing technology is improved, and provides that a kind of alpha crystalline form content height, impurity are few, the production method of ultramicrofine alpha-silicon nitride powders, satisfies the silicon nitride practical application request.
The present invention adopts the silica flour direct nitridation method, and promptly purified silica flour generates silicon nitride by nitrogen to the silica flour internal divergence under the high temperature in nitrogen atmosphere.But in nitrogenizing reaction, also be accompanied by the sintering process of silica flour, hindered the further nitrogenize of silica flour, the present invention improves its synthesis technique, in the silica flour biscuit, introduce silicon nitride and make thinner, improve the nitrogenize efficient of silica flour, silicon amount residual in the product is reduced, and to the nitriding temperature that influence the silicon nitride transformation efficiency, nitriding velocity, and technological factor such as silicon particle size inquire into, with realization the object of the invention.
Technical scheme is as follows:
(1) at first by mechanical activation mode pre-treatment silica flour, makes raw material silica flour refinement and decrystallized, thereby improve solid state reaction agent activity, strengthen Si-N
2Between the reaction of gas-solid phase interface, improve Si-N under low nitrogen temperature and the low pressure
2The heat release combustion velocity.During grinding, the silicon nitride ball milling that adds 3 times of the polymethyl acrylic acid of water, silica flour weight 0.2% of silica flour weight 90% and silica flour weight is situated between, and prepares abrasive material.
(2) add α-Si
3N
4With nano amorphous Si
3N
4Mixing prevents silica flour from sintering as thinner, and the while is as the nucleus of resultant; Silica flour and mixing diluents is even.Composite thinning agent α-Si
3N
4With nano amorphous Si
3N
4Weight ratio is 1: 1; The composite thinning agent addition is 20% of a silica flour weight.
(3) dry silica flour and thinner under the nitrogen protection atmosphere under the normal pressure, feed nitrogen with certain flow, displace furnace air; Be heated to 1350 ℃ then, slowly rotate burner, prevent that on the one hand the silica flour bonding wall and the nitrogenize product that melt from luming, material can be disperseed on the other hand, the reinforcement silica flour contacts with nitrogen, and silica flour and nitrogen are fully reacted.
(4) be cooled to room temperature after, put into and be embedded with teflon-lined ball grinder or nylon jar and grind synthetic Si
3N
4Powder: add Si
3N
4The water of weight 90%, Si
3N
4The polymethyl acrylic acid of weight 0.2% and Si
3N
4The silicon nitride ball milling that weight is 3 times is situated between, and grinds synthetic Si
3N
4Powder.After grinding 5-15h, the size range of powder is at 0.696 μ m-0.515 μ m.Sieve filtering mill of slurry is situated between, grinds lumps after the oven dry after sieve.
Can adopt gradient temperature programming type of heating by microcomputerized control in actual production, segmentation is incubated, heats up at a slow speed, improves the effect of silicon powder nitride.
Principle and advantage are: the present invention at first adopts mechanical activation silicon grain, reduces powder particles, crystal grain thinning, and the microstrain and the defective of increase crystal grain inside increase Si-N
2Reaction interface plays and strengthens Si-N
2The effect of reaction, thus the reagent activity improved, temperature of reaction is reduced significantly.This technological process does not need high temperature and high pressure environment, and is simple to operate, and raw material is easy to get, and the high and low cost of product purity, efficient, Environmental Safety, energy-conservation are an economy, the efficient and technology circuit that can carry out scale operation.
High-content micron α-Si that the present invention makes
3N
4Technical indicator meets or exceeds Q/GYHT001-2010, and its minimum particle diameter, very big specific surface area and higher chemical property can significantly improve the sintering densification degree of silicon nitride, reduce sintering temperature, save energy.Because the granular size of ceramic powder has determined the microtexture and the macro property of stupalith, if the particle packing of silicon nitride powder is even, firing contraction unanimity and uniform crystal particles grows up, the microdefect that particle hour is produced more is more little, the intensity of prepared material is just corresponding high more, so just fragility be can overcome effectively, snappiness and processability improved.Its performance difference of silicon nitride of different α, β phase content, high-content micron α-Si that the present invention is made
3N
4Be applied in the stupalith, microstructure shows, crystal grain, crystal boundary and all be in nanometer level (1nm～100nm), and the intensity of stupalith is increased substantially in conjunction with size between them, many deficiencies of engineering ceramics have been overcome, for frontier has been opened up in the application that substitutes engineering ceramics.
