CN1673182A - Crystal phase controllable zirconium dioxide/carbon nanometer composite powder and its prepn process - Google Patents
Crystal phase controllable zirconium dioxide/carbon nanometer composite powder and its prepn process Download PDFInfo
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- CN1673182A CN1673182A CN 200510023959 CN200510023959A CN1673182A CN 1673182 A CN1673182 A CN 1673182A CN 200510023959 CN200510023959 CN 200510023959 CN 200510023959 A CN200510023959 A CN 200510023959A CN 1673182 A CN1673182 A CN 1673182A
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Abstract
The present invention provides one kind of crystal phase controllable zirconium/carbon nanotube composite powder and its in-situ synthesis process. The present invention features that acidifying treated carbon nanotube is set in water solution of ZrOCl2.8H2O as Zr source to in-situ synthesize zirconium/carbon nanotube composite powder at 150-200 deg.c under hydrothermal condition. The process is simple, and the obtain material has carbon nanotube content over 85 wt% and nanometer zirconium dioxide particles distributed homogeneously on the wall of the carbon nanotube. Under optimized condition, nanometer zirconium dioxide crystal may cover the carbon nanotube completely, and the present invention realizes the close combination between nanometer zirconium dioxide crystal and carbon nanotube.
Description
Technical field
The invention relates to the preparation method of a kind of nano zirconium dioxide original position parcel carbon nanotube and zirconium/carbon dioxide nano-tube nano composite granule, belong to field of nanocomposite materials.
Technical background
Since S.Iijima found carbon nanotube, the research of carbon nanotube and related science thereof had caused that people pay close attention to greatly.Because it has unique one dimension hollow structure, superpower electricity and mechanical property, bigger specific surface area (120-300m
2/ g), better adsorption capability, carbon nanotube and matrix material thereof can be widely used as enhancing body, hydrogen storage material, field emmision material, nano-device and the electrode materials of matrix material.The mechanical property of its excellence (the Young's modulus 1TPa of Single Walled Carbon Nanotube particularly, the Young's modulus 950GPa of multi-walled carbon nano-tubes) and low density be called as the limiting form of composite material reinforcement body, to be equipped with high performance carbon nano tube compound material be one of main direction of carbon nanotube research as strengthening system with it in recent years.But, owing to exist stronger Van der Waals force to make it be difficult to be dispersed among the matrix between carbon nanotube, and the chemically reactive on its surface is low causes reasons such as consistency difference with matrix to make the carbon nano tube compound material of preparing not show that ideal strengthens, toughening effect, especially is in the matrix material of matrix with the pottery.Ma etc. join carbon nanotube in the SiC pottery, found that bending strength has only increased by about 10% (R.Z.Ma, J.Wu, B.Q.Wei, J.Liang, D.H.Wu, J..Mater.Sci., 1998,33 5243-5246).People such as Peigney and Kamalakaran has done a large amount of work to carbon nanotube/alumina composite material, but does not still obtain satisfied result.(E.Flahaut，A.Peigney，Ch.Laurent，Ch.Marlière，F.Chastel?and?A.Rousset，Acta?Mater.，2000，48[14]：3803-3812；R.Kamalakaran，F.Lupo，N.Grobert，D.Lozano-Castello，N.Y.Jin-Phillipp?and?M.Rühle，Carbon，2003，41[14]：2737-2741)。Studies show that, the inorganic species of carbon nano tube surface parcel one deck can improve greatly carbon nanotube and inorganic matrix consistency (K.Hernadi, E.Couteau, J.W.Seo and L.Forro, Langmuir, 2003,19[17]: 7026-7029).
Zirconium white is one of important engineering stupalith, be often used as to strengthen the mechanical property that body improves material, and it also has application widely aspect catalysis, air-sensitive, the fuel cell.Zirconium dioxide and composite study thereof are the focuses in the investigation of materials always, relate to but the research of zirconium/carbon dioxide nanometer composite powder is rare, particularly that crystalline phase is controlled zirconium/carbon dioxide nanometer composite powder then rarely has report as strengthening body.Lupo etc. are with [Zr (OH)
4NH
2O; N=8-16] for utilizing hydrothermal crystallization method, presoma prepared the zirconium/carbon dioxide nanometer composite powder at 200 ℃, but the zirconium dioxide of this method preparation is the monocline phase, and does not realize that interface stronger between zirconium dioxide and carbon nanotube combines.Realize that the stronger interface of carbon nanotube and matrix combines and crystalline phase controllable compound powder is that people thirst for the problem that solves for a long time always, therefore preparing with carbon nanotube has zirconium/carbon dioxide nanometer composite powder than strong interfacial bond, and the research that realizes zirconium dioxide crystalline phase controllable pair carbon nano tube compound material all has certain meaning with using.
