CN107793174B - 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 77
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 75
- 239000000835 fiber Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 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
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 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
- 102000008946 Fibrinogen Human genes 0.000 claims description 45
- 108010049003 Fibrinogen Proteins 0.000 claims description 45
- 229940012952 fibrinogen Drugs 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000012545 processing Methods 0.000 claims description 27
- 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
- 238000000465 moulding Methods 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 11
- 238000003756 stirring Methods 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
- 238000001816 cooling Methods 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
- 238000004321 preservation Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 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
- 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 25
- 230000008569 process Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 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 13
- 239000000243 solution Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- 239000002135 nanosheet Substances 0.000 description 7
- 238000009423 ventilation Methods 0.000 description 7
- 239000004964 aerogel Substances 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 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
- 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
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002156 mixing 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
- FBPFZTCFMRRESA-ZXXMMSQZSA-N D-iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 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
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon 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
- 230000008859 change Effects 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
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency 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
- 230000005611 electricity Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/58—
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—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
- 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
- C04B35/583—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 based on boron nitride
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
- C04B35/62286—Fibres based on nitrides
- C04B35/6229—Fibres based on nitrides based on boron nitride
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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 technique
Boron nitride material is damaged 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 corrosion resistance, in aerospace, 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 material 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 for preparing the type using easy method
Kind method preparation is using boron nitride nanosheet and nanotube as the aeroge of structural unit or foaming structure.
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 generate boron nitride displace charcoal, obtained by boron nitride nanosheet construct 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, through aoxidize except obtained after carbon being cooperateed with by boron nitride nano-tube with nanometer sheet constructing 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, and the bubble being interconnected to form by hexagonal boron nitride hollow and thin-walled pipe has been obtained after template is corroded
Foam structure, which 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 aqueous solution and obtains uniformly using modified hydroxylating boron nitride nanosheet as construction unit
System has obtained the aeroge based on boron nitride nanosheet by the method for freeze forming, and the aeroge is by high molecular polymerization
Object is as binder, and with excellent elasticity and higher compression strength, but the presence of polymer limits boron nitride high temperature resistant
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 structural unit, though there is lightweight, high porosity
The features such as, but its mechanical strength is not usually 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 binder and just can guarantee stable structure, undoubtedly limits the application range of this class formation.In addition, mould
Since the restriction effect of template size and reaction occur before needing harsh atmosphere, complexity toxic in plate synthesis process
Body is driven, such method is difficult to realize the production preparation of mass, and conventional freezing moulding process is with the solvent in material system
Low temperature is frozen into template and carries out building for structural unit, although breaching the size limitation of intrinsic template, simple process needs
Hydrophilic surface is carried out to structural units such as boron nitride nanosheets to be modified, and is related to complicated reaction and process conditions, it is unfavorable
In popularization.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of sides for preparing boron nitride porous ceramic material of simplicity
Method, and the three-dimensional net structure material based on boron nitride fiber structural unit is obtained, specific technical solution is as follows:
The invention discloses a kind of preparation methods of boron nitride fiber three-dimensional structure material, the specific steps are as follows:
S1, synthesis fibrinogen: at a certain temperature, melamine and boric acid is added to the water and are stirred until completely molten
Solution continues held for some time, is then cooled to room temperature solution, and flocky precipitate is precipitated, and stands, and suction filtration obtains solid precipitating
Object；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
Amount is 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, is completely dissolved subsequent continuation of insurance temperature 10-30 minutes, then by solution
It is cooled to 20-30 DEG C；
Further, it is filtered after standing 10-24 hours and obtains solid sediment；
Further, by solid sediment heat preservation and dryness 5-24 hours at a temperature of 50-80 DEG C, the threadiness of white is obtained
Solid；