Description of drawings
Fig. 1 process route chart of the present invention;
The composite thinning agent adding proportion is to the influence of nitridation process during the following nitrogenize 10min of 350 ℃ of Figure 21;
The silicon nitride XRD spectrum of Fig. 3 after the different mechanical activation time handles;
Fig. 4 composite thinning agent add 20% and nitridation time when being 10min nitriding temperature to the influence of nitridation process;
350 ℃ of following composite thinning agents of Figure 51 add the influence to nitridation process of 20% o'clock nitridation time;
Make the XRD spectrum of silicon nitride under Fig. 6 experiment condition of the present invention;
Make the silicon nitride particle size distribution figure under Fig. 7 experiment condition of the present invention.
Crystal formation is analyzed with Bruker D8 FOCUS type X-ray diffraction
Embodiment
For the present invention is better illustrated, as follows for embodiment in conjunction with process of the test:
1, main raw material(s): silica flour, technical grade, purity 〉=99.7%; α-Si
3N
4, micron amorphous Si
3N
4With nano amorphous Si
3N
4High pure nitrogen, purity 99.99% is commercially available product.
2, experimental technique
At first grind concrete grammar: the silicon nitride ball milling that adds 3 times of the polymethyl acrylic acid of water, silica flour weight 0.2% of silica flour weight 90% and silica flour weight is situated between, and prepares abrasive material.Put into and be embedded with teflon-lined ball grinder or nylon jar, in agitated ball mill and two big or small planetary ball mills, grind respectively.Milling time is respectively 5,10,15,20,25 ..., 50,100h, the granularity Detection analysis is carried out in sampling respectively.After grinding reaches needed granularity, stop to grind.Sieve filtering mill of slurry is situated between, grinds lumps after the oven dry after sieve.
Silica flour and α-Si after then will activating
3N
4Or micron amorphous Si
3N
4Or nano amorphous Si
3N
4Thinner is packed in the roasting kiln furnace chamber.Before beginning heating, the nitrogen flow feeding roasting kiln furnace chamber with 2.0L/min continues 30min, air in the displacement furnace chamber.Feed with the 1.0L/min nitrogen flow then, slowly rotate roasting kiln, can prevent that on the one hand the silica flour bonding wall and the nitrogenize product that melt from luming, material can be disperseed on the other hand, the reinforcement silica flour contacts with nitrogen.After experiment is finished, treat that sample hose is cooled to room temperature after, pour out and collect product, add Si
3N
4The water of weight 90%, Si
3N
4The polymethyl acrylic acid of weight 0.2% and Si
3N
4The silicon nitride ball milling that weight is 3 times is situated between, and grinds synthetic Si
3N
4Powder is analyzed sample.
3, result and discussion
3.1 the thinner kind is to the influence of nitridation process
Silica flour is the synthetic Si of direct nitrogenize under very high temperature
3N
4The time, fusing appears in silica flour, forms pelletizing easily, and is obvious from sintering phenomenon, causes the pore between the powder to block sealing, hindered the further nitrogenize of silica flour.Therefore, in silica flour, add an amount of Si
3N
4As thinner, be the effective way of avoiding occurring above-mentioned phenomenon.When the adding proportion of three kinds of thinners is respectively 50%, nitriding temperature is 1350 ℃, and nitridation time is 10min, and the silicon nitride of production is as shown in table 1.
Silicon nitride was formed when table 1 added the different sorts thinner
As can be seen, under the same conditions, add α-Si
3N
4As thinner, the transformation efficiency of silicon is the highest, reaches 99.4%, and adds micron amorphous Si
3N
4As thinner, the transformation efficiency of silicon is lower, has only 77.6%, therefore, uses α-Si
3N
4As thinner, more help promoting silicon to Si
3N
4Conversion, but the β phase content is higher in the nitrogenize product, because α-Si
3N
4At high temperature will change mutually to β.With micron amorphous Si
3N
4Compare, select nano amorphous Si for use
3N
4During as thinner, the transformation efficiency of silicon is higher, β-Si in the nitrogenize product
3N
4Content is lower.With regard to the transformation efficiency that promotes silicon, α-Si
3N
4Best results, secondly be nano amorphous Si
3N
4, micron amorphous Si
3N
4Effect relatively poor, and with nano amorphous Si
3N
4During for thinner, β-Si in the nitrogenize product
3N
4Content is lower.Therefore,, make in the nitrogenize product β phase content keep lower simultaneously, select α-Si for use in order to obtain the transformation efficiency of higher silicon
3N
4With nano amorphous Si
3N
4Mixing is preferable selection as thinner.
