CN106830011B - A kind of preparation method of nitrolim dispersed nano particle - Google Patents
A kind of preparation method of nitrolim dispersed nano particle Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- STRTXDFFNXSZQB-UHFFFAOYSA-N calcium;cyanamide Chemical compound [Ca+2].NC#N STRTXDFFNXSZQB-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000002121 nanofiber Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 238000004176 ammonification Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 21
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- BNWPUUZJGBXAFM-UHFFFAOYSA-N azane oxalonitrile Chemical compound N.N#CC#N BNWPUUZJGBXAFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 13
- 239000012071 phase Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229910002230 La2Zr2O7 Inorganic materials 0.000 description 1
- 229910002333 LaMO3 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 241000565675 Oncomelania Species 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JLCRXCPXQLBSEM-UHFFFAOYSA-N calcium diisocyanate Chemical compound [Ca++].[N-]=C=O.[N-]=C=O JLCRXCPXQLBSEM-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002837 defoliant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 238000005121 nitriding Methods 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/16—Cyanamide; Salts thereof
- C01C3/18—Calcium cyanamide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention relates to a kind of preparation methods of nitrolim dispersed nano particle, belong to technical field of nanometer material preparation.The method preparation CaCN that the present invention is combined using electrostatic spinning technique with cyanogen ammonification technology2Dispersed nano particle.The present invention includes four steps: (1) preparing spinning solution；(2) PVP/Ca (NO is prepared3)2Composite nano fiber is prepared using electrostatic spinning technique；(3) CaCO is prepared3Nanofiber, high-temperature heat treatment PVP/Ca (NO3)2Composite nano fiber obtains CaCO3Nanofiber；(4) CaCN is prepared2Dispersed nano particle, using graphite boat and ammonia by CaCO3Nanofiber carries out cyanogen ammonification, obtains CaCN2Dispersed nano particle has good crystallinity, belongs to trigonal system, and diameter is 250 ± 0.27nm.Of the invention preparation method is simple, can produce in batches, have broad application prospects.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, a kind of nitrolim dispersed nano particle is in particulard relate to
Preparation method.
Background technique
Nitrolim CaCN2It is a kind of important nitrogenous fertilizer, it is also possible to make defoliant and herbicide；In chemical industry, cyanogen ammonia
Changing calcium is to prepare cyanamide, dicyandiamide, melamine and the raw material for replacing triazine, and these compounds can be further processed into
Thiocarbamide and guanidine.In steel and iron industry, nitrolim is directly used as carbon steel and low-alloyed nitriding medium and pig iron desulfurizer, is alternatively arranged as
Evil-force loses agent and mitigates corrosion of the salt water to steel.In terms of three-protection design, nitrolim can be used for removing the formaldehyde in waste water.Cyanogen ammonification
Another important use of calcium is manufacture pesticide, such as oncomelania killer.CaCN at present2Research concentrate on bulky grain powder material side
Face is mainly prepared using the methods of high temperature gas-solid phase synthesi and solid-solid phase synthesi, such as in the industrial production, using in height
CaCN is prepared with nitrogen treatment calcium carbide powder under temperature2Powder；With urea and CaO or CaCO3Reaction, obtains calcium cyanate Ca (OCN)2
Afterwards, CaCN is thermally decomposed to yield at high temperature2Powder.CaCN is had no at present2The report of dispersed nano particle.
One related electrospinning process (electrospinning) of the U.S. Patent Publication of Patent No. 1975504
Technical solution, this method is a kind of effective ways for preparing continuous micro nanometer fiber with macro length, by
Formhals was proposed first in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making electrification
Polymer solution or melt is sprayed by the traction of electrostatic force by nozzle in electrostatic field, invests the receiving screen on opposite, thus real
Existing wire drawing, then solvent evaporation or melt are cooled to room temperature and solidify at normal temperature, obtain micro nanometer fiber.In the past 10 years,
Occur preparing inorganic compound such as oxide nanofiber using electrospinning process in inorfil preparation technical field
Technical solution, the oxide include TiO2、ZrO2、Y2O3、Y2O3:RE3+(RE3+=Eu3+、Tb3+、Er3+、Yb3+/Er3+)、
NiO、Co3O4、Mn2O3、Mn3O4、CuO、Fe3O4、SiO2、Al2O3、ZnO、CdO、Nb2O5、MoO3、CeO2、SnO2、LaMO3(M=
Fe、Cr、Mn、Co、Ni、Al)、Y3Al5O12、La2Zr2O7Equal metal oxides and composite oxide of metal.Electrostatic spinning technique energy
It is enough continuously to prepare big L/D ratio micrometer fibers or nanofiber.It has no at present using electrostatic spinning technique and cyanogen ammonification technology phase
In conjunction with method prepare CaCN2The report of dispersed nano particle.
