CN103224224A - Super thick wall tadpole-like boron nitride nanometer powder preparation method - Google Patents
Super thick wall tadpole-like boron nitride nanometer powder preparation method Download PDFInfo
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Abstract
The present invention relates to a super thick wall tadpole-like boron nitride nanometer powder preparation method, which comprises the following steps: (1) weighing raw materials such as sodium silicate, magnesium nitrate, and boron powder; (2) respectively preparing the sodium silicate and the magnesium nitrate into solutions with a certain concentration, adding the boron powder to the sodium silicate solution, adding ethanol in a dropwise manner, and carrying out ultrasonic stirring; (3) slowly adding the magnesium nitrate solution to the sodium silicate-boron powder mixing solution in a dropwise manner, and concurrently carrying out ultrasonic stirring, such that a grayish white colloid slowly appears; and carrying out standing suction filtration on the mixed solution after completing the addition, washing to achieve a neutral state, and placing the filter cake in a muffle furnace to carry out low temperature annealing to obtain a Si-Mg-O porous solid material; and (4) carrying out a reaction of the Si-Mg-O porous material and ammonia gas, and carrying out purification and drying to obtain the super thick wall tadpole-like boron nitride nanometer powder. According to the present preparation, the precursor preparation process is simple, energy consumption is low, and the precursor is porous, and can be directly used for mass preparation of the tadpole-like boron nitride nanometer powder without purification.
Description
Technical field
The present invention relates to a kind of preparation method of hyper-thick pipe tadpole shape boron nitride nanometer powder, be mainly used in nano material and field of ceramic material preparation, significant to the synthetic and application of boron nitride and matrix material thereof.
Background technology
Low-dimensional boron nitride micro-nano material mainly comprises nanocrystalline, unidimensional nano wire, nano belt, fiber, the whisker of zero dimension, nanometer sheet of two dimension or the like, they have the character of many uniquenesses, have important application prospects in fields such as optics, electricity, machinery, the energy, biological medicines.Wherein, the research of one-dimensional boron nitride micro-nano material and application are especially noticeable.
Internal structure according to the one-dimensional boron nitride nano material is divided, and mainly comprises two types: the boron nitride nano-tube that has hollow structure 1); 2) solid boron nitride nanometer line, fiber, whisker and the nano belt etc. that do not have hollow structure in the middle of.Boron nitride nano-tube has similar structure to CNT (carbon nano-tube), but because the B-N key in the boron nitride nano-tube has part ion key characteristic, has caused the two both to have similar place in properties, also has a lot of differences.Boron nitride nano-tube Young's modulus 1.1 ~ 1.3TPa, Young's modulus 0.5 ~ 0.6TPa, its hard and soft degree is suitable with CNT (carbon nano-tube), can be used for enhancing, the toughness reinforcing and modification of types of material such as metal, glass, pottery and polymer.Boron nitride nano-tube has excellent more chemical stability, thermostability and biocompatibility than carbon nanotube.Studies show that its be wide can gap semiconductor (being about 5.5eV), and electric property is not subjected to the influence of its diameter and chirality, is a kind of good insulation performance body and wide bandgap semiconductor materials.These unique character make boron nitride nano-tube at high performance composite, hydrogen storage material, radioprotective and neutron absorbing material, nano-medicament carrier, and being used for numerous areas such as salt water sepn and desalination, semiconductor device and nano-sensor has important application prospects.The non-hollow boron nitride nanometer one-dimensional material of an other class, belong to very important non-oxidized substance high temperature and strengthen toughness reinforcing composite ceramic material, performance is better than carbon fiber, shows that mainly this type of material can substitute carbon fiber and use under electrical isolation, saturating ripple, oxidation and hot conditions.Boron nitride one dimension micro-nano material changeful on pattern and internal structure, different physics or chemical property have been caused, thereby be applicable to various technical applications, the microtexture of research boron nitride one-dimensional material and the relation between pattern and its corresponding physical or the chemical fundamentals performance have great importance.