Scanning electron microscope (SEM) photograph and X ray diffracting spectrum show that the solid is the molecular crystal of 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 fibrinogen；
S2, the molding of fibrinogen three-dimensional structure:
S201, S1 product is added to the water, heating stirring obtains the slurry with mobility；
Further, the additive amount of S1 product is every 5.0~22.5 grams of 100 milliliters of water, preferred 10.0~17.5 grams；
Further, it is heated to 50-95 DEG C, keep the temperature and is stirred 0.5~5.0 hour, the slurry with mobility is obtained；
Preferably, solvent selects deionized water；
S202, slurry is poured into mold, 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 forms, and liquid nitrogen frozen can quickly prepare sample,
But a small amount of defect can be generated to structure, the temperature of liquid nitrogen frozen is at -80~-20 DEG C；Temperature controls then using liquid nitrogen as cold source, ethyl alcohol
For refrigerant, specific cryogenic temperature is adjusted by adjusting the temperature of ethyl alcohol, the condition for reaching freeze forming is controllable, liquid nitrogen
The temperature control of freezing is the prior art, and the time of freeze forming is usually no more than 1 hour；
Molding is freezed alternatively, being put into refrigerator, refrigerator freezing is conducive to the stabilization of sample structure, and refrigerator freezing temperature is about
It can control for -12~-5 DEG C of molding times at 10-24 hours；It is preferred that freeze forming in refrigerator；
The time of freeze forming is subject to slurry curing, can not do special requirement；
Further, the temperature of low-temperature vacuum drying is 0 DEG C between room temperature, preferred 5~20 DEG C, air pressure 40~
200Pa, time are 72-120 hours；
S3, inorganization processing: under certain atmosphere, S2 product is subjected to high temperature inorganic processing；
Further, in ammonia, perhaps nitrogen is warming up to perhaps under the mixed atmosphere of argon gas or three's arbitrary proportion
1~5 hour is kept the temperature 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 product is subjected to high-temperature crystallization processing, is finally produced
Object；
Further, under the nitrogen perhaps mixed atmosphere of argon gas or the two arbitrary proportion, it is warming up to 1600~
2000 DEG C keep the temperature 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 placed in progress high-temperature crystallization processing in boron nitride crucible.
A kind of to implement product made from above-mentioned boron nitride fiber three-dimensional structure material preparation method, the material is to pass through nitrogen
Change the three-dimensional net structure of boron fibre building, structural 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 phase, and wherein boron nitride fiber diameter is 2~15 microns, and material volume density is
24~110 millis gram/cc, porosity is 93.4~98.8%, since the material is with the nitridation with high length-diameter ratio pattern
Boron fibre is structural unit, excellent in mechanical performance, and compression strength reaches 0.007~0.038 megapascal.
Further, the porosity and density of the material can be by changing M2B fibrinogen in S2 step aqueous solvent
Additive amount is regulated and controled；
The material has the characteristics that lightweight, high-strength, hydrophobic, can be used for the processing of oily wastewater pollution object, functional composite material increases
By force, noble metal catalyst load etc..
The invention has the benefit that
Product obtained by the method for the present invention be using boron nitride fiber as the macroscopic three dimensional network structure (Fig. 3) of structural unit,
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 that boron nitride is the lower 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-intensitive 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 pollutant processing, also can be used as the enhancing of functional composite material
Body, precious metal catalyst agent carrier.
The method of the present invention based on melamine and boric acid water-bath synthesis M2B fibrinogen method, by freeze forming with
Drying constructs M2B fibrinogen three-dimensional net structure；Fibrinogen network structure is converted to by conventional heat treatment process
Boron nitride fiber network structure.The method overcome templates to be difficult to the shortcomings that preparing large size product, also avoid directly with
The functional modification process that boron nitride material assembling three-dimensional structure need to carry out, the whole synthesis condition for not being related to complexity and toxicity
Raw material, low in cost, simple process is environmentally protective, is suitble to prepare with scale.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture of 1 gained M2B fibrinogen of the preferred embodiment of the present invention
Fig. 2 is the X ray diffracting spectrum of 1 gained M2B fibrinogen of the preferred embodiment of the present invention
Fig. 3 is the optical photograph of 1 gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention；
Fig. 4 is the scanning electron microscopic picture of 1 gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention；
Fig. 5 is the element power spectrum of 1 gained boron nitride fiber of the preferred embodiment of the present invention；
Fig. 6 is the X ray diffracting spectrum of 1 gained boron nitride fiber of the preferred embodiment of the present invention；
Fig. 7 is the transmission electron microscope picture of 1 gained boron nitride fiber of the preferred embodiment of the present invention；
Fig. 8 is the optical photograph that 1 gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention is bubbled through the water column；
Fig. 9 is the oils of 1 gained boron nitride fiber three-dimensional net structure of preferred embodiment of the present invention absorption floating on water
Optical photograph.
Figure 10 is the compression performance test curve of 1 gained boron nitride fiber three-dimensional net structure of the preferred embodiment of the present invention；
Specific embodiment
Invention is further described in detail with attached drawing with reference to embodiments.The attached drawing constituted part of this application
It is used to provide further understanding of the present invention, the illustrative embodiments of the present invention and their descriptions are used to explain the present invention, not
Constitute inappropriate limitation of the present invention.
