CN107793174A - Preparation method of boron nitride fiber three-dimensional structure material and product thereof - Google Patents
Preparation method of boron nitride fiber three-dimensional structure material and product thereof Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 76
- 239000000835 fiber Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004327 boric acid Substances 0.000 claims abstract description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 238000007710 freezing Methods 0.000 claims abstract description 8
- 230000008014 freezing Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 206010061592 cardiac fibrillation Diseases 0.000 claims description 45
- 230000002600 fibrillogenic effect Effects 0.000 claims description 45
- 238000012545 processing Methods 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 230000006835 compression Effects 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 7
- LXIJGELKPWRBPD-UHFFFAOYSA-N boric acid 1,3,5-triazine-2,4,6-triamine Chemical compound OB(O)O.OB(O)O.NC1=NC(N)=NC(N)=N1 LXIJGELKPWRBPD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000010276 construction Methods 0.000 description 9
- 238000009423 ventilation Methods 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 7
- 239000004964 aerogel Substances 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000372132 Hydrometridae Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241001529486 Roussea Species 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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Abstract
The invention provides a preparation method of a boron nitride fiber three-dimensional structure material and a product thereof. The method takes Melamine and boric acid as raw materials and water as a reaction medium, and prepares M.2B (English name: Melamine diborate) fibril by simple water bath synthesis; further taking the raw material as a raw material, and adopting a freezing forming process to obtain a three-dimensional network structure based on the fibril; the fibril three-dimensional structure is converted into a boron nitride fiber three-dimensional structure by means of a conventional heat treatment process. The technical method provided by the invention has the advantages of simple process, low raw material cost and environmental protection, and the material provided by the invention is a three-dimensional network structure taking boron nitride fibers as structural units, has the characteristics of light weight, high strength and hydrophobicity, and has wide application prospects in the fields of pollutant treatment, catalyst carriers and enhanced functional composite materials.
Description
Technical field
The present invention relates to technical field of ceramic material, and in particular to a kind of system of boron nitride fiber three-dimensional net structure material
Preparation Method and its product.
Background technology
Boron nitride material damages because of its high-temperature stability, good electrical insulating property, high heat conductance, low-k and low dielectric
The features such as consumption, excellent inoxidizability and chemical resistance, in Aero-Space, electrical engineering, microelectronic component and metallurgical work
The fields such as industry all have a wide range of applications.
Three-dimensional boron nitride porous ceramic has the characteristics such as lightweight, high-specific surface area, at sewage as a member therein
Reason, noble metal catalyst load and composite preparation etc. have important application value.In recent years, researcher causes
Power presently mainly passes through template synthesis method and freeze forming two in the boron nitride material that the type is prepared using easy method
Kind of method prepares the aeroge or foaming structure using boron nitride nanosheet and nanotube as construction unit.
For Rousseas et al. using charcoal-aero gel as template, boron oxide is raw material, in a nitrogen atmosphere by occurring with template
Carbothermic reduction reaction generation boron nitride displace charcoal, obtained by boron nitride nanosheet structure aeroge (M.Rousseas,
A.Goldstein,W.Mickelson,et al.,Synthesis of highly crystalline sp2-bonded
boron nitride aerogels[J].ACS nano,7(2013)8540-8546.)。
Song et al. generates hexagonal boron nitride using carbon nano tube/graphene aeroge as template, using chemical gas phase reaction
Film, it is oxidized remove obtained being cooperateed with nanometer sheet by boron nitride nano-tube after carbon build aerogel structure (Y.X.Song,