Over past ten years, the preparation method of one-dimensional boron nitride micro-nano material mainly contains arc discharge method, laser ablation method, mechanical ball milling method, carbon nanotube substitution method, chemical Vapor deposition process (CVD), solvent-thermal method etc.Wherein be expected to prepare in enormous quantities the one-dimensional boron nitride preparation methods mechanical ball milling annealing method is arranged, contain B presoma CVD method and laser ablation method.For example, laser ablation method obtains boron nitride nano-tube after bombarding block boron nitride, pure boron or boron-containing compound with laser in highly compressed argon gas or nitrogen atmosphere exactly.With respect to additive method synthetic boron nitride nano-tube, the resulting product number of plies of laser ablation method is less, mostly is single-walled pipe, because the reaction times is short, the product caliber homogeneous of formation, structure are more orderly, and shortcoming is the energy consumption height, output is very low, is not suitable for promoting and industrialization.The mechanical ball milling annealing method is exactly at first the boracic raw material to be passed through high-energy ball milling 100-150h, then at high temperature in (〉=1000 ℃) and the nitrogen atmosphere ball milling product is carried out obtaining boron nitride nano-tube after the anneal.Compare with arc discharge method, laser ablation method, the mechanical ball milling method does not need high-end equipment, and has tangible low temperature advantage, but this method mechanical milling process required time is oversize, time consumption and energy consumption.Chemical Vapor deposition process (CVD) ultimate principle is carried out chemical reaction after utilizing gas reactant and solid reactant contacts in reactive atmosphere exactly, obtains the process of stable solid product at last.This kind method is synthesizing one-dimensional boron nitride micro-nano material one of the most promising method in enormous quantities, by different material choose and control suitable preparation technology parameter, both can obtain boron nitride nano-tube and also can obtain other one-dimensional boron nitride material.Because it does not need most advanced and sophisticated synthesis device, possess the prospect of a large amount of preparation one-dimensional boron nitride micro-nano materials, be fit to promote and industrialization.
Summary of the invention
Technical problem to be solved by this invention is the preparation method that a kind of hyper-thick pipe tadpole shape boron nitride nanometer powder is provided at the deficiency of above-mentioned prior art existence, the present invention prepares the simple for process of presoma, energy consumption is low, presoma is a vesicular, does not need can be directly used in preparation tadpole shape boron nitride nanometer powder in enormous quantities through purifying.
The present invention for the technical scheme that problem adopted of the above-mentioned proposition of solution is:
A kind of preparation method of hyper-thick pipe tadpole shape boron nitride nanometer powder, it comprises the steps:
(1) according to Si:Mg:B mol ratio 1:1:(10 ~ 40) take by weighing water glass, magnesium nitrate and boron powder raw material respectively;
(2) be dissolved in water glass, magnesium nitrate in the distilled water respectively, stirring is configured to sodium silicate solution and magnesium nitrate solution, then the boron powder is added in the sodium silicate solution, drip ethanol and (play dissemination, boron powder homodisperse is got final product), ultrasonic and stir, obtain water glass-boron powder mixed solution;
(3) magnesium nitrate solution is slowly splashed into water glass-boron powder mixed solution, the control solution PH is 7.2-8.5, carries out ultrasonic agitation simultaneously, and the canescence colloid slowly occurs, after being added dropwise to complete mixed solution is left standstill, and suction filtration, washing leaching cake is to neutral; Obtain the Si-Mg-O cellular solid after then filter cake directly being put into the retort furnace low-temperature annealing;
(4) the Si-Mg-O porous material is descended and ammonia gas react 6 ~ 12h at 1100 ~ 1400 ℃, obtain crude product; Then crude product is purified and drying, can obtain hyper-thick pipe tadpole shape boron nitride nanometer powder.
Press such scheme, described boron powder is the amorphous nano rank, and the median size size is 50 nanometers, and purity is greater than 95wt%.
Because Magnesium Silicate q-agent generally can form precipitation in the PH scope is 7.2-8.5, pH value is too high may to form magnesium hydrate precipitate, is alkaline reagents so be used to regulate the reagent of pH.
Press such scheme, during described preparation water glass-boron powder mixed solution, ultrasonic, churning time is 30 ~ 60min.
Press such scheme, the speed that drips magnesium nitrate solution in the described step (3) is 4 ~ 10ml/min, and the ultrasonic agitation time is 60-120min, and time of repose is 60 ~ 180min.
Press such scheme, stress relief annealed temperature is 500 ~ 750 ℃ in the described retort furnace, and soaking time is 60-120min.
Press such scheme, ammonia flow is 0.5 ~ 5L/min in the described step (4).