Embodiment
In following embodiment, be using nitrogen or argon gas purity >=99.99% high pure nitrogen or argon gas；Other institutes
The chemical reagent used is obtained by routine business approach unless otherwise specified.The circulation of water used in the present invention filters
Machine, freeze drier are known device.
Embodiment 1
S1, synthesis fibrinogen: 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, the two molar ratio are 1:3, and it is straight which is put into heating stirring in 85 DEG C of water-baths
It is completely dissolved, continues insulated and stirred 30 minutes to solute, form colourless transparent solution；Cooling, analysis is subsequently placed at 30 DEG C
Sediment out is obtained by filtration solid sediment, is placed in 50 DEG C of thermostatic drying chambers and keeps the temperature 24 hours, obtain after standing 24 hours
White solid after to drying, the scanning electron microscope (SEM) photograph of Fig. 1 show it as fiber morphology, and the X ray diffracting spectrum of Fig. 2 shows its knot
Structure is C3N6H6·2H3BO3Molecular crystal, i.e. M2B；
S2, the molding of fibrinogen three-dimensional structure: deionized water, every 100 milliliters of deionizations is added in dry M2B fibrinogen
Water adds 10.0 grams of fibrinogens, forms within insulated and stirred 2 hours the slurry of mobility under 80 DEG C of water bath conditions, is poured into cylinder
In shape mold, 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 obtains dry cylindrical fibrinogen three-dimensional net structure；
S3, inorganization processing: fibrinogen three-dimensional net structure is put into tube furnace, is passed through with 1.0 liters/min of flow
Nitrogen is warming up to 1000 DEG C with 5 DEG C/min of rates, keeps the temperature 1 hour, then stops ventilation, and cooled to room temperature；
S4, high-temperature crystallization processing: the inorganization obtained intermediate product that handles 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 rates, keep the temperature 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 fibrinogen prepared in the present embodiment, and Fig. 2 corresponds to M2B fibrinogen
X ray diffracting spectrum.Fig. 3 show the optical photograph of cylindrical boron nitride fiber three-dimensional net structure, and the scanning electricity in Fig. 4
Mirror illustrates the fibre bundle pattern inside network structure, 2~15 microns of diameter distribution, combines for plurality of fibers
The fibre bundle of formation, corresponding element power spectrum confirms that fiber is mainly made of boron, nitrogen in Fig. 5, and the X-ray in Fig. 6
Diffraction spectra also demonstrates that fibrous crystal structure is the boron nitride phase of 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 phase in network structure.Fig. 8 show prepared boron nitride fiber three
Dimension network structure may float on the water surface, be 45 milligrams/cube li by the bulk density that quality and volume calculate the product
Rice, Fig. 9 then show that structure absorption floats on the oils on the water surface, and porosity 97.3% is saturated absorption oils volume and its
The ratio between total volume obtains its pressure resistance in deformation 50% by the compression performance of omnipotent testing machine for mechanical properties test article
Degree is 0.016 megapascal.
To sum up, the product has lightweight, high-strength and hydrophobic characteristic, it can be used for the processing of oily wastewater pollution object, function
Composite material enhancing, noble metal catalyst load etc..
Embodiment 2
S1, synthesis fibrinogen: melamine and boric acid being added to the water, melamine and boric acid are added to the water, and every 100
Milliliter water adds 1.26 grams of melamines and 1.24 grams of boric acid, and the two molar ratio is 1:2, which is put into 80 DEG C of water-baths
For heating stirring until solute is completely dissolved, continuation insulated and stirred 10 minutes forms colourless transparent solution；It is subsequently placed at 20 DEG C
Sediment is precipitated in lower cooling, after standing 10 hours, solid sediment is obtained by filtration, is placed in 80 DEG C of thermostatic drying chambers and keeps the temperature 5
Hour, the M2B fibrinogen of the white after being dried；
S2, the molding of fibrinogen three-dimensional structure: dry M2B fibrinogen is added to the water, every 100 milliliters of water addition 5.0
Gram fibrinogen forms the slurry of mobility for insulated and stirred 0.5 hour under 50 DEG C of water bath conditions, is poured into cylindrical die
In, it is cooled down under 20 DEG C of environment and stands 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 obtains dry cylindrical fibrinogen three-dimensional net structure；
S3, inorganization processing: fibrinogen three-dimensional net structure is put into tube furnace, is passed through argon gas, and flow is 0.8 liter/
Minute, 1000 DEG C are warming up to 10 DEG C/min of rates, keeps the temperature 1 hour, then stops ventilation, and cooled to room temperature；
S4, high-temperature crystallization processing: the inorganization obtained intermediate product that handles 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 rates, keep the temperature 5 hours, then stop ventilation, and naturally cold
But to room temperature, boron nitride fiber three-dimensional net structure is obtained, bulk density is 24 millis gram/cc, and porosity is
98.6%, compression strength is 0.007 megapascal.