When preparing nano material using electrostatic spinning technique, the type of raw material, the molecular weight of high polymer templates, spinning solution
Composition, spinning process parameters and heat treatment process all has a major impact the morphology and size of final products.The present invention uses
The method that electrostatic spinning technique is combined with cyanogen ammonification technology prepares CaCN2Dispersed nano particle.With calcium nitrate tetrahydrate Ca
(NO3)2·4H2O is raw material, and deionized water and n,N-Dimethylformamide DMF solvent is added, and it is poly- to add high polymer templates
Vinylpyrrolidone PVP obtains spinning solution, then carries out electrostatic spinning, under the best experimental conditions, prepares PVP/Ca
(NO3)2It is heat-treated in air, prepares the CaCO of pure phase by composite nano fiber3Nanofiber, using graphite boat
With ammonia NH3By CaCO3Nanofiber carries out cyanogen ammoniated treatment, has prepared the CaCN of pure phase2Dispersed nano particle.
Summary of the invention
Preparation CaCN in the background technology2Bulky grain powder is harmonious using high temperature gas-solid phase synthesi and solid-solid
At the methods of method.In order in CaCN2Material Field provides a kind of novel nano material, and we have invented CaCN2Dispersed nano
The preparation method of particle.
The invention is realized in this way preparing the spinning solution with certain viscosity for electrostatic spinning first, apply
Electrostatic spinning technique carries out electrostatic spinning and prepares PVP/Ca (NO under the best experimental conditions3)2Composite nano fiber, will
It is heat-treated in air, prepares the CaCO of pure phase3Nanofiber, using graphite boat and ammonia NH3Carried out cyanogen ammonia
Change, has prepared the CaCN of pure phase2Dispersed nano particle.It the steps include:
(1) spinning solution is prepared
Calcium source uses calcium nitrate tetrahydrate Ca (NO3)2·4H2O, high polymer templates use polyvinylpyrrolidone
PVP, molecular weight 90000 use deionized water and n,N-Dimethylformamide DMF for solvent, by 1.5007g Ca (NO3)2·
4H2O is added in 4.0174g deionized water, after magnetic agitation is completely dissolved, 7.9826g DMF is added, adds 1.5016g
PVP continues stirring 6h and obtains colorless and transparent spinning solution；
(2) PVP/Ca (NO is prepared3)2Composite nano fiber
Spinning solution is injected in the 10mL syringe with 1mL plastic spray gun head, graphite rod is inserted into spinning solution,
With the positive terminal of copper wire connection graphite rod and high-voltage DC power supply, the earth terminal of high-voltage DC power supply is put with vertical
The wire netting set copper wire connect and ground, reception device of the wire netting as composite nano fiber, lance head and horizontal plane
Angle is 15 °, and the spacing of lance head and receiving screen wire netting is 15cm, and spinning voltage 13kV, room temperature is 20-25 DEG C,
Relative humidity is 40%-60%, carries out electrostatic spinning and obtains PVP/Ca (NO3)2Composite nano fiber；
(3) CaCO is prepared3Nanofiber
By the PVP/Ca (NO3)2Composite nano fiber is put into temperature programmed control Muffle furnace and is heat-treated, with 1 DEG C/
The heating rate of min rises to 500 DEG C and keeps the temperature 5h, is down to 200 DEG C later with the rate of temperature fall of 1 DEG C/min, then certainly with furnace body
It is so cooled to room temperature, obtains CaCO3Nanofiber；
(4) CaCN is prepared2Dispersed nano particle
By the CaCO3Nanofiber is placed in high purity graphite boat, is carried out in vacuum tube furnace with the ammonia of flowing
Cyanogen ammoniated treatment is warming up to 950 DEG C, after heat preservation for 24 hours with 1 DEG C/min, then is cooled to 100 DEG C with 1 DEG C/min, then certainly with furnace body
It is so cooled to room temperature, obtains CaCN2Dispersed nano particle, diameter are 250 ± 0.27nm.