B.Li,S.Yang,et al.,Ultralight boron nitride aerogels via template-assisted
chemical vapor deposition[J],Sci.Rep-UK,5(2015)10337.)。
Yin and Ashton et al. are using nickel foam as template, using ammonia borine as raw material, are existed by the method for chemical vapor deposition
Boron nitride pellicle is formed in template, the bubble being interconnected to form by hexagonal boron nitride hollow and thin-walled pipe has been obtained after template is corroded
Foam structure, the structure has good elasticity, but its compression strength is only tens pas.(J.Yin,X.Li,J.Zhou,et al.,
Ultralight three-dimensional boron nitride foam with ultralow permittivity
and superelasticity[J].,Nano.Lett.,13(2013)3232-3236.T.S.Ashton and
A.L.Moore,Three-dimensional foam-like hexagonal boron nitride nanomaterials
via atmospheric pressure chemical vapor deposition[J].,J.Mater.Sci,50(2015)
6220-6226.)。
Lei et al. is prepared for amination modified boron nitride nanosheet from hexagonal boron nitride powder, and is dispersed in water
The colloidal solution of high concentration is obtained, ultralight boron nitride aeroge is obtained by way of freeze forming and low temperature drying
(W.W.Lei,V.Mochalin,D.Liu,et al.,Boron nitride colloidal solutions,ultralight
aerogels and freestanding membranes through one-step exfoliation and
functionalization[J].Nat.Commun.,6(2015)8849.)。
Zeng et al. is scattered in the aqueous solution and obtained uniformly using modified hydroxylating boron nitride nanosheet as construction unit
System, the aeroge based on boron nitride nanosheet is obtained by the method for freeze forming, the aeroge is by high molecular polymerization
Thing has excellent elastic and higher compression strength, but the presence of polymer limits boron nitride high temperature resistant as binding agent
Performance (X.Zeng, L.Ye, S.Yu, et al., Facile preparation of the superelastic and of performance
ultralow dielectric boron nitride nanosheet aerogels via freeze-casting
process[J].,Chem.Mater.,27(2015)5849-5855.)。
Above-mentioned three-dimensional porous boron nitride structural material is using nano material as construction unit, though there is lightweight, high porosity
The features such as, but its mechanical strength is not generally high, is easily destroyed in use, and nanometer chip architecture need to also be by intolerant to height
The high molecular polymer of temperature makees binding agent and just can guarantee that Stability Analysis of Structures, undoubtedly limits the application of this class formation.In addition, mould
Because the restriction effect of template size and reaction occur before needing harsh atmosphere, complexity poisonous in plate building-up process
Body is driven, prepared by the production that such method is difficult to mass, and conventional freezing moulding process is with the solvent in material system
Low temperature is frozen into template and carries out building for construction unit, although breaching the size limitation of intrinsic template, technique is simple, needs
Hydrophilic surface modification is carried out to construction units such as boron nitride nanosheets, is related to reaction and the process conditions of complexity, it is unfavorable
In popularization.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of easy side for preparing boron nitride porous ceramic material
Method, and the three-dimensional net structure material based on boron nitride fiber construction unit is obtained, specific technical scheme is as follows：
The invention discloses a kind of preparation method of boron nitride fiber three-dimensional structure material, comprise the following steps that：
S1, synthesis fibrillation：At a certain temperature, melamine and boric acid are added to the water and are stirred until completely molten
Solution, continue held for some time, solution is then cooled to room temperature, separate out flocky precipitate, stand, suction filtration obtains solid precipitation
Thing；By solid sediment heat preservation and dryness at a certain temperature, the fibrous solids of white are obtained；
Further, the molar ratio of melamine and boric acid is 1:2~5, the addition of melamine in every 100 milliliters of water
Measure as 1.26~2.52 grams；Preferably, the molar ratio of melamine and boric acid is 1:3；
Preferably, solvent selects deionized water；
Further, stirring and dissolving temperature is 80-95 DEG C, follow-up continuation of insurance warm 10-30 minutes is completely dissolved, then by solution
It is cooled to 20-30 DEG C；
Further, filtered after standing 10-24 hours and obtain solid sediment；
