CN102674406B - Preparation method of nano-tubular magnesium oxide - Google Patents
Preparation method of nano-tubular magnesium oxide Download PDFInfo
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- CN102674406B CN102674406B CN 201110426954 CN201110426954A CN102674406B CN 102674406 B CN102674406 B CN 102674406B CN 201110426954 CN201110426954 CN 201110426954 CN 201110426954 A CN201110426954 A CN 201110426954A CN 102674406 B CN102674406 B CN 102674406B
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 47
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 55
- 239000000347 magnesium hydroxide Substances 0.000 claims description 52
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 52
- 159000000003 magnesium salts Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 8
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 36
- 239000003795 chemical substances by application Substances 0.000 abstract description 17
- 238000001354 calcination Methods 0.000 abstract description 15
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000000877 morphologic effect Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 6
- 239000000470 constituent Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 18
- 238000002003 electron diffraction Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000004364 calculation method Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002071 nanotube Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 125000006850 spacer group Chemical group 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000976924 Inca Species 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
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- 239000012190 activator Substances 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
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- 230000010165 autogamy Effects 0.000 description 1
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- 239000013590 bulk material Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- WALYXZANOBBHCI-UHFFFAOYSA-K magnesium sodium trichloride hydrate Chemical compound O.[Cl-].[Na+].[Mg+2].[Cl-].[Cl-] WALYXZANOBBHCI-UHFFFAOYSA-K 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of nano-tubular magnesium oxide, and the preparation method comprises the following steps of: 1) firstly preparing a nano-tubular magnesium oxide precursor; and 2) carrying out three-stage calcination on the magnesium oxide precursor obtained by the step 1), so as to convert the magnesium oxide precursor into the nano-tubular magnesium oxide. The tubular magnesium oxide precursor is divided into the three-stage calcination according to the preparation method disclosed by the invention, wherein the first stage is an adsorbed water removal and organic small molecule volatilization decomposition stage, the second stage is a constituent water removal stage, and the third stage is a template agent decomposition stage. Heat preservation is performed for 1-2 hours, 2-3 hours and 1-2 hours respectively in the three stages, and the nano-tubular magnesium oxide precursor is calcinated step by step to obtain the tubular magnesium oxide, so that the nano-tubular magnesium oxide can not be damaged or agglomerated when being calcinated, and the crystal size and morphological characteristic of the nano-tubular magnesium oxide precursor can be maintained. The nano-tubular magnesium oxide has the length of 80-200nm, and the pipe diameter of 8-20nm.
Description
Technical field
The present invention relates to a kind of nanotube-shaped magnesian preparation method, belong to technical field of inorganic nanometer material.
Background technology
Japan has taken the lead in since report finds carbon nanotube since the nineties in last century, and nano-tube material is because of its unique microtexture, and electricity, optics, magnetic, mechanical property and the potential application in the nano-device structure and receive much concern.Thus, the technology of preparing of nano-scale tube material and applied research thereof become the focus of domestic and international advanced subject.Magnesium oxide is as a kind of important inorganic industrial raw material, in the fields such as pottery, coating, catalysis, material of construction, refractory materials and superconducting material, have a wide range of applications, also can be used as the promotor of filler, rubber of polishing agent, tackiness agent, paint, paper and activator, infrared stealth absorbing material etc.The application of its uniqueness is especially arranged in current war industry as infrared absorbing material.
The nano level magnesium oxide of special crystalline form is less because of particle diameter, specific surface area is large, general effect with nano materials such as small-size effect, surface and interface effect, quantum size effect, macroscopic quantum effects, compare with bulk material, have the excellent properties such as high rigidity, high-melting-point, high reactive behavior, strong adsorptivity, good low-temperature sintering, high resistivity.In recent years, the developed country such as American-European-Japanese has studied the nano magnesia of multiple crystalline form, and has obtained many achievements in the application facet of nano magnesia.