Under these conditions, with α-Si
3N
4With nano amorphous Si
3N
4Mixing is as thinner, and silicon nitride is formed as table 2:
Table 2
So select α-Si for use in the subsequent experimental
3N
4With nano amorphous Si
3N
4Composite thinning agent, both part by weight are 1: 1.
3.2 the thinner adding proportion is to the influence of nitridation process
When nitriding temperature be 1450 ℃, when nitridation time is 10min, the composite thinning agent adding proportion is to the influence of nitridation process as shown in Figure 2.
In silica flour, do not add Si
3N
4The time, residual a large amount of free silica in the product, and the thicker metal pelletizing of a large amount of diameters appears, this is that because at high temperature pelletizing is formed in the silica flour fusing, nitrogenizing reaction only carries out on the pelletizing surface.When in silica flour, adding an amount of composite thinning agent, after the silicon of silicon powder surface is fused into liquid phase,, stoped liquid-state silicon to form pelletizing because thinner is dispersed in around the silica flour, promoted the carrying out of nitrogenizing reaction, the nitrogenize product is the shot shape.By accompanying drawing 2 as can be known, along with the increase of thinner adding proportion in the experiment material, the transformation efficiency of silicon obviously increases, but when the thinner adding proportion surpassed 10%, the transformation efficiency of silicon changed not obvious.Simultaneously, along with the increase of thinner adding proportion, β-Si in the nitrogenize product
3N
4Content but reducing, its reason is that the thinner adding proportion is many more, the easier thinner surface that is dispersed in of the silicon liquid of fusing, easier evaporation cause liquid phase to reduce, thereby β reduces mutually.Therefore, after taking all factors into consideration, adding proportion is 20% o'clock, nitriding result the best.
3.3 the influence of silica flour mechanical activation
With granularity is 44 μ m, and purity is composite thinning agent α-Si of 5 μ m greater than the silica flour and the mean particle size of 98% (massfraction)
3N
4Powder mixes, and the powder that mixes is put into the high energy vibration ball mill mix and activation treatment, and both mass ratioes are 10: 2, and vibrational frequency is 23.2Hz.With X-ray diffraction (x-ray diffraction, XRD) instrument (Cu K
a) respectively to grinding 8h, the composition of the pre-treatment powder of 12h is analyzed.
By accompanying drawing 3 as can be seen: along with the prolongation of milling time, the diffraction peak intensity of Si obviously descends, and it is generally acknowledged that mechanical mill can cause the abundant refinement of silica flour; Simultaneously, the long-range order degree of the inner atomic arrangement of powder particle descends, and the non-crystallization degree of powder obviously improves.Under the effect of mechanical force, initial period mainly is the minimizing of powder granule size and the increase of surface-area in the process of lapping, but after acquiring a certain degree, owing to balance appears in short grained gathering, the size that is powder no longer changes with the prolongation of milling time, but this balance and do not mean that the constant of powder property, if continue to apply mechanical force, energy just can store in a variety of forms, causes that powder section is decrystallized.This mechanical activation causes that amorphous and nanocrystalline coexistence improve reactive behavior in the reagent, helps silica flour directly to generate Si in burning synthetic mode under lower nitrogen temperature and pressure
3N
4Powder.In sum, adopt mechanical activation 8h.
3.4 nitriding temperature is to the influence of nitridation process
When the thinner adding proportion be 20%, when nitridation time is 10min, nitriding temperature is to the influence of nitridation process as shown in Figure 4.In 1050 ℃～1550 ℃ temperature ranges, along with nitriding temperature increases, the transformation efficiency of silicon constantly increases, and free silicone content constantly reduces in the nitrogenize product, also showed increased of β phase content in the nitrogenize product.When nitriding temperature be 1350 ℃, when nitridation time is 10min, the transformation efficiency of silicon reaches 98.6%, silica flour is nitrogenize fully basically, α-Si
3N
4Content reaches more than 95%.When nitriding temperature is higher than 1350 ℃, continue the rising nitriding temperature, the transformation efficiency of silicon is constant substantially, but the β phase content continues to increase.Therefore, for obtaining high content of alpha-Si
3N
4, selecting nitriding temperature is 1350 ℃.