Further, by solid sediment at a temperature of 50-80 DEG C heat preservation and dryness 5-24 hours, obtain white threadiness
Solid；
Scanning electron microscope (SEM) photograph and X ray diffracting spectrum show molecular crystal of the solid for threadiness, chemical formula C3N6H6·
2H3BO3, comprising 1 melamine (English name Melamine) and 2 boric acid molecules (English name Boric acid), therefore it is called
M2B fibrillation；
S2, the shaping of fibrillation three-dimensional structure：
S201, S1 products are added to the water, heating stirring, obtain the slurry with mobility；
Further, the addition of S1 products is every 5.0~22.5 grams of 100 milliliters of water, preferable 10.0~17.5 grams；
Further, 50-95 DEG C is heated to, is incubated and stirs 0.5~5.0 hour, obtains the slurry with mobility；
Preferably, solvent selects deionized water；
S202, slurry poured into mould, cooling and standings, low-temperature vacuum drying is then carried out after freeze forming, is had
Effigurate three-dimensional net structure；
Further, the natural cooling in 20-30 DEG C of environment, after standing 5-24 hours, by its freeze forming；
Further, the method for freeze forming or realized with liquid nitrogen flash freezer is molded, and liquid nitrogen frozen can quickly prepare sample,
But a small amount of defect can be produced to structure, the temperature of liquid nitrogen frozen is at -80~-20 DEG C；Temperature control is then using liquid nitrogen as low-temperature receiver, ethanol
For refrigerant, specific cryogenic temperature is adjusted by adjusting the temperature of ethanol, it is controllable to reach the condition of freeze forming, liquid nitrogen
The temperature control of freezing is prior art, and the time of freeze forming is usually no more than 1 hour；
Or be put into refrigerator and freeze shaping, refrigerator freezing is advantageous to the stabilization of sample structure, and refrigerator freezing temperature is about
It can be controlled in 10-24 hours for -12~-5 DEG C of molding times；It is preferred that freeze forming in refrigerator；
The time of freeze forming is defined by slurry curing, can not do special requirement；
Further, the temperature of low-temperature vacuum drying be 0 DEG C between room temperature, preferable 5~20 DEG C, air pressure 40~
200Pa, time are 72-120 hours；
S3, inorganization processing：Under certain atmosphere, S2 products are subjected to high temperature inorganic processing；
Further, in ammonia, either under nitrogen or argon gas, or the mixed atmosphere of three's arbitrary proportion, it is warming up to
1~5 hour is incubated at 800~1000 DEG C；Further, throughput be 0.8~1.0 liter/min, heating rate be 5~10 DEG C/
Minute；
Preferably, under ammonia atmosphere；
S4, high-temperature crystallization processing：Under certain atmosphere, S3 products are subjected to high-temperature crystallization processing, finally produced
Thing；
Further, in nitrogen, either under the mixed atmosphere of argon gas or the two arbitrary proportion, it is warming up to 1600~
2000 DEG C are incubated 1~5 hour；Further, throughput is 0.8~1.0 liter/min, and heating rate is 5~10 DEG C/min；
Preferably, in a nitrogen atmosphere,
Preferably, the holding temperature of high-temperature crystallization processing is 1700~1900 DEG C；
Preferably, the intermediate product is positioned over progress high-temperature crystallization processing in boron nitride crucible.
One kind implements product made from above-mentioned boron nitride fiber three-dimensional structure material preparation method, and the material is to pass through nitrogen
Change the three-dimensional net structure of boron fibre structure, construction unit is that more boron nitride fibers combine the fibre bundle to be formed, and boron nitride is fine
Dimension microstructure is turbostratic graphite shape, i.e. t-BN phases, and wherein a diameter of 2~15 microns of boron nitride fiber, material volume density is
24~110 millis gram/cc, porosity is 93.4~98.8%, because the material is with the nitridation with high length-diameter ratio pattern
Boron fibre is construction unit, and its excellent in mechanical performance, compression strength reaches 0.007~0.038 MPa.
Further, the porosity of the material and density can be by changing M2B fibrillation in S2 step aqueous solvents
Addition is regulated and controled；
The material has the characteristics of lightweight, high-strength, hydrophobic, increases available for the processing of oily wastewater pollution thing, functional composite material
By force, noble metal catalyst load etc..