Studies show that, compare with traditional phosphorous or halogen organic fire-retardant that the advantage such as that nano magnesia has is nontoxic, tasteless, addition is little is the perfect additive of exploitation fire-retardant fibre.Nano magnesia has excellent shielding ultraviolet rays ability, is the preferred material of development functionality makeup, fiber and clothes.Nano magnesia and superpolymer or other Material cladding have good microwave absorption coefficient in addition, and it not only can make the compaction material of makeup, face powder, paint, and can be used as the polish etc. of compaction material, fat-splitting agent or the pharmaceuticals of rubber.
Nano magnesia also has good sterilizing ability.U.S. Nanoscale company had once done systematic research to the bactericidal property of nano magnesia, the result shows: nano magnesia has unusual outstanding killing effect (in 20 minutes to multiple virus, bacterium and fungi, the killing effect of bacterium is 100%), being much better than common silver is sterilant (in 60 minutes, the killing effect of bacterium is 100%); And nano magnesia has higher adsorptive power to chlorine, the chlorine of adsorbable own wt 20%, thus further strengthened germicidal action.From SAR virus since Global prevalence, United States Government is recommended in hospital and the public place uses the nano magnesia sterilization material, so nano magnesia is promoted rapidly in the fields such as medical treatment, public health, chemical weapons and chemical and biological weapons (being mainly used in chemical decomposition and biological poison gas).At present common nano magnesia crystalline form is laminar, bar-shaped, thread etc.
Summary of the invention
The purpose of this invention is to provide a kind of nanotube-shaped magnesian preparation method.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of nanotube-shaped magnesian preparation method, and its step is as follows:
1) adopting solubility magnesium salts preparation magnesium ion concentration is the magnesium salt solution of 0.01～1.5mol/L, under 30-60 ℃ of whipped state, adjust the pH value to 9 of magnesium salt solution～14 with alkali lye, continue stirring reaction 1～4 hour, and added polyoxyethylene glycol or the sodium polyacrylate of magnesium salts weight 1～10wt% in the reaction process; With the throw out washing that generates, dry, after grinding the magnesium hydroxide presoma;
2) with step 1) the magnesium hydroxide presoma that obtains, be heated to 265～280 ℃ of insulations 1～2 hour with 4～15 ℃/minute heat-up rates, be heated to 285～430 ℃ of insulations 2～3 hours with 4～15 ℃/minute heat-up rate again, then be heated to 435～500 ℃ of insulations 1～2 hour with 4～15 ℃/minute heat-up rate, stopped heating is cooled to room temperature, obtains tubular nanometer magnesium oxide.
Described magnesium salts is magnesium chloride, magnesium nitrate, sal epsom or magnesium acetate.
The solvent that described magnesium salt solution adopts is that deionized water, dehydrated alcohol or deionized water and dehydrated alcohol volume ratio are 20: 80～50: 50 mixed solvent.
The temperature of described drying is 80～100 ℃.
The magnesian length of described tubular nanometer is 80～200 nanometers, and caliber is 8～20 nanometers.
Preparation method of the present invention at first prepares tubulose magnesium hydroxide presoma; adopt polyoxyethylene glycol or sodium polyacrylate etc. as crystal control agent; induce the magnesium hydroxide of generation to form tubulose magnesium hydroxide structure at polyoxyethylene glycol or sodium polyacrylate surface; and this tubular structure stablized and protect, under normal pressure and lesser temps, just can make tubulose magnesium hydroxide presoma.The sign of tubulose magnesium hydroxide presoma as shown in Figure 1, 2, 3.
Crystal control agent is many-sided to the crystal affects on the growth.It can affect the solubleness of material and the character of solution, even can significantly change the crystal habit of crystal.Because selective adsorption often occurs in the anisotropy of crystal, crystal control agent on the different crystal faces of crystal.This absorption often makes the growth of some crystal face be hindered, thereby has changed the relative growth rate of each crystal face, thereby reaches the purpose of the profile of control crystal.Crystal control agent can be adsorbed in crystal face, step or the kinking of magnesium hydroxide crystal, and the replacement lattice ion, hinders migration and the absorption of lattice ion, thereby suppresses the growth of crystal.Can be adsorbed on Mg as adding the autogamy crystal control agent in the reaction system
2+The surface forms complex compound, induces OH
-Can only be at certain angle and Mg
2+Interact, form metasable state hexagon magnesium hydroxide nucleus.From the molecule power theory of crystal growth, crystal control agent can be regarded the energy that changes various process of growth as.