Press such scheme, method of purification is earlier crude product to be dispersed in the distilled water in the described step (4), adds 5mol/L hydrochloric acid and 10mol/L hydrofluoric acid, in 60 ℃ of following heated and stirred 12 ~ 24h, suction filtration, washing and washing with alcohol then are again at 80 ℃ of following vacuum-drying 12 ~ 24h.
Press such scheme, it is hyper-thick pipe tadpole shape structure that the present invention prepares the boron nitride nanometer powder, and the tadpole top end diameter is 1 ~ 2 μ m, and the tail end diameter is less than 50nm, and length is 10 ~ 15 μ m, and diameter is diminished to tail end gradually by the tadpole top, changes evenly.
Send out in the preparation process of the super thick tadpole shape boron nitride nanometer powder that the present invention relates to and give birth to following chemical reaction process:
Na
2SiO
3 + Mg(NO
3)
2 + nB→MgSiO
3@nB↓+ 2NaNO
3 (1)
MgSiO
3@nB →MgO-SiO
2-nB (2)
NH
3 →N* + 1.5H
2↑ (3)
MgO-SiO
2-nB + N*→ BN+ SiO
2+ MgO (4)
Among the present invention, the possible reaction mechanism of preparation hyper-thick pipe tadpole shape boron nitride nanometer powder is: the method for at first utilizing the collosol and gel co-precipitation, evenly generate clad nano boron amorphous powder of sedimentary while of Magnesium Silicate q-agent, assisting down of ultrasonic and stirring technique, make nano amorphous boron powder can be evenly distributed on (suc as formula 1) on the Magnesium Silicate q-agent precipitophore; The MgSiO that suction filtration is obtained
3The @nB filter cake is annealed in 500 ~ 750 ℃ of retort furnaces, then obtains porous B-Si-Mg-O solid precursor MgO-SiO
2-nB (suc as formula 2); In the presoma annealing process, ammonia at first is decomposed into active nitrogen-atoms N* and H about 540 ℃
2(suc as formula 3); According to the VLS growth mechanism, under the high temperature reduction atmospheric condition, highly active B* and N* atom are at boron source catalyst S iO
2The @B surface forms the BN nucleus, and along with the continuous supply of B* and N*, BN nanometer tadpole is with SiO
2Nanoparticle is slowly grown for the growth basic point, and this process of growth can not stop, and runs out of up to B* or N* atom.
Compared with prior art, beneficial effect of the present invention is:
First, the present invention be simple and easy to material be raw material, at first obtained the solid porous presoma of equally distributed B-Si-Mg-O by collosol and gel co-precipitation-stress relief annealed method, then presoma is annealed under hot conditions and obtain novel hyper-thick pipe tadpole shape boron nitride nanometer powder, the tadpole top end diameter is 1 ~ 2 μ m, and the tail end diameter is less than 50nm, and length is 10 ~ 15 μ m, diameter is diminished to tail end gradually by the tadpole top, changes evenly.
The second, the present invention prepares the simple for process of presoma, and energy consumption is low, and presoma does not need can be directly used in preparation tadpole shape boron nitride nanometer powder through purifying; The solid porous presoma chemical property of the B-Si-Mg-O for preparing is stable, at high temperature also has excellent mechanical intensity, is analogous to other Powdered or block raw material, is more conducive to gas-solid phase reaction and prepares hyper-thick pipe tadpole shape boron nitride nanometer powder in enormous quantities.
The 3rd, the hyper-thick pipe tadpole shape boron nitride nanometer powder that the present invention prepares, the photochemical catalysis composite nano materials that can be used as the potential novelty, in addition, in view of obtaining product is the hollow boron nitride nanometer material of hyper-thick pipe, the intensity that had both had the boron nitride nanometer fiber, the toughness that also has the thin-walled boron nitride nano-tube, because the tadpole shape pattern of its wedge shape forms pinning effect easily in matrix material, these excellent character make its toughness reinforcing field of enhancing at matrix material have important application prospects simultaneously.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of hyper-thick pipe tadpole shape boron nitride nanometer powder.
Fig. 2 is scanning electron microscope (FSEM) photo of hyper-thick pipe tadpole shape boron nitride nanometer powder.
Fig. 3 is X-ray energy spectrum (EDS) figure of hyper-thick pipe tadpole shape boron nitride nanometer powder.