Beneficial effects of the present invention are：
Product is the macroscopic three dimensional network structure (Fig. 3) using boron nitride fiber as construction unit obtained by the inventive method,
Scanning electron microscopic picture (Fig. 4) shows that boron nitride fiber diameter is about 2~15 microns, and element power spectrum (Fig. 5) demonstrates the fiber and is
High-purity boron nitride, X ray diffracting spectrum (Fig. 6) show boron nitride for the relatively low random graphits structure of crystallinity, transmission electron microscope
Picture (Fig. 7) also directly confirms this crystal structure.Fig. 8 and Fig. 9 confirms gained boron nitride fiber three-dimensional network knot respectively
Structure has lightweight, hydrophobic and high intensity characteristic, and Figure 10, which illustrates the structure, can effectively absorb oily substance.It is this to be based on nitrogen
The three-dimensional net structure material for changing boron fibre can be applied to organic pollution processing, also can be as the enhancing of functional composite material
Body, precious metal catalyst agent carrier.
The inventive method based on melamine and boric acid water-bath synthesis M2B fibrillation method, by freeze forming with
Drying constructs M2B fibrillation three-dimensional net structures；Fibrillation network structure is converted into by the Technology for Heating Processing of routine
Boron nitride fiber network structure.The method overcome template be difficult to prepare large scale product the shortcomings that, it also avoid directly with
The functional modification process that boron nitride material assembling three-dimensional structure need to be carried out, the overall synthesis condition for not being related to complexity and toxicity
Raw material, cost is cheap, and technique is simple, green, is adapted to prepare with scale.
Brief description of the drawings
Fig. 1 is the scanning electron microscopic picture of the gained M2B fibrillation of the preferred embodiment of the present invention 1
Fig. 2 is the X ray diffracting spectrum of the gained M2B fibrillation of the preferred embodiment of the present invention 1
Fig. 3 is the optical photograph of the gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention 1；
Fig. 4 is the scanning electron microscopic picture of the gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention 1；
Fig. 5 is the element power spectrum of the gained boron nitride fiber of the preferred embodiment of the present invention 1；
Fig. 6 is the X ray diffracting spectrum of the gained boron nitride fiber of the preferred embodiment of the present invention 1；
Fig. 7 is the transmission electron microscope picture of the gained boron nitride fiber of the preferred embodiment of the present invention 1；
Fig. 8 is the optical photograph that the gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention 1 is bubbled through the water column；
Fig. 9 is the oils of the gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention 1 absorption floating on water
Optical photograph.
Figure 10 is the compression performance test curve of the gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention 1；
Embodiment
The present invention is described in further detail with accompanying drawing with reference to embodiments.Form the accompanying drawing of the part of the application
For providing a further understanding of the present invention, schematic description and description of the invention is used to explain the present invention, not
Form inappropriate limitation of the present invention.
Embodiment
In following examples, be using nitrogen or argon gas purity >=99.99% high pure nitrogen or argon gas；Other institutes
The chemical reagent used, unless otherwise specified, obtained by routine business approach.Water circulation used filters in the present invention
Machine, freeze drier are known device.