3.5 nitridation time is to the influence of nitridation process
When the thinner adding proportion be 20%, when nitriding temperature is 1350 ℃, nitridation time is to the influence of nitridation process as shown in Figure 5.Along with the prolongation of nitridation time, free silicone content reduces gradually in the nitrogenize product, and the transformation efficiency of silicon increases gradually.Under 1350 ℃, behind the nitrogenize 10min, free silica only is 0.7% in the nitrogenize product, and the transformation efficiency of silicon has arrived 98.6%, α-Si
3N
4Content reaches 95%.Therefore, prolong nitridation time, can obviously improve nitrogenization speed, help the carrying out of nitrogenizing reaction, but along with the prolongation of nitridation time, the β phase content also increases gradually in the nitrogenize product, therefore, for obtaining high content of alpha-Si
3N
4, select 10min proper.
3.6 the XRD analysis of silicon nitride
Gained silicon nitride product of the present invention is carried out XRD analysis, and from the XRD of accompanying drawing 6 spectrum as seen: contain small-amount free Si the sample, quantitative XRD analysis result shows α-Si in the product
3N
4Content greater than 95%.The combustion processes of silica flour in nitrogen belongs to the gas-permeable combustion mode, and so-called infiltration burning is meant that the gas-phase reaction agent is present in the hole of silica flour base, reaction beginning, the N in the hole
2After being consumed, insufficient N
2Must be transferred to reaction front from the space outside the silica flour base.The prerequisite that the infiltration burning is carried out is to avoid silica flour fusing, reunion.If the fusing of a large amount of silica flours, N
2Just can not in time be penetrated into Si-N
2Reaction front, thus cause reaction not exclusively.In fact, the method that adopt to add thinner both can reduce temperature of reaction, can guarantee that again silica flour in the reaction process is unlikely fusing and reunites and be the molten bath, thereby guarantee at lower N
2The combusting under pressure building-up reactions is fully carried out.
3.7 ball milling change of granularity
The change of granularity of grinding the different time powder sees Table 3.Can find out that from table 3 when vertical ball mill ground 5h, the granularity of powder had been reduced to the magnitude of about 0.7 μ m (0.696 μ m), the magnitude that causes 0.7 μ m just falls in later and 35h and asteroid ball mill and major planets ball mill are respectively at 15h.Powder refine to 0.5 μ m submicron order, and vertical grinder need grind 15h, and asteroid grinding machine and major planets grinding machine need to grind the time about 30h and 50h respectively.The efficient of efficiency ratio vertical ball mill that planetary mills is described is much lower.With the increase of milling time, the fine size of powder is difficult to refinement again, even increases on the contrary along with milling time increases granularity during to (d50=0.5 μ m) left and right sides to a certain degree.This be since powder carefully to a certain degree taking place due to the agglomeration.
Table 3 grinds the granularity of different time powder
| 20 | 0.804 | ||
| 25 | 0.593 | ||
| 30 | 0.727 | ||
| 35 | 0.465 | 0.696 | |
| 40 | 0.731 | ||
| 50 | 0.763 | 0.468 | |
| 100 | 0.888 |
Repeatedly investigate conditions such as different steps temperature, nitrogen flow and furnace pressure to silicon nitride α in the sample mutually, β mutually and the influence of remaining silicone content, the result is as shown in table 4 below:
Product under table 4 different technology conditions is formed
| Sequence number | α-Dan Huagui (%) | Beta-silicon nitride (%) | Silicon (%) |
| 1 | ?74 | 25 | 1 |
| 2 | ?83 | 14 | 3 |
| 3 | ?77 | 22 | 2 |
| 4 | ?84 | 14 | 2 |
| 5 | ?79 | 20 | 1 |
| 6 | ?89.4 | 9.1 | 0.5 |
| 7 | ?94.4 | 5.1 | 0.4 |
| 8 | ?97.6 | 2.1 | 0.3 |
| 9 | ?95.2 | 4.6 | 0.4 |
| 10 | ?96.4 | 3.2 | 0.4 |
Determine relatively that processing condition of the present invention are: (1) at first by mechanical activation mode pre-treatment silica flour, makes raw material silica flour refinement and decrystallized, thereby improves solid state reaction agent activity, strengthens Si-N
2Between the reaction of gas-solid phase interface, improve Si-N under low nitrogen temperature and the low pressure
2The heat release combustion velocity.During grinding, the silicon nitride ball milling that adds 3 times of the polymethyl acrylic acid of water, silica flour weight 0.2% of silica flour weight 90% and silica flour weight is situated between, and prepares abrasive material.