Embodiment 3
S1, synthesis fibrinogen: 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, the two molar ratio are 1:5, which 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 be precipitated
Starch is obtained by filtration solid sediment, is placed in 60 DEG C of thermostatic drying chambers and keeps the temperature 15 hours, done after standing 24 hours
White solid after dry, i.e. M2B fibrinogen；
S2, the molding of fibrinogen three-dimensional structure: dry M2B fibrinogen is added to the water, every 100 milliliters of water addition 22.5
Gram fibrinogen forms the slurry of mobility for insulated and stirred 5 hours under 95 DEG C of water bath conditions, is poured into cylindrical die,
It is cooled down under 25 DEG C of environment and stands 24 hours, be subsequently placed into refrigerator freezing and form 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 dry cylindrical fibrinogen three-dimensional net structure；
S3, inorganization processing: fibrinogen three-dimensional net structure is put into tube furnace, is passed through with 1.0 liters/min of flow
Mixing ratio is the ammonia and argon gas of 4:1, is warming up to 800 DEG C with 5 DEG C/min of rates, keeps the temperature 5 hours, then stops ventilating, and from
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 rates, keeps the temperature 1 hour, then stops logical nitrogen, and certainly
It is so cooled to room temperature, obtains boron nitride fiber three-dimensional net structure, bulk density is 110 millis gram/cc, and porosity is
93.4%, compression strength is 0.038 megapascal.
Embodiment 4
S1, synthesis fibrinogen: 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, the two molar ratio are 1:3, which 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 at cooling under 25 DEG C of environment, it is heavy to be precipitated
Starch is obtained by filtration solid sediment, is placed in 60 DEG C of thermostatic drying chambers and keeps the temperature 24 hours, done after standing 15 hours
M2B fibrinogen after dry；
S2, the molding of fibrinogen three-dimensional structure: M2B fibrinogen is added to the water, 7.5 grams of fibrils are added in every 100 milliliters of water
Dimension forms the slurry of mobility for insulated and stirred 2 hours under 60 DEG C of water bath conditions, is poured into cylindrical die, at 25 DEG C
It is cooled down under environment and stands 12 hours, then with liquid nitrogen by its freeze forming, cryogenic temperature is -20 DEG C, and 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 fibrinogen three-dimensional net structure；
S3, inorganization processing: fibrinogen three-dimensional net structure is put into tube furnace, is passed through ammonia, and flow is 0.9 liter/
Minute, 1000 DEG C are warming up to 8 DEG C/min of rates, keeps the temperature 1 hour, then stops ventilation, and cooled 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 rates, keeps the temperature 1 hour, then stops ventilation, and naturally
It is cooled to room temperature, obtains boron nitride fiber three-dimensional net structure, bulk density is 36 millis gram/cc, and porosity is
97.8%, compression strength is 0.011 megapascal.
Embodiment 5
S1, synthesis fibrinogen: melamine and boric acid are added to the water, every 100 milliliters of water, 1.26 grams of melamines with
The system is put into 85 DEG C of water-baths heating stirring until solute is completely dissolved, continued insulated and stirred 30 minutes by 1.84 grams of boric acid,
Form colourless transparent solution；It is subsequently placed at 30 DEG C to cool down at room temperature, sediment is precipitated, after standing 24 hours, be obtained by filtration
Solid sediment is placed in 60 DEG C of thermostatic drying chambers and keeps the temperature 24 hours, the M2B fibrinogen after being dried；
S2, the molding of fibrinogen three-dimensional structure: deionized water, every 100 milliliters of water, 17.5 grams of fibrils are added in M2B fibrinogen
Dimension forms the slurry of mobility for insulated and stirred 2 hours under 85 DEG C of water bath conditions, is poured into cylindrical die, at 30 DEG C
It is cooled down under environment and stands 12 hours, then with liquid nitrogen by its freeze forming 0.5 hour, cryogenic temperature is -50 DEG C, is 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 fibrinogen three-dimensional net structure；
S3, inorganization processing: fibrinogen three-dimensional net structure is put into tube furnace, is passed through ammonia, and flow is 1.0 liters/
Minute, 900 DEG C are warming up to 10 DEG C/min of rates, keeps the temperature 3 hours, then stops ventilation, and 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 the nitrogen and argon gas that mixing ratio is 1:1, and is warming up to 1900 DEG C with 10 DEG C/min of rates, and heat preservation 1 is small
When, then stop logical nitrogen, and cooled to room temperature, obtains boron nitride fiber three-dimensional net structure, bulk density 94
Milli gram/cc, porosity 94.3%, compression strength are~0.031 megapascal.