Embodiment 1
S1, synthesis fibrillation：Melamine and boric acid are added in deionized water, every 100 ml deionized water addition
1.26 grams of melamines and 1.86 grams of boric acid, both molar ratios are 1:3, it is straight that the system is put into heating stirring in 85 DEG C of water-baths
It is completely dissolved to solute, continues insulated and stirred 30 minutes, forms colourless transparent solution；It is subsequently placed at 30 DEG C and cools down, analyses
Go out sediment, after standing 24 hours, be filtrated to get solid sediment, be placed in being incubated 24 hours in 50 DEG C of thermostatic drying chambers, obtain
To dried white solid, Fig. 1 scanning electron microscope (SEM) photograph shows that it is fiber morphology, and Fig. 2 X ray diffracting spectrum shows its knot
Structure is C3N6H6·2H3BO3Molecular crystal, i.e. M2B；
S2, the shaping of fibrillation three-dimensional structure：Dry M2B fibrillation is added into deionized water, every 100 milliliters of deionizations
Water adds 10.0 grams of fibrillation, and 2 hours slurries for forming mobility of insulated and stirred, are poured into cylinder under 80 DEG C of water bath conditions
In shape mould, being cooled down under 30 DEG C of environment and stand 5 hours, be subsequently placed into refrigerator and freezed, cryogenic temperature is -12 DEG C, with
After be put into low temperature drying 120 hours in freeze drier, temperature maintains 5 DEG C or so, and freeze drying chamber air pressure maintains 120 pas
Left and right, obtain the cylindrical fibrillation three-dimensional net structure of drying；
S3, inorganization processing：Fibrillation three-dimensional net structure is put into tube furnace, is passed through with 1.0 liters/min of flow
Nitrogen, 1000 DEG C are warming up to 5 DEG C/min of speed, is incubated 1 hour, then stops ventilation, and naturally cool to room temperature；
S4, high-temperature crystallization processing：The intermediate product that inorganization processing obtains is put into graphite furnace, with 1.0 liters/min
Flow be passed through nitrogen, and be warming up to 1700 DEG C with 5 DEG C/min of speed, be incubated 3 hours, then stop ventilation, and natural cooling
To room temperature, boron nitride fiber three-dimensional net structure is obtained.
Fig. 1 is the scanning electron microscopic picture of M2B fibrillation prepared in the present embodiment, and Fig. 2 corresponds to M2B fibrillation
X ray diffracting spectrum.Fig. 3 show the optical photograph of cylindrical boron nitride fiber three-dimensional net structure, and the scanning in Fig. 4 is electric
Mirror illustrates the fibre bundle pattern inside network structure, 2~15 microns of its diameter distribution, is combined for plurality of fibers
The fibre bundle of formation, corresponding element power spectrum confirms that fiber is mainly made up of boron, nitrogen in Fig. 5, and the X ray in Fig. 6
Diffraction spectra also demonstrate that the boron nitride phase that fibrous crystal structure is partially crystallizable, and the transmission electron microscope picture in Fig. 7 shows three dimensional network
Boron nitride fiber microstructure is turbostratic graphite shape, i.e. t-BN phases in network structure.Fig. 8 show prepared boron nitride fiber three
Dimension network structure may float on the water surface, and the bulk density that the product is calculated by quality and volume is 45 milligrams/cube li
Rice, Fig. 9 then show the oils that structure absorption is floated on the water surface, and its porosity 97.3% is saturated absorption oils volume and its
The ratio between cumulative volume, by the compression performance of omnipotent testing machine for mechanical properties test article, obtain its pressure resistance in deformation 50%
Spend for 0.016 MPa.
Sum it up, the product has lightweight, high-strength and hydrophobic characteristic, available for the processing of oily wastewater pollution thing, function
Composite enhancing, noble metal catalyst load etc..
Embodiment 2
S1, synthesis fibrillation：Melamine and boric acid are added to the water, melamine and boric acid are added to the water, every 100
Milliliter water adds 1.26 grams of melamines and 1.24 grams of boric acid, and both molar ratios are 1:2, the system is put into 80 DEG C of water-baths
Heating stirring is completely dissolved up to solute, continues insulated and stirred 10 minutes, forms colourless transparent solution；It is subsequently placed at 20 DEG C
Lower cooling, sediment is separated out, after standing 10 hours, be filtrated to get solid sediment, be placed in being incubated 5 in 80 DEG C of thermostatic drying chambers
Hour, obtain dried white M2B fibrillation；
S2, the shaping of fibrillation three-dimensional structure：Dry M2B fibrillation is added to the water, every 100 milliliters of water addition 5.0
Gram fibrillation, 0.5 hour slurry for forming mobility of insulated and stirred, is poured into cylindrical die under 50 DEG C of water bath conditions
In, cooled down under 20 DEG C of environment and stand 24 hours, then using liquid nitrogen by its freeze forming, cryogenic temperature is -80 DEG C, then
Low temperature drying 120 hours in freeze drier are put into, temperature maintains 20 DEG C or so, and freeze drying chamber air pressure maintains 200 pas
Left and right, obtain the cylindrical fibrillation three-dimensional net structure of drying；
S3, inorganization processing：Fibrillation three-dimensional net structure is put into tube furnace, is passed through argon gas, flow is 0.8 liter/
Minute, 1000 DEG C are warming up to 10 DEG C/min of speed, is incubated 1 hour, then stops ventilation, and naturally cool to room temperature；
S4, high-temperature crystallization processing：The intermediate product that inorganization processing obtains is put into graphite furnace, with 0.8 liter/min
Flow be passed through nitrogen, and be warming up to 1600 DEG C with 10 DEG C/min of speed, be incubated 5 hours, then stop ventilation, and naturally cold
But to room temperature, boron nitride fiber three-dimensional net structure is obtained, its bulk density is 24 millis gram/cc, and porosity is
98.6%, compression strength is 0.007 MPa.