(2) add α-Si
3N
4With nano amorphous Si
3N
4Mixing prevents silica flour from sintering as thinner, and the while is as the nucleus of resultant; Silica flour and mixing diluents is even.Composite thinning agent α-Si
3N
4With nano amorphous Si
3N
4Weight ratio is 1: 1; The composite thinning agent addition is 20% of a silica flour weight.
(3) dry silica flour and thinner under the nitrogen protection atmosphere under the normal pressure, feed nitrogen with certain flow, displace furnace air; Be heated to 1350 ℃ then, slowly rotate burner, prevent that on the one hand the silica flour bonding wall and the nitrogenize product that melt from luming, material can be disperseed on the other hand, the reinforcement silica flour contacts with nitrogen, and silica flour and nitrogen are fully reacted.
(4) be cooled to room temperature after, put into and be embedded with teflon-lined ball grinder or nylon jar and grind synthetic Si
3N
4Powder: add Si
3N
4The water of weight 90%, Si
3N
4The polymethyl acrylic acid of weight 0.2% and Si
3N
4The silicon nitride ball milling that weight is 3 times is situated between, and grinds synthetic Si
3N
4Powder.After grinding 5-15h, the size range of powder is at 0.696 μ m-0.515 μ m.Sieve filtering mill of slurry is situated between, grinds lumps after the oven dry after sieve.
Under above-mentioned optimum process condition, carry out multiple batches of middle experiment altogether.Pilot product is carried out to branch relatively with external expensive goods product, and data are as shown in table 5:
Table 5 representative sample both at home and abroad compares
| Sample | α-Dan Huagui (%) | Beta-silicon nitride (%) | Silicon (%) |
| Product of the present invention | ?97.6 | ?2.1 | 0.3 |
| Japan | ?97.1 | ?2.9 | 0 |
The silicon nitride product that adopts technology of the present invention to make is suitable with external like product quality.Therefrom select a batch products and carried out sreen analysis: granularity the results are shown in accompanying drawing 7 with MICROTRACX100 particle size analyzer (U.S.) check and analysis instrument.
From the sreen analysis report as can be known, its volume average particle size D (4,3) is 1.591 microns, and surface-area median size D (3,2) is 0.128 micron, and its main distributed areas are between 0.04 to 0.3 micron.
To product characterize comprehensively the result, the submicron that the present invention produces, micron silicon nitride have good purity and crystallinity, characteristics such as density is big and thermal expansivity is little, hardness is big, Young's modulus is high and thermostability, chemical stability and electrical insulating property be good, can the body pottery or two kinds of forms of ceramic matric composite be widely used in industries such as metallurgy, space flight, aviation, petrochemical complex, machinery, electronics, can substitute external product fully.The submicron that the present invention produces, micron silicon nitride are applied to ceramic field and have intensity height, good, the strong characteristics of workability of snappiness, good market prospects.
Claims (5)
1. the production method of a high content of alpha crystalline form alpha-silicon nitride powders is characterized in that, realizes as follows:
(1) at first by mechanical activation mode pre-treatment silica flour; The silicon nitride ball milling that adds 3 times of the polymethyl acrylic acid of water, silica flour weight 0.2% of silica flour weight 90% and silica flour weight during grinding is situated between, and prepares abrasive material;
(2) add α-Si
3N
4With nano amorphous Si
3N
4Composite thinning agent is with silica flour and thinner α-Si
3N
4Mix; The composite thinning agent addition is 20% of a silica flour weight;
(3) dry silica flour and thinner under the nitrogen protection under the normal pressure, feed nitrogen with certain flow, displace furnace air; Be heated to 1350 ℃ then, slowly rotate burner, silica flour and nitrogen are fully reacted, nitridation time is 15min;
(4) be cooled to room temperature after, put into and be embedded with teflon-lined ball grinder or nylon jar and grind synthetic Si
3N
4Powder; The filtering of then sieving mill is situated between, and grinds lumps after the oven dry after sieve.
2. the production method of alpha-silicon nitride powders as claimed in claim 1 is characterized in that, adds Si when step (4) is ground
3N
4The water of weight 90%, Si
3N
4The polymethyl acrylic acid of weight 0.2% and Si
3The silicon nitride ball milling that N weight is 3 times is situated between, and grinds synthetic Si
3N
4Powder.