The consumption of crystal control agent is comparatively remarkable on the pattern impact of magnesium hydroxide crystal, experimental results show that the consumption of crystal control agent will strictly be controlled in certain scope.The consumption of crystal control agent is too small, does not just reach the purpose of control crystal morphology.The consumption of crystal control agent is excessive, just may the performance of product be exerted an influence, such as whiteness, dispersiveness even can not get required crystalline form and nano tubular structure.For producing nanotubes shape magnesium hydroxide presoma, the consumption of crystal control agent should adopt 1～10wt% of magnesium salts weight that reaction adds to be advisable among the present invention.
Then nanotube-shaped magnesium hydroxide presoma is divided into the three phases calcining, first stage is the volatilization catabolic phase of desorption attached water and organic molecule, and outlet temperature is 265～280 ℃; Subordinate phase is for taking off the water of constitution stage, and in 285 ℃～430 ℃ temperature-rise period, nanotube-shaped magnesium hydroxide little by little loses water of constitution and forms magnesium oxide; Three phases is for decomposing the crystal control agent stage, and the decomposition temperature of crystal control agent is 435～500 ℃.Three constant temperature steps of corresponding selection, per stage is incubated respectively 1-2 hour, and 2-3 hour, 1-2 hour, progressively calcine nanotube-shaped magnesium hydroxide presoma, finally make product naturally cool to room temperature, obtain tubular nanometer magnesium oxide.The present invention passes through the control of heat-up rate and the selection of calcining at constant temperature, guarantee the not damaged or reunion in calcination process of nanotube-shaped magnesium hydroxide, keep crystallographic dimension and the morphological specificity of nanotube-shaped magnesium hydroxide presoma, thereby obtained preferably nanotube-shaped magnesium oxide of quality.The sign of tubulose magnesium oxide presoma is shown in Fig. 4,5,6.
Nanotube-shaped magnesium oxide of the present invention, its length are 80-200nm, and caliber is 8-20nm.
The bitter earth nano pipe has extremely important application prospect in fields such as the energy, biomedicine, aerospace.The bitter earth nano pipe can be used for making the fuel cell less, lighter, that usefulness is higher, and it can also be used for storing the hydrogen as the energy.Because himself is lightweight, has hollow structure, can be used as the good container of storage of hydrogen, the hydrogen density of storage even also higher than the density of liquid state or solid hydrogen.Suitably heating, hydrogen just can slow release out.Available bitter earth nano pipe is made the hydrogen storage vessel of light portable.The bitter earth nano pipe can be used as inorganic medicine carrying particle and develops antitumor, antiviral, the antibacterial novel strategic medicine in current biomedical boundary.Its special application is also arranged, as purifying agent for polluted water Absorption of Heavy Metal ion etc. aspect environment protection.Especially the application on aerospace has its unique distinction especially.The outer material that the bitter earth nano pipe can be used as aerospacecraft not only has the intrinsic resistant to elevated temperatures characteristic of magnesium oxide material, and can absorb various harm rays in the universe etc. because of its unique tubular structure.In a word, the bitter earth nano pipe has extremely wide prospect in the application of the every field such as scientific research, technology, the energy, biomedicine, aerospace, military affairs.
Description of drawings
Fig. 1 be the inventive method X-ray diffractogram of preparing the nanotube-shaped magnesium hydroxide of gained (German Brooks D8Advance x-ray diffractometer, take Cu-k α as source of radiation,
); As seen from Figure 1, all diffraction peaks all can be corresponding with the standard card JCPDS 7-239 of hexagonal system magnesium hydroxide (spacer P-3ml (164)), and without the existence of other crystalline phase diffraction peak, illustrate that product is mainly the hexagonal system magnesium hydroxide;
Fig. 2 is for adopting the inventive method to prepare the TEM electron diffraction photo (NEC JEM-2100 type super-resolution transmission electron microscope, England Oxford INCA energy spectrometer) of the nanotube-shaped magnesium hydroxide of gained; From the electron diffraction photo of gained sample as can be known, this is hexagonal crystallographic texture.Confirm that further products obtained therefrom is the magnesium hydrate hexagonal crystalline structure.