The CaCN in above process2Dispersed nano particle has good crystallinity, belongs to trigonal system, directly
Diameter is 250 ± 0.27nm, realizes goal of the invention.
Detailed description of the invention
Fig. 1 is CaCN2The XRD spectra of dispersed nano particle；
Fig. 2 is CaCN2The SEM photograph of dispersed nano particle, the figure double as Figure of abstract；
Fig. 3 is CaCN2The diameter distribution histogram of dispersed nano particle；
Fig. 4 is CaCN2The EDS spectrogram of dispersed nano particle.
Specific embodiment
Calcium nitrate tetrahydrate Ca (NO selected by the present invention3)2·4H2O, the polyvinylpyrrolidone that molecular weight is 90000
PVP, n,N-Dimethylformamide DMF, ammonia are commercially available analysis net product；The self-control of deionized water laboratory；Glass used
Instrument, crucible and equipment are common instrument and equipments in laboratory.
Embodiment: by 1.5007g Ca (NO3)2·4H2O is added in 4.0174g deionized water, and magnetic agitation is completely molten
Xie Hou is added 7.9826g DMF, adds 1.5016g PVP, continues stirring 6h and obtains colorless and transparent spinning solution；By spinning
Liquid injects in the 10mL syringe with 1mL plastic spray gun head, and graphite rod is inserted into spinning solution, connects graphite with copper wire
The positive terminal of stick and high-voltage DC power supply, by the earth terminal of high-voltage DC power supply and the wire netting copper being disposed vertically
The angle of line connect and ground, reception device of the wire netting as composite nano fiber, lance head and horizontal plane is 15 °, spray gun
The spacing of head and receiving screen wire netting is 15cm, and spinning voltage 13kV, room temperature is 20-25 DEG C, relative humidity 40%-
60%, it carries out electrostatic spinning and obtains PVP/Ca (NO3)2Composite nano fiber；By the PVP/Ca (NO3)2Composite nano fiber
It is put into temperature programmed control Muffle furnace and is heat-treated, rise to 500 DEG C with the heating rate of 1 DEG C/min and keep the temperature 5h, later with 1
DEG C/rate of temperature fall of min is down to 200 DEG C, then with furnace body cooled to room temperature, obtain CaCO3Nanofiber；It will be described
CaCO3Nanofiber is placed in high purity graphite boat, in vacuum tube furnace with flowing ammonia carry out cyanogen ammoniated treatment, with 1 DEG C/
Min is warming up to 950 DEG C, after heat preservation for 24 hours, then is cooled to 100 DEG C with 1 DEG C/min, then with furnace body cooled to room temperature, obtains
CaCN2Dispersed nano particle.The CaCN2Dispersed nano particle have good crystallinity, the d value of diffraction maximum and
Relative intensity and CaCN2PDF standard card (32-0161) listed by d value it is consistent with relative intensity, belong to trigonal system, see
Shown in Fig. 1；The CaCN2Dispersed nano particle has good pattern, of uniform size, as shown in Figure 2；Use Shapiro-
Wilk method is to CaCN2The diameter of dispersed nano particle carries out normal distribution-test, under 95% confidence level, diameter distribution
Belong to normal distribution, diameter is 250 ± 0.27nm, as shown in Figure 3；The CaCN2Dispersed nano particle is by Ca, C and N member
Element composition, the Pt conductive layer of sample surfaces plating when Pt element is tested from SEM, as shown in Figure 4.