Fig. 4 is transmission electron microscope (TEM) photo of hyper-thick pipe tadpole shape boron nitride nanometer powder.
Fig. 5 is high difference transmission electron microscope (HRTEM) photo of hyper-thick pipe tadpole shape boron nitride nanometer powder.
Fig. 6 is selected area electron diffraction (SAED) image of hyper-thick pipe tadpole shape boron nitride nanometer powder.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Used water glass (Na among the following embodiment
2SiO
39H
2O), magnesium nitrate (Mg (NO
3)
26H
2O) all be analytical reagent.
Rigaku D/MAX-LLIA type x-ray powder diffraction instrument (going into=1.5406 dusts) is used in the X-ray diffraction analysis (XRD) of products therefrom among the following embodiment, and 2 θ are the 10-80 degree; Observe pattern with Hitachi S-4800 type scanning electronic microscope (FSEM); With JEM2100-F and JEM2010 type transmission electron microscope (TEM) study sample internal microstructure, product is ultra-sonic dispersion in dehydrated alcohol, is added drop-wise on the copper mesh.The elemental composition analysis uses the JEM2100-F type to carry EDS.
Embodiment 1
A kind of preparation method of hyper-thick pipe tadpole shape boron nitride nanometer powder, it comprises following step:
(1) takes by weighing water glass (Na respectively according to Si:Mg:B mol ratio 1:1:10
2SiO
39H
2O) 8.65 g, magnesium nitrate (Mg (NO
3)
26H
2O) 7.75 g and nano amorphous boron powder 3.25 g are as raw material for standby;
(2) be dissolved in water glass, magnesium nitrate in the distilled water respectively, stirring is configured to sodium silicate solution and magnesium nitrate solution, then the boron powder is added in the sodium silicate solution, drips 15ml ethanol (ethanol plays dissemination), ultrasonic and stir 30min, obtain water glass-boron powder mixed solution;
(3) magnesium nitrate solution is slowly splashed into water glass-boron powder mixed solution, rate of addition is 5ml/min, carries out ultrasonic agitation simultaneously, drips saturated NaOH solution and regulates pH value 7.8, and the canescence colloid slowly occurs, and the ultrasonic agitation time is 90min; After being added dropwise to complete mixed solution is left standstill 120min, suction filtration, washing is to neutral; Filter cake is directly put into 600 ℃ of insulations of retort furnace 90min, obtain the Si-Mg-O cellular solid;
(4) the Si-Mg-O porous material is descended and ammonia gas react 10h at 1250 ℃, ammonia flow 1L/min obtains crude product; Crude product is dispersed in the distilled water, add 5mol/L hydrochloric acid and 10mol/L hydrofluoric acid, in 60 ℃ of following heated and stirred 12h, suction filtration, washing and washing with alcohol then, at 80 ℃ of following vacuum-drying 24h, can obtain canescence hyper-thick pipe tadpole shape boron nitride nanometer powder 6.71g again.
Fig. 1 has provided X-ray diffraction (XRD) collection of illustrative plates of the hyper-thick pipe tadpole shape boron nitride nanometer powder for preparing.As shown in Figure 1, Analysis of X RD result as can be known, the sample XRD spectra is consistent with JCPDF card #73-2095; By each crystal face d value in the spectrogram, calculating the product lattice constant is a=0.2500 nm, c=0.6491 nm, and with standard card a=0.2501 nm, c=0.6600nm conforms to substantially, shows that product is the hexagonal boron nitride structure.
Fig. 2 has provided the hyper-thick pipe tadpole shape boron nitride nanometer powder FSEM photo (a is local low power figure, the local high power figure of b) for preparing.By photo as seen, the boron nitride nanometer powder that the present invention prepares is a wall tadpole shape structure, and the tadpole top end diameter is about 1.2 μ m, the about 40nm of tail end diameter, and length is about 12 μ m, and diameter is diminished to tail end gradually by the tadpole top, changes evenly; Judge that from the FSEM photo tadpole shape one-dimentional structure content is greater than 95%.
Fig. 3 has provided the typical area E DS spectrogram of hyper-thick pipe tadpole shape boron nitride nanometer powder for preparing.As shown in Figure 3, the atomic molar ratio of boron and nitrogen is B:N=1:1.08; The existence of oxygen element may be due to surface hydrolysis or the doping silicon dioxide; The existence of magnesium elements may be in the sample due to the small amount of impurities.