Fig. 3 is for adopting the inventive method to prepare (80,000 times of the TEM transmission electron microscope photos of the nanotube-shaped magnesium hydroxide of gained, the H-800 of Hitachi type transmission electron microscope, drip behind the sample preparation employing dehydrated alcohol ultra-sonic dispersion and bearing on the copper mesh of carbon film, air drying), can be found out that by Fig. 2 and 3 product is about long 80-150nm, minor axis 10nm, dispersiveness nanotube-shaped magnesium hydroxide (hexagonal system) preferably;
Fig. 4 be the magnesian X-ray diffractogram of gained nanotube of the present invention (German Brooks D8Advance x-ray diffractometer, source of radiation are Cu-k α palladium,
); As seen from Figure 4, all diffraction peaks all can be corresponding with the standard card JCPDS 45-946 of isometric system magnesium oxide (Fm-3m (225)), and without the existence of other crystalline phase diffraction peak, illustrate that product is mainly isometric system magnesium oxide;
Fig. 5 is the magnesian TEM electron diffraction of gained nanotube of the present invention photo (NEC JEM-2100 type super-resolution transmission electron microscope, England Oxford INCA energy spectrometer).From the electron diffraction photo of gained nanotube magnesium oxide sample as can be known, this is cubic crystal structure (isometric system, Fm3m spacer).Confirm that further products obtained therefrom is magnesium oxide cubic-crystal structure.
Fig. 6 is the magnesian TEM transmission electron microscope photo of gained nanotube of the present invention (100,000 times) (NEC JEM-2100 type super-resolution transmission electron microscope, air drying was being born on the copper mesh of carbon film in dropping after the dehydrated alcohol ultra-sonic dispersion was adopted in sample preparation); Can be found out that by Fig. 5 and 6 product is about long 80-150nm, minor axis 10nm, dispersiveness nanotube-shaped magnesium oxide (isometric system) preferably;
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1:
The nanotube-shaped magnesian preparation method of present embodiment comprises the steps:
1) compound concentration is the magnesium chloride brine of 0.01mol/L;
2) under normal pressure and 30 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 9 with alkali lye, continue stirring reaction 1h, add polyoxyethylene glycol in reaction process, add-on is the 1wt% of magnesium chloride;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 80 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 4 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 265 ℃, 285 ℃, 435 ℃ lower insulations 1 hour, 2 hours, 1.5 hours, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
The nanotube-shaped magnesium oxide powder product of present embodiment uses German Brooks D8Advance x-ray diffractometer, and source of radiation is Cu-k α palladium,
Measure.Typical XRD diffraction spectrogram as shown in Figure 4, ordinate zou is the intensity of diffraction peak among the figure, X-coordinate is scanning angle 2 θ, and magnesia crystal consistent among all diffraction peak positions of curve and the JCPDS45-946 illustrates that this product is the magnesia crystal structure in the accompanying drawing 4.And the equal obvious broadening of the diffraction peak of curve in the accompanying drawing 4 shows that as calculated these crystal grain all have the feature of nanoparticle.By the estimation of Debye-Scherrer formula as can be known: this magnesia crystal is respectively 9.7nm, 9.9nm, 14.7nm in the size of (111), (200) and (220) direction.Again with above-mentioned nanotube-shaped magnesium oxide sample dispersion in ethanol, behind ultra-sonic dispersion, drip and to bear on the copper mesh of carbon film air drying.Use NEC JEM-2100 type super-resolution transmission electron microscope (100,000 times) to observe as can be known, the product sample topography is the nanocrystal tubular structure (as shown in Figure 6) of length 80 nanometers, caliber 10 nanometers.And to nanotube-shaped magnesium oxide powder product shooting electron diffraction photo, as shown in Figure 5.Further be defined as magnesium oxide cubic crystal structure (isometric system, Fm3m spacer) through demarcating polynary ring and adopting trial effect nuclear method to calculate.