Summary of the invention
The object of the present invention is to provide a kind of composite granule and preparation method with tight interfacial combined function.The present invention makes its surface produce electronegative active group by the acidification carbon nanotube, utilizes the active group and the ZrOCl of carbon nano tube surface
28H
2The electrostatic attraction effect of the complexing ion that O forms in the aqueous solution is adsorbed in carbon nano tube surface with the precursor in situ of zirconium, and along with the carrying out of hydro-thermal reaction, in the carbon nano tube surface nucleation, and then original position generates ZrO to this complexing ion by esterification
2The composite granule of/carbon nanotube.The method that is provided is simple, and is easy to operate, do not need special equipment, and realized zirconium dioxide nanocrystalline with the combining closely of carbon nanotube, be the effective way of preparation zirconium/carbon dioxide nanometer composite powder.
Characteristics of the present invention are: with ZrOCl
28H
2O is a raw material, original position parcel carbon nanotube under 150-200 ℃ of hydrothermal condition.
Concrete steps are:
(1) with the multi-walled carbon nano-tubes oven dry, removes the moisture that is contained;
(2) dried carbon nano-tube with concentrated nitric acid in 140 ℃ of reflow treatment 6-8 hours carbon nano tube surface introducing-OH ,-COOH or-CO isoreactivity group, use deionized water wash, dry for standby then;
(3) with ZrOCl
28H
2O is dissolved into and is made into the solution that concentration is 0.3-0.009M in the water;
(4) with step 2) carbon nano tube modified joins in the solution with step (3) preparation ultrasonic 15-60 minute;
(5) mixing solutions that step 4) is obtained is put into autoclave, can obtain ZrO at 150-200 ℃ of following hydro-thermal 12-24 hour
2The composite granule of nanoparticle original position parcel carbon nanotube.
(6) product respectively washs 3 times through water, dehydrated alcohol, promptly obtains the composite granule of the nanocrystalline parcel carbon nanotube of zirconium dioxide after the drying.
The characteristics of the method for nano zirconium dioxide parcel carbon nanotube provided by the invention are:
(1) by acidification carbon nano tube surface introduce introducing-OH ,-COOH ,-CO isoreactivity group, and make carbon nano tube surface electronegative.The active group that utilizes carbon nano tube surface with ZrOCl
28H
2The complexing ion that forms in the O aqueous solution ([Zr (OH)
24H
2O]
4 8+) the electrostatic attraction effect, the precursor in situ of zirconium is adsorbed in carbon nano tube surface, along with the carrying out of hydro-thermal reaction, in the carbon nano tube surface nucleation, and then original position generates ZrO to this complexing ion by esterification
2The composite granule of/carbon nanotube
(2) the zirconium source is fixed on carbon nano tube surface by esterification, zirconium dioxide is nanocrystalline spherical in shape, and particle size is 4-5nm, in content of carbon nanotubes during greater than 85wt%, the zirconium dioxide nano-crystalline granule is evenly distributed on the tube wall of carbon nanotube, also has small part to be filled in the carbon nanotubes lumen.Content of carbon nanotubes is during less than 85wt%, and then carbon nanotube is closely wrapped up by the zirconium dioxide nano-crystalline granule.Realized that carbon nanotube combines (seeing embodiment for details) with strong interface between zirconium dioxide.
(3) by changing ZrOCl
28H
2The concentration of O solution is adjusted the zirconium/carbon dioxide nanometer composite powder that zirconium dioxide and the mass percent of carbon nanotube can obtain different crystalline phases.When content of carbon nanotubes during less than 5wt%, the monocline of zirconium dioxide exists mutually in the carbon nano-tube composite powder of the nanocrystalline parcel of original position synthetic zirconium dioxide of gained; When content of carbon nanotubes during greater than 85wt%, zirconium dioxide exists mutually with the four directions; When content of carbon nanotubes during between 5-85wt%, monocline coexists as in the composite granule with cubic zirconium dioxide mutually mutually.