Embodiment 3
S1, synthesis fibrillation：Melamine and boric acid are added in deionized water, every 100 milliliters of water adds 2.52 gram three
Poly cyanamid and 6.20 grams of boric acid, both molar ratios are 1:5, the system is put into heating stirring in 95 DEG C of water-baths until solute is complete
Fully dissolved, continues insulated and stirred 30 minutes, forms colourless transparent solution；It is subsequently placed at 30 DEG C to cool down at room temperature, it is heavy to separate out
Starch, after standing 24 hours, solid sediment is filtrated to get, is placed in being incubated 15 hours in 60 DEG C of thermostatic drying chambers, is done
White solid after dry, i.e. M2B fibrillation；
S2, the shaping of fibrillation three-dimensional structure：Dry M2B fibrillation is added to the water, every 100 milliliters of water addition 22.5
Gram fibrillation, 5 hours slurries for forming mobility of insulated and stirred, are poured into cylindrical die under 95 DEG C of water bath conditions,
Cooled down under 25 DEG C of environment and stand 24 hours, be subsequently placed into refrigerator freezing and be molded 24 hours, cryogenic temperature is -5 DEG C, is then put
Entering low temperature drying 72 hours in freeze drier, temperature maintains 5 DEG C or so, and freeze drying chamber air pressure maintains 40 pas or so,
Obtain the cylindrical fibrillation three-dimensional net structure of drying；
S3, inorganization processing：Fibrillation three-dimensional net structure is put into tube furnace, is passed through with 1.0 liters/min of flow
Mixing ratio is 4:1 ammonia and argon gas, 800 DEG C are warming up to 5 DEG C/min of speed, is incubated 5 hours, then stop ventilation, and certainly
So it is cooled to room temperature；
S4, high-temperature crystallization processing：The inorganization obtained intermediate product of handling is put into boron nitride crucible, with 1.0 liters/
The flow of minute is passed through nitrogen, and is warming up to 2000 DEG C with 5 DEG C/min of speed, is incubated 1 hour, then stops logical nitrogen, and certainly
Room temperature so is cooled to, obtains boron nitride fiber three-dimensional net structure, its bulk density is 110 millis gram/cc, and porosity is
93.4%, compression strength is 0.038 MPa.