Embodiment 2:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium nitrate alcoholic solution of 1mol/L;
2) under normal pressure and 40 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 14 with alkali lye, continue stirring reaction 2h, add polyoxyethylene glycol in reaction process, add-on is the 2wt% of magnesium nitrate;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 80 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 10 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 275 ℃, 290 ℃, 450 ℃ lower insulations 2 hours, 2 hours, 1 hour, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 150 nanometers, and caliber is 15 nanometers.
Embodiment 3:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium chloride solution (solvent is the mixing solutions of deionized water and dehydrated alcohol, and blending ratio is 20: 80) of 1.5mol/L;
2) under normal pressure and 60 ℃ of whipped states, adjust above-mentioned magnesium chloride solution pH value to 14 with alkali lye, continue stirring reaction 4h, add sodium polyacrylate in reaction process, add-on is the 3wt% of magnesium salts;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 90 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 15 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 280 ℃, 430 ℃, 500 ℃ lower insulations 1 hour, 3 hours, 2 hours, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 200 nanometers, and caliber is 20 nanometers.
Embodiment 4:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium acetate aqueous solution of 0.5mol/L;
2) under normal pressure and 60 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 10 with alkali lye, continue stirring reaction 2h, add polyoxyethylene glycol in reaction process, add-on is the 5wt% of magnesium acetate;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 90 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 10 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 270 ℃, 300 ℃, 435 ℃ lower insulations 1 hour, 2 hours, 2 hours, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 100 nanometers, and caliber is 8 nanometers.
Embodiment 5:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the Adlerika (solvent is the mixing solutions of deionized water and dehydrated alcohol, and blending ratio is 50: 50) of 0.8mol/L;
2) under normal pressure and 50 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 11 with alkali lye, continue stirring reaction 3h, add polyoxyethylene glycol in reaction process, add-on is the 4wt% of magnesium salts;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 80 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 6 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 275 ℃, 350 ℃, 435 ℃ lower insulations 2 hours, 2 hours, 2 hours, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 150 nanometers, and caliber is 20 nanometers.
Embodiment 6:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium nitrate alcoholic solution of 0.3mol/L;
2) under normal pressure and 60 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 13 with alkali lye, continue stirring reaction 1.5h, add polyoxyethylene glycol or sodium polyacrylate in reaction process, add-on is the 6wt% of magnesium salts;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 80 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 10 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 265 ℃, 400 ℃, 480 ℃ lower insulations 1 hour, 2 hours, 1 hour, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 80 nanometers, and caliber is 10 nanometers.
Embodiment 7:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium sulfate solution of 0.06mol/L;
2) under normal pressure and 40 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 12 with alkali lye, continue stirring reaction 2h, add sodium polyacrylate in reaction process, add-on is the 7wt% of magnesium salts;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 80 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 4 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 280 ℃, 380 ℃, 440 ℃ lower insulations 1 hour, 2 hours, 2 hours, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 80 nanometers, and caliber is 15 nanometers.
Embodiment 8:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium nitrate solution (solvent is the mixing solutions of deionized water and dehydrated alcohol, and blending ratio is 40: 60) of 0.6mol/L;
2) under normal pressure and 30 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 9 with alkali lye, continue stirring reaction 3h, add polyoxyethylene glycol in reaction process, add-on is the 8wt% of magnesium salts;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 80 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 6 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 280 ℃, 390 ℃, 470 ℃ lower insulations 1 hour, 3 hours, 2 hours, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 200 nanometers, and caliber is 10 nanometers.
Embodiment 9:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium acetate alcoholic solution of 0.01mol/L;
2) under normal pressure and 40 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 12 with alkali lye, continue stirring reaction 2.5h, add sodium polyacrylate in reaction process, add-on is the 9wt% of magnesium salts;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 80 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 14 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 275 ℃, 400 ℃, 500 ℃ lower insulations 1 hour, 2 hours, 1 hour, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 80 nanometers, and caliber is 15 nanometers.