Claims (9)
1. a kind of preparation method of boron nitride fiber three-dimensional structure material, it is characterised in that: implement according to the following steps:
S1, synthesis fibrinogen: at a certain temperature, melamine and boric acid being added to the water and are stirred up to being completely dissolved,
Hereafter continue held for some time under constant temperature conditions, be then cooled to room temperature solution, flocky precipitate is precipitated, 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；
The molar ratio of the melamine and boric acid is 1:2~5, and the additive amount 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 subsequent continuation of insurance temperature 10-30 minutes, is then cooled to solution
20-30℃；It is 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；
S2, the molding of fibrinogen three-dimensional structure:
S201, S1 product is added to the water, heating stirring obtains the slurry with mobility；
The additive amount of the S1 product is every 5.0~22.5 grams of 100 milliliters of water, the condition of the heating stirring are as follows: be heated to 50-
It 95 DEG C, keeps the temperature and stirs 0.5~5.0 hour；
S202, slurry is poured into mold, 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；
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 formed with liquid nitrogen flash freezer, or be put into refrigerator and freeze molding；
The condition of the low-temperature vacuum drying are as follows: temperature is 0 DEG C between room temperature, and 40~200Pa of air pressure, the time is that 72-120 is small
When；
S3, inorganization processing: under certain atmosphere, high temperature inorganicization processing；
High temperature inorganicization processing the specific steps are in ammonia perhaps nitrogen perhaps argon gas or three's arbitrary proportion
Mixed atmosphere under, be warming up at 800~1000 DEG C and keep the temperature 1~5 hour；Throughput is 0.8~1.0 liter/min, heating rate
It is 5~10 DEG C/min；
S4, high-temperature crystallization processing: under certain atmosphere, high-temperature crystallization processing obtains final product；
High-temperature crystallization processing the specific steps are in the nitrogen perhaps mixed atmosphere of argon gas or the two arbitrary proportion
Under, it is warming up to 1600~2000 DEG C and keeps the temperature 1~5 hour；Further, throughput is 0.8~1.0 liter/min, and heating rate is
5~10 DEG C/min.
2. a kind of preparation method of boron nitride fiber three-dimensional structure material according to claim 1, which is characterized in that in S1
In S2 step, solvent selects deionized water.
3. a kind of preparation method of boron nitride fiber three-dimensional structure material according to claim 1, which is characterized in that
In S202 step: liquid nitrogen flash freezer realizes molding temperature at -80~-20 DEG C；
Alternatively, the molding temperature of refrigerator freezing is -12~-5 DEG C.
4. a kind of preparation method of boron nitride fiber three-dimensional structure material according to claim 1, which is characterized in that in S2
In step, the additive amount of S1 product in water is every 10.0~17.5 grams of 100 milliliters of water.
5. a kind of preparation method of boron nitride fiber three-dimensional structure material according to claim 1, which is characterized in that S3 step
Middle selection ammonia, S4 step select nitrogen.
6. a kind of preparation method of boron nitride fiber three-dimensional structure material according to claim 1, which is characterized in that in S4
In step, high-temperature crystallization processing carries out in boron nitride crucible.
7. a kind of boron nitride fiber three-dimensional structure material being prepared by any means described in claim 1~6, feature exist
In the material is the three-dimensional net structure constructed by boron nitride fiber, microcosmic upper for turbostratic graphite shape structure, i.e. t-BN
Phase, wherein boron nitride fiber diameter is 2~15 microns, and material volume density is 24~110 millis gram/cc, and porosity is
93.4~98.8%, compression strength is 0.007~0.038 megapascal.
8. a kind of boron nitride fiber three-dimensional structure material according to claim 7, which is characterized in that the volume of the material
Density and adjustable porosity.
9. a kind of application of boron nitride fiber three-dimensional structure material according to claim 7, which is characterized in that the material is answered
For the processing of oily wastewater pollution object, functional composite material enhancing, noble metal catalyst load.
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