Certainly, the invention may also have other embodiments, without deviating from the spirit and substance of the present invention, ripe
It knows those skilled in the art and makes various corresponding changes and modifications, but these corresponding changes and change in accordance with the present invention
Shape all should fall within the scope of protection of the appended claims of the present invention.
Claims (2)
1. a kind of preparation method of nitrolim dispersed nano particle, which is characterized in that using electrostatic spinning technique and cyanogen ammonia
The method that change technology combines is high polymer templates using polyvinylpyrrolidone PVP, using deionized water and N, N- diformazan
Base formamide DMF is solvent, uses graphite boat and ammonia NH3Cyanogen ammonification is carried out, preparing product is nitrolim CaCN2Monodisperse
Nano particle the steps include:
(1) spinning solution is prepared
Calcium source uses calcium nitrate tetrahydrate Ca (NO3)2·4H2O, use deionized water and n,N-Dimethylformamide DMF for
Solvent, by 1.5007g Ca (NO3)2·4H2O is added in 4.0174g deionized water, after magnetic agitation is completely dissolved, is added
7.9826g DMF adds 1.5016g PVP, continues stirring 6h and obtains colorless and transparent spinning solution；
(2) PVP/Ca (NO is prepared3)2Composite nano fiber
Spinning solution is injected in the 10mL syringe with 1mL plastic spray gun head, graphite rod is inserted into spinning solution, copper is used
Line connects the positive terminal of graphite rod and high-voltage DC power supply, by the earth terminal of high-voltage DC power supply be disposed vertically
Wire netting copper wire connect and ground, reception device of the wire netting as composite nano fiber, the angle of lance head and horizontal plane
It is 15 °, the spacing of lance head and receiving screen wire netting is 15cm, and spinning voltage 13kV, room temperature is 20-25 DEG C, relatively
Humidity is 40%-60%, carries out electrostatic spinning and obtains PVP/Ca (NO3)2Composite nano fiber；
(3) CaCO is prepared3Nanofiber
By the PVP/Ca (NO3)2Composite nano fiber is put into temperature programmed control Muffle furnace and is heat-treated, with 1 DEG C/min's
Heating rate rises to 500 DEG C and keeps the temperature 5h, is down to 200 DEG C later with the rate of temperature fall of 1 DEG C/min, then with furnace body natural cooling
To room temperature, CaCO is obtained3Nanofiber；
(4) CaCN is prepared2Dispersed nano particle
By the CaCO3Nanofiber is placed in high purity graphite boat, carries out cyanogen ammonification with the ammonia of flowing in vacuum tube furnace
Processing is warming up to 950 DEG C, after heat preservation for 24 hours with 1 DEG C/min, then is cooled to 100 DEG C with 1 DEG C/min, then with furnace body natural cooling
To room temperature, CaCN is obtained2Dispersed nano particle has good crystallinity, belongs to trigonal system, and diameter is 250 ±
0.27nm。
2. a kind of preparation method of nitrolim dispersed nano particle according to claim 1, which is characterized in that high score
Subtemplate agent is the polyvinylpyrrolidone of molecular weight Mr=90000.
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| CN104562296A (en) * | 2014-12-29 | 2015-04-29 | 长春理工大学 | Er/Yb co-doped dioxo-lanthanum cyanamide up-conversion luminescence nanofibers and preparation method thereof |
| CN104593905A (en) * | 2014-12-29 | 2015-05-06 | 长春理工大学 | Erbium-doped lanthanum mono-cyanamide dioxide up-conversion light-emitting nanofiber and preparation method thereof |
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| GB1072664A (en) * | 1965-03-04 | 1967-06-21 | Suddeutsche Kalkstickoff Werke | Process for the production of calcium cyanamide |
| CN104562296A (en) * | 2014-12-29 | 2015-04-29 | 长春理工大学 | Er/Yb co-doped dioxo-lanthanum cyanamide up-conversion luminescence nanofibers and preparation method thereof |
| CN104593905A (en) * | 2014-12-29 | 2015-05-06 | 长春理工大学 | Erbium-doped lanthanum mono-cyanamide dioxide up-conversion light-emitting nanofiber and preparation method thereof |
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