Embodiment 10:
A kind of nanotube-shaped magnesian preparation method, it comprises the steps:
1) compound concentration is the magnesium nitrate aqueous solution of 0.08mol/L;
2) under normal pressure and 60 ℃ of whipped states, adjust above-mentioned magnesium salt solution pH value to 9 with alkali lye, continue stirring reaction 3.5h, add polyoxyethylene glycol in reaction process, add-on is the 10wt% of magnesium salts;
3) with step 2) throw out that forms after washing, in vacuum drying oven, dry, dry by the fire after powder grinds and have flowing property, bake out temperature is 100 degree, after then grinding the magnesium hydroxide presoma;
4) magnesium hydroxide is placed retort furnace, under 12 ℃/minute temperature rise rate, in air atmosphere, the magnesium hydroxide presoma is carried out the control calcining of three phases, respectively 265 ℃, 420 ℃, 500 ℃ lower insulations 2 hours, 3 hours, 2 hours, then make product naturally cool to room temperature, namely obtain nanotube-shaped magnesian white powder.
Through XRD test analysis and calculation of correlation and TEM electron diffraction analysis and the test of grain morphology size as can be known:
The nanotube-shaped magnesian length of present embodiment is 100 nanometers, and caliber is 8 nanometers.
All the other are identical except the intensity at peak and peak width at half height have nuance for spectrogram in the present embodiment 2～10 among the XRD spectra of nanotube-shaped magnesium oxide product and the embodiment 1.The polynary ring style of TEM electron diffraction is identical with embodiment 1, and tem observation product shape appearance figure is nano tubular structure.
Claims (5)
1. nanotube-shaped magnesian preparation method, it is characterized in that: its step is as follows:
1) adopting solubility magnesium salts preparation magnesium ion concentration is the magnesium salt solution of 0.01～1.5mol/L, under the temperature whipped state of normal pressure, 30-60 ℃, adjust the pH value to 9 of magnesium salt solution～14 with alkali lye, continue stirring reaction 1～4 hour, and added polyoxyethylene glycol or the sodium polyacrylate of magnesium salts weight 1～10wt% in the reaction process; With the throw out washing that generates, dry, after grinding the magnesium hydroxide presoma;
2) with step 1) the magnesium hydroxide presoma that obtains, be heated to 265～280 ℃ of insulations 1～2 hour with 4～15 ℃/minute heat-up rates, be heated to 285～430 ℃ of insulations 2～3 hours with 4～15 ℃/minute heat-up rate again, then be heated to 435～500 ℃ of insulations 1～2 hour with 4～15 ℃/minute heat-up rate, stopped heating is cooled to room temperature, obtains tubular nanometer magnesium oxide.
2. nanotube-shaped magnesian preparation method according to claim 1, it is characterized in that: described magnesium salts is magnesium chloride, magnesium nitrate, sal epsom or magnesium acetate.
3. nanotube-shaped magnesian preparation method according to claim 1, it is characterized in that: the solvent that described magnesium salt solution adopts is that deionized water, dehydrated alcohol or deionized water and dehydrated alcohol volume ratio are 20: 80～50: 50 mixed solvent.
4. nanotube-shaped magnesian preparation method according to claim 1 is characterized in that: step 1) temperature of described drying is 80～100 ℃.
5. nanotube-shaped magnesian preparation method according to claim 1, it is characterized in that: the magnesian length of described tubular nanometer is 80～200 nanometers, caliber is 8～20 nanometers.
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| CN1556034A (en) * | 2004-01-09 | 2004-12-22 | 山东师范大学 | Synthesis method of magnesium hydroxide nano pipe |
| CN101555027A (en) * | 2009-05-08 | 2009-10-14 | 南京大学 | Method for preparing magnesium hydrate nanotube |
| US20100044478A1 (en) * | 2008-08-25 | 2010-02-25 | Industrial Technology Research Institute | Nanotization of magnesium-based hydrogen storage material |
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| US20100044478A1 (en) * | 2008-08-25 | 2010-02-25 | Industrial Technology Research Institute | Nanotization of magnesium-based hydrogen storage material |
| CN101555027A (en) * | 2009-05-08 | 2009-10-14 | 南京大学 | Method for preparing magnesium hydrate nanotube |
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