Fig. 4 has provided the typical TEM photo of hyper-thick pipe tadpole shape boron nitride nanometer powder (a is local low power figure, and b is top high power figure) for preparing.As shown in Figure 4, the boron nitride nanometer tadpole is about 11 μ m, and diameter is diminished to tail end gradually by the tadpole top, change evenly, and inside, tadpole top is coated with other nanoparticle.
Fig. 5 has provided typical HRTEM photo of hyper-thick pipe tadpole shape boron nitride nanometer powder and the top EDS spectrogram (a is single tube low power figure, and b is tube wall high power figure, and c is top high power figure, and d is a top EDS spectrogram) for preparing.Known to Fig. 5, the boron nitride nanometer tadpole has degree of crystallinity and lattice fringe preferably clearly, and spacing is about 0.34nm, corresponding to (002) crystal face of hexagonal boron nitride.By boron nitride tadpole top EDS spectrum analysis as can be known, it is B, N, O and Si that element is contained in the end.Boron nitride tadpole top HRTEM photo shows that the inner nano grain surface in top is coated with the crystallizing layer of 1 ~ 2nm thickness, and spacing is about 0.34nm, corresponding to (002) crystal face of hexagonal boron nitride, illustrates that this coating layer is a boron nitride.The measurement of granule interior spacing is about 0.62nm, corresponding to (201) crystal face of PDF card JCPDF#51-1379 silicon-dioxide, illustrates that inner nanoparticle is a silicon-dioxide.
Fig. 6 has provided the typical SAED photo of hyper-thick pipe tadpole shape boron nitride nanometer powder for preparing.Show that by calculating five diffraction ring d values 0.3486,0.2103,0.1662,0.1256 and 0.1184nm correspond respectively to (002), (101), (004), (110) and (112) crystal face among the JCPDF#73-2095.
Embodiment 2
A kind of preparation method of hyper-thick pipe tadpole shape boron nitride nanometer powder, it comprises following step:
(1) takes by weighing water glass (Na respectively according to Si:Mg:B mol ratio 1:1:20
2SiO
39H
2O) 7.20 g, magnesium nitrate (Mg (NO
3)
26H
2O) 6.55 g and nano amorphous boron powder 5.45 g are as raw material for standby;
(2) be dissolved in water glass, magnesium nitrate in the distilled water respectively, stirring is configured to sodium silicate solution and magnesium nitrate solution, then the boron powder is added in the sodium silicate solution, drips 10ml ethanol (ethanol plays dissemination), ultrasonic and stir 60min, obtain water glass-boron powder mixed solution;
(3) magnesium nitrate solution is slowly splashed into water glass-boron powder mixed solution, rate of addition is 10ml/min, carries out ultrasonic agitation simultaneously, drips saturated NaOH solution and regulates pH value 8.5, and the canescence colloid slowly occurs, and the ultrasonic agitation time is 120min; After being added dropwise to complete mixed solution is left standstill 60min, suction filtration, washing is to neutral; Filter cake is directly put into 500 ℃ of insulations of retort furnace 120min, obtain the Si-Mg-O cellular solid;
(4) the Si-Mg-O porous material is descended and ammonia gas react 6h at 1400 ℃, ammonia flow 0.5L/min obtains crude product; Crude product is dispersed in the distilled water, add 5mol/L hydrochloric acid and 10mol/L hydrofluoric acid, in 60 ℃ of following heated and stirred 24h, suction filtration, washing and washing with alcohol then, at 80 ℃ of following vacuum-drying 12h, can obtain canescence hyper-thick pipe tadpole shape boron nitride nanometer powder 10.45g again.