Embodiment 4
S1, synthesis fibrillation：Melamine and boric acid are added in deionized water, every 100 milliliters of water adds 1.26 gram three
Poly cyanamid and 1.86 grams of boric acid, both molar ratios are 1:3, the system is put into heating stirring in 85 DEG C of water-baths until solute is complete
Fully dissolved, continues insulated and stirred 20 minutes, forms colourless transparent solution；It is subsequently placed under 25 DEG C of environment and cools down, it is heavy to separate out
Starch, after standing 15 hours, solid sediment is filtrated to get, is placed in being incubated 24 hours in 60 DEG C of thermostatic drying chambers, is done
M2B fibrillation after dry；
S2, the shaping of fibrillation three-dimensional structure：M2B fibrillation is added to the water, every 100 milliliters of water adds 7.5 grams of fibrils
Dimension, 2 hours slurries for forming mobility of insulated and stirred, are poured into cylindrical die, at 25 DEG C under 60 DEG C of water bath conditions
Cooled down under environment and stand 12 hours, be then -20 DEG C by its freeze forming, cryogenic temperature with liquid nitrogen, it is dry to be subsequently placed into freezing
Low temperature drying 120 hours in dry machine, temperature maintain 20 DEG C or so, and freeze drying chamber air pressure maintains 50 pas or so, is done
Dry cylindrical fibrillation three-dimensional net structure；
S3, inorganization processing：Fibrillation three-dimensional net structure is put into tube furnace, is passed through ammonia, flow is 0.9 liter/
Minute, 1000 DEG C are warming up to 8 DEG C/min of speed, is incubated 1 hour, then stops ventilation, and naturally cool to room temperature；
S4, high-temperature crystallization processing：The inorganization obtained intermediate product of handling is put into boron nitride crucible, with 0.9 liter/
The flow of minute is passed through nitrogen, and is warming up to 1700 DEG C with 8 DEG C/min of speed, is incubated 1 hour, then stops ventilation, and naturally
Room temperature is cooled to, obtains boron nitride fiber three-dimensional net structure, its bulk density is 36 millis gram/cc, and porosity is
97.8%, compression strength is 0.011 MPa.
Embodiment 5
S1, synthesis fibrillation：Melamine and boric acid are added to the water, every 100 milliliters of water, 1.26 grams of melamines with
1.84 grams of boric acid, the system is put into 85 DEG C of water-baths heating stirring until solute is completely dissolved, continues insulated and stirred 30 minutes,
Form colourless transparent solution；It is subsequently placed at 30 DEG C to cool down at room temperature, separates out sediment, after standing 24 hours, is filtrated to get
Solid sediment, it is placed in being incubated 24 hours in 60 DEG C of thermostatic drying chambers, obtains dried M2B fibrillation；
S2, the shaping of fibrillation three-dimensional structure：M2B fibrillation is added into deionized water, every 100 milliliters of water, 17.5 grams of fibrils
Dimension, 2 hours slurries for forming mobility of insulated and stirred, are poured into cylindrical die, at 30 DEG C under 85 DEG C of water bath conditions
Cooled down under environment and stand 12 hours, be then -50 DEG C by its freeze forming 0.5 hour, cryogenic temperature with liquid nitrogen, be subsequently placed into
Low temperature drying 90 hours in freeze drier, temperature maintain 12 DEG C or so, and freeze drying chamber air pressure maintains 50 pas or so, obtains
To dry cylindrical fibrillation three-dimensional net structure；
S3, inorganization processing：Fibrillation three-dimensional net structure is put into tube furnace, is passed through ammonia, flow is 1.0 liters/
Minute, 900 DEG C are warming up to 10 DEG C/min of speed, is incubated 3 hours, then stops ventilation, and naturally cool to room temperature；
S4, high-temperature crystallization processing：The inorganization obtained intermediate product of handling is put into boron nitride crucible, with 1.0 liters/
The flow of minute is passed through mixing ratio as 1:1 nitrogen and argon gas, and 1900 DEG C are warming up to 10 DEG C/min of speed, insulation 1 is small
When, then stop logical nitrogen, and room temperature is naturally cooled to, boron nitride fiber three-dimensional net structure is obtained, its bulk density is 94
Milli gram/cc, porosity 94.3%, compression strength are~0.031 MPa.
Claims (10)
- A kind of 1. preparation method of boron nitride fiber three-dimensional structure material, it is characterised in that：Implement according to the following steps：S1, synthesis fibrillation：At a certain temperature, melamine and boric acid are added to the water and are stirred up to being completely dissolved, Hereafter continue held for some time under constant temperature, solution is then cooled to room temperature, separate out flocky precipitate, stand, take out Filter obtains solid sediment；By solid sediment heat preservation and dryness at a certain temperature, the fibrous solids of white are obtained；S2, the shaping of fibrillation three-dimensional structure：S201, S1 products are added to the water, heating stirring, obtain the slurry with mobility；S202, slurry poured into mould, cooling and standings, low-temperature vacuum drying is then carried out after freeze forming, obtain having one The three-dimensional net structure of setting shape；S3, inorganization processing：Under certain atmosphere, high temperature inorganicization processing；S4, high-temperature crystallization processing：Under certain atmosphere, high-temperature crystallization processing, final product is obtained.