3. the production method of alpha-silicon nitride powders as claimed in claim 1 is characterized in that, composite thinning agent α-Si
3N
4With nano amorphous Si
3N
4Weight ratio is 1: 1.
4. as the production method of one of them described alpha-silicon nitride powders of claim 1-3, it is characterized in that, adopt vertical lapping machine mechanical activation silica flour 8h; Adopt vertical lapping machine to grind Si
3N
4Powder 7-10h.
5. as the production method of one of them described alpha-silicon nitride powders of claim 1-3, it is characterized in that used type of heating adopts the gradient temperature-programmed mode to carry out by microcomputerized control.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807196A (en) * | 2012-08-26 | 2012-12-05 | 西安科技大学 | Method for preparing silicon nitride nano material |
| CN104495765A (en) * | 2014-12-09 | 2015-04-08 | 浙江大学 | Method for preparing high alpha-phase silicon nitride by utilizing porous silicon |
| CN104528672A (en) * | 2014-12-17 | 2015-04-22 | 青岛桥海陶瓷新材料科技有限公司 | Preparation method of alpha-silicon nitride |
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| CN115432676A (en) * | 2021-06-04 | 2022-12-06 | 中国科学院过程工程研究所 | System and method for preparing high-quality silicon nitride powder by using multistage fluidized bed |
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| CN102807196A (en) * | 2012-08-26 | 2012-12-05 | 西安科技大学 | Method for preparing silicon nitride nano material |
| CN102807196B (en) * | 2012-08-26 | 2013-12-25 | 西安科技大学 | Method for preparing silicon nitride nano material |
| CN104495765A (en) * | 2014-12-09 | 2015-04-08 | 浙江大学 | Method for preparing high alpha-phase silicon nitride by utilizing porous silicon |
| CN104528672A (en) * | 2014-12-17 | 2015-04-22 | 青岛桥海陶瓷新材料科技有限公司 | Preparation method of alpha-silicon nitride |
| CN105480957A (en) * | 2016-01-18 | 2016-04-13 | 沈阳工业大学 | Method for preparing non-grinding high-purity fully granulated silicon nitride powder by adopting direct nitriding method |
| CN105884374B (en) * | 2016-06-15 | 2018-10-30 | 杭州硅诺科技有限公司 | A method of preparing super alpha-phase silicon nitride using nano-tube |
| CN105884374A (en) * | 2016-06-15 | 2016-08-24 | 杭州硅诺科技有限公司 | Method for preparing ultrahigh alpha-phase silicon nitride by means of silicon nanotubes |
| CN107698264A (en) * | 2016-08-09 | 2018-02-16 | 河北高富氮化硅材料有限公司 | A kind of preparation method of modified alpha-phase silicon nitride powder |
| CN107285288A (en) * | 2017-07-12 | 2017-10-24 | 深圳市东川技术研究有限公司 | The preparation method of nano silicon nitride powders |
| CN110357050A (en) * | 2019-07-03 | 2019-10-22 | 南昌大学 | The shaft-like beta phase silicon nitride raw powder's production technology such as a kind of |
| CN115432676A (en) * | 2021-06-04 | 2022-12-06 | 中国科学院过程工程研究所 | System and method for preparing high-quality silicon nitride powder by using multistage fluidized bed |
| CN115432676B (en) * | 2021-06-04 | 2024-03-26 | 中国科学院过程工程研究所 | System and method for preparing high-quality silicon nitride powder by multistage fluidized bed |
| CN113563088A (en) * | 2021-07-30 | 2021-10-29 | 淄博国创中心先进车用材料技术创新中心 | Porous silicon nitride ceramic component and method for producing same |
| CN114790107A (en) * | 2022-04-29 | 2022-07-26 | 江苏大学 | Preparation of SiO by utilizing polycrystalline silicon cutting waste at low temperature 2 -Si 3 N 4 Method for compounding ceramic |
| CN116216662A (en) * | 2023-02-01 | 2023-06-06 | 江苏富乐华功率半导体研究院有限公司 | Synthesis method of silicon nitride powder |
| CN116216662B (en) * | 2023-02-01 | 2023-10-27 | 江苏富乐华功率半导体研究院有限公司 | Synthesis method of silicon nitride powder |
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