Product is analyzed as can be known through XRD, FSEM, TEM/HRTEM, proves that product is a hyper-thick pipe tadpole shape boron nitride nanometer powder, and the tadpole top end diameter is about 1.5 μ m, the about 50nm of tail end diameter, length is about 15 μ m, and diameter is diminished to tail end gradually by the tadpole top, changes evenly.Judge that from the FSEM photo tadpole shape one-dimentional structure content is greater than 90%.。
Embodiment 3
A kind of preparation method of hyper-thick pipe tadpole shape boron nitride nanometer powder, it comprises following step:
(1) takes by weighing water glass (Na respectively according to Si:Mg:B mol ratio 1:1:40
2SiO
39H
2O) 7.25g, magnesium nitrate (Mg (NO
3)
26H
2O) 6.50 g and nano amorphous boron powder 10.90 g are as raw material for standby;
(2) be dissolved in water glass, magnesium nitrate in the distilled water respectively, stirring is configured to sodium silicate solution and magnesium nitrate solution, then the boron powder is added in the sodium silicate solution, drips 20ml ethanol (ethanol plays dissemination), ultrasonic and stir 60min, obtain water glass-boron powder mixed solution;
(3) magnesium nitrate solution is slowly splashed into water glass-boron powder mixed solution, rate of addition is 4ml/min, carries out ultrasonic agitation simultaneously, drips saturated NaOH solution and regulates pH value 7.2, and the canescence colloid slowly occurs, and the ultrasonic agitation time is 60min; After being added dropwise to complete mixed solution is left standstill 180min, suction filtration, washing is to neutral; Filter cake is directly put into 750 ℃ of insulations of retort furnace 60min, obtain the Si-Mg-O cellular solid;
(4) the Si-Mg-O porous material is descended and ammonia gas react 12h at 1100 ℃, ammonia flow 5L/min obtains crude product; Crude product is dispersed in the distilled water, add 5mol/L hydrochloric acid and 10mol/L hydrofluoric acid, in 60 ℃ of following heated and stirred 24h, suction filtration, washing and washing with alcohol then, at 80 ℃ of following vacuum-drying 24h, can obtain canescence hyper-thick pipe tadpole shape boron nitride nanometer powder 19.25g again.
Product is analyzed as can be known through XRD, FSEM, TEM/HRTEM, proves that product is a hyper-thick pipe tadpole shape boron nitride nanometer powder, and the tadpole top end diameter is about 1 μ m, the about 30nm of tail end diameter, length is about 10 μ m, and diameter is diminished to tail end gradually by the tadpole top, changes evenly.Judge that from the FSEM photo tadpole shape one-dimentional structure content is greater than 90%.
Embodiment 4
A kind of preparation method of hyper-thick pipe tadpole shape boron nitride nanometer powder, it comprises following step:
(1) takes by weighing water glass (Na respectively according to Si:Mg:B mol ratio 1:1:30
2SiO
39H
2O) 5.85 g, magnesium nitrate (Mg (NO
3)
26H
2O) 5.25 g and nano amorphous boron powder 6.55 g are as raw material for standby;
(2) be dissolved in water glass, magnesium nitrate in the distilled water respectively, stirring is configured to sodium silicate solution and magnesium nitrate solution, then the boron powder is added in the sodium silicate solution, drips 15ml ethanol (ethanol plays dissemination), ultrasonic and stir 120min, obtain water glass-boron powder mixed solution;
(3) magnesium nitrate solution is slowly splashed into water glass-boron powder mixed solution, rate of addition is 8ml/min, carries out ultrasonic agitation simultaneously, drips saturated NaOH solution and regulates pH value 8.0, and the canescence colloid slowly occurs, and the ultrasonic agitation time is 90min; After being added dropwise to complete mixed solution is left standstill 150min, suction filtration, washing is to neutral; Filter cake is directly put into 700 ℃ of insulations of retort furnace 90min, obtain the Si-Mg-O cellular solid;
(4) the Si-Mg-O porous material is descended and ammonia gas react 10h at 1300 ℃, ammonia flow 3L/min obtains crude product; Crude product is dispersed in the distilled water, add 5mol/L hydrochloric acid and 10mol/L hydrofluoric acid, in 60 ℃ of following heated and stirred 24h, suction filtration, washing and washing with alcohol then, at 80 ℃ of following vacuum-drying 24h, can obtain canescence hyper-thick pipe tadpole shape boron nitride nanometer powder 12.35g again.
Product is analyzed as can be known through XRD, FSEM, TEM/HRTEM, proves that product is a hyper-thick pipe tadpole shape boron nitride nanometer powder, and the tadpole top end diameter is about 1.5 μ m, the about 40nm of tail end diameter, length is about 12 μ m, and diameter is diminished to tail end gradually by the tadpole top, changes evenly.Judge that from the FSEM photo tadpole shape one-dimentional structure content is greater than 95%.