- A kind of 2. preparation method of boron nitride fiber three-dimensional structure material according to claim 1, it is characterised in that：In S1 steps：The molar ratio of the melamine and boric acid is 1:2~5, the addition of melamine is 1.26 in every 100 milliliters of water ~2.52 grams, stirring and dissolving temperature is 80-95 DEG C, is completely dissolved follow-up continuation of insurance warm 10-30 minutes, is then cooled to solution 20-30℃；Filtered after standing 10-24 hours；The condition of the heat preservation and dryness is heat preservation and dryness 5-24 hours at a temperature of 50-80 DEG C；In S201 steps：The addition of the S1 products is every 5.0~22.5 grams of 100 milliliters of water, and the condition of the heating stirring is：It is heated to 50- 95 DEG C, it is incubated and stirs 0.5~5.0 hour；In S202 steps：The condition of the cooling and standings is the natural cooling in 20-30 DEG C of environment, stands 5-24 hours；The freeze forming, or realized and be molded with liquid nitrogen flash freezer, or be put into refrigerator and freeze shaping；The condition of the low-temperature vacuum drying is：For temperature for 0 DEG C between room temperature, 40~200Pa of air pressure, the time is that 72-120 is small When；In S3 steps：The high temperature inorganicization processing concretely comprises the following steps, in ammonia, either nitrogen or argon gas, or three's arbitrary proportion Mixed atmosphere under, be warming up at 800~1000 DEG C and be incubated 1~5 hour；Throughput is 0.8~1.0 liter/min, heating rate For 5~10 DEG C/min；In S4 steps：High-temperature crystallization processing concretely comprises the following steps, in nitrogen, the either mixed atmosphere of argon gas or the two arbitrary proportion Under, it is warming up to 1600~2000 DEG C and is incubated 1~5 hour；Further, throughput is 0.8~1.0 liter/min, and heating rate is 5~10 DEG C/min.
- 3. the preparation method of a kind of boron nitride fiber three-dimensional structure material according to claim 2, it is characterised in that in S1 In being walked with S2, solvent selects deionized water.
- A kind of 4. preparation method of boron nitride fiber three-dimensional structure material according to claim 2, it is characterised in thatIn S202 steps：Liquid nitrogen flash freezer realizes the temperature of shaping at -80~-20 DEG C；Or the temperature of refrigerator freezing shaping is -12~-5 DEG C.
- 5. the preparation method of a kind of boron nitride fiber three-dimensional structure material according to claim 2, it is characterised in that in S2 In step, addition of the S1 products in water is every 10.0~17.5 grams of 100 milliliters of water.
- 6. the preparation method of a kind of boron nitride fiber three-dimensional structure material according to claim 2, it is characterised in that S3 is walked Middle to select ammonia, S4 steps select nitrogen.
- 7. the preparation method of a kind of boron nitride fiber three-dimensional structure material according to claim 2, it is characterised in that in S4 In step, the intermediate product is positioned over progress high-temperature crystallization processing in boron nitride crucible.
- 8. a kind of boron nitride fiber three-dimensional structure material being prepared by any means claim 1~7 described, its feature exist Be the three-dimensional net structure built by boron nitride fiber in, the material, it is microcosmic it is upper be turbostratic graphite shape structure, i.e. t-BN A diameter of 2~15 microns of phase, wherein boron nitride fiber, material volume density are 24~110 millis gram/cc, and porosity is 93.4~98.8%, compression strength is 0.007~0.038 MPa.
- A kind of 9. boron nitride fiber three-dimensional structure material according to claim 8, it is characterised in that the volume of the material Density and adjustable porosity.
- A kind of 10. application of boron nitride fiber three-dimensional structure material according to claim 8, it is characterised in that the material Applied to the processing of oily wastewater pollution thing, functional composite material enhancing, noble metal catalyst load.
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