Claims (8)
1. the preparation method of a hyper-thick pipe tadpole shape boron nitride nanometer powder is characterized in that it comprises the steps:
(1) according to Si:Mg:B mol ratio 1:1:(10 ~ 40) take by weighing water glass, magnesium nitrate and boron powder raw material respectively;
(2) water glass, magnesium nitrate are dissolved in respectively in the distilled water, are configured to sodium silicate solution and magnesium nitrate solution, then the boron powder is added in the sodium silicate solution, dropping ethanol ultra-sonic dispersion also stirs, and obtains water glass-boron powder mixed solution;
(3) magnesium nitrate solution is slowly splashed into water glass-boron powder mixed solution, regulator solution PH is 7.2-8.5, carries out ultrasonic agitation simultaneously, and the canescence colloid slowly occurs, after being added dropwise to complete mixed solution is left standstill, and suction filtration, washing leaching cake is to neutral; Obtain the Si-Mg-O cellular solid after then filter cake directly being put into the retort furnace low-temperature annealing;
(4) the Si-Mg-O porous material is descended and ammonia gas react 6 ~ 12h at 1100 ~ 1400 ℃, obtain crude product; Then crude product is purified and drying, can obtain hyper-thick pipe tadpole shape boron nitride nanometer powder.
2. the preparation method of a kind of hyper-thick pipe tadpole shape boron nitride nanometer powder according to claim 1 is characterized in that described boron powder is the amorphous nano rank, and the median size size is 50nm, and purity is greater than 95wt%.
3. the preparation method of a kind of hyper-thick pipe tadpole shape boron nitride nanometer powder according to claim 1 is characterized in that ultrasonic in the described step (2), churning time is 30 ~ 60min.
4. the preparation method of a kind of hyper-thick pipe tadpole shape boron nitride nanometer powder according to claim 1, the speed that it is characterized in that dropping magnesium nitrate solution in the described step (3) is 4 ~ 10ml/min, the ultrasonic agitation time is 60-120min, and time of repose is 60 ~ 180min.
5. the preparation method of a kind of hyper-thick pipe tadpole shape boron nitride nanometer powder according to claim 1 is characterized in that stress relief annealed temperature is 500 ~ 750 ℃ in the described retort furnace, and soaking time is 60-120min.
6. the preparation method of a kind of hyper-thick pipe tadpole shape boron nitride nanometer powder according to claim 1 is characterized in that ammonia flow is 0.5 ~ 5L/min in the described step (4).
7. the preparation method of a kind of hyper-thick pipe tadpole shape boron nitride nanometer powder according to claim 1, it is characterized in that method of purification is earlier crude product to be dispersed in the distilled water in the described step (4), add 5mol/L hydrochloric acid and 10mol/L hydrofluoric acid, in 60 ℃ of following heated and stirred 12 ~ 24h, suction filtration, washing and washing with alcohol then are again at 80 ℃ of following vacuum-drying 12 ~ 24h.
8. the described preparation method of claim 1 ~ 7 obtains hyper-thick pipe tadpole shape boron nitride nanometer powder.
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| CN106882772A (en) * | 2017-04-14 | 2017-06-23 | 武汉理工大学 | A kind of preparation method of the controllable boron nitride nano-tube of caliber |
| CN110817814A (en) * | 2019-12-06 | 2020-02-21 | 桂林理工大学 | Preparation method and product of thin-wall BN micro-tube with one-dimensional hierarchical structure |
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| CN101244812A (en) * | 2008-02-26 | 2008-08-20 | 武汉理工大学 | Method for manufacturing flying saucer shaped nano-hexagonal boron nitride powder |
| CN101786884A (en) * | 2010-02-10 | 2010-07-28 | 武汉工程大学 | Preparation method of boron nitride nano-tube |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106882772A (en) * | 2017-04-14 | 2017-06-23 | 武汉理工大学 | A kind of preparation method of the controllable boron nitride nano-tube of caliber |
| CN106882772B (en) * | 2017-04-14 | 2018-10-23 | 武汉理工大学 | A kind of preparation method for the boron nitride nano-tube that caliber is controllable |
| CN110817814A (en) * | 2019-12-06 | 2020-02-21 | 桂林理工大学 | Preparation method and product of thin-wall BN micro-tube with one-dimensional hierarchical structure |
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| CN103224224B (en) | 2014-12-03 |
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