(4) technology is simple, does not need to use any tensio-active agent, need not specific installation.The zirconium/carbon dioxide nanometer composite powder of preparation is the good presoma of preparation composite ceramics, also can be used as the enhancing body of other material, and is expected to certain application prospect is arranged aspect quick, the catalysis dividing.
Description of drawings
The X-ray diffraction spectrogram of nano zirconium dioxide/carbon nanotube that the reactant of Fig. 1 different concns obtains
(a)0.3M，(b)0.03M，(c)0.008M
The transmission electron microscope photo of the synthetic parcel of the nano zirconium dioxide original position that the reactant of Fig. 2 different concns obtains carbon nano-tube composite powder, wherein, (a) and (b) 0.07M, (c) and (d) 0.008M.
Embodiment
Further specify substantive distinguishing features of the present invention and obvious improvement with following indefiniteness embodiment, thereby illustrate wound point of the present invention.
Embodiment 1
Carbon nanotube is put into 140 ℃ baking oven baking 24 hours to remove the moisture of carbon nanotube, with its reflow treatment 6 hours in concentrated nitric acid, use deionized water wash then, dry.Immerse the ZrOCl of 0.3M after the 72mg acidification at the carbon pipe
28H
2In the O aqueous solution, be placed in 40 milliliters of autoclaves in ultra-sonic dispersion 15-60 minute,, naturally cool to room temperature then 150 ℃ of following hydro-thermal reactions 24 hours.The product that obtains respectively washs three times through water, dehydrated alcohol, promptly obtains the composite granule of nano zirconium dioxide parcel carbon nanotube after the oven dry.Fig. 1 (a) is the composite granule X-ray diffraction spectrogram of the zirconium dioxide parcel carbon nanotube of present embodiment preparation.All peak is all corresponding to the diffraction peak of monocline phase zirconium dioxide among the figure, corresponding to JCPDS card No.3717484, because content of carbon nanotubes is less on the one hand, the broadening peak of main peak coverlet monoclinic phase zirconium dioxide (111) face of carbon nanotube is covered on the other hand, is difficult to distinguish the diffraction peak of carbon nanotube among the figure.Find out that thus what obtain under these processing condition is monocline phase zirconium dioxide original position parcel carbon nano-tube composite powder.Content of carbon nanotubes is less than 5wt%.
Embodiment 2
Carbon nanotube is put into 140 ℃ baking oven baking 24 hours to remove the moisture of carbon nanotube, with its reflow treatment 8 hours in concentrated nitric acid, use deionized water wash then, dry.Immerse the ZrOCl of 0.07M after the 72mg acidification at the carbon pipe
28H
2In the O aqueous solution, be placed in 40 milliliters of autoclaves in ultra-sonic dispersion 15-60 minute,, naturally cool to room temperature then 180 ℃ of following hydro-thermal reactions 18 hours.The product that obtains respectively washs three times through water, dehydrated alcohol, promptly obtains the composite granule of nano zirconium dioxide parcel carbon nanotube after the oven dry.Fig. 1 (b) is the composite granule X-ray diffraction spectrogram of the zirconium dioxide parcel carbon nanotube of present embodiment preparation.As seen from the figure, except the diffraction peak of carbon nanotube and monocline phase zirconium dioxide, the diffraction peak of cubic phase zirconium dioxide (111) face has appearred, this illustrate cubic phase zirconium dioxide and monocline mutually zirconium dioxide coexist as in the matrix material, but mutually based on monocline.Fig. 2 (c), (d) are the transmission electron microscope photos that the zirconium dioxide original position of (different amplification) preparation under these processing condition is wrapped up the composite granule of carbon nanotube.As seen from the figure, carbon nanotube is closely coated by the zirconium dioxide nanoparticle, almost can't see carbon nanotube.
Embodiment 3
Carbon nanotube is put into 140 ℃ baking oven baking 24 hours to remove the moisture of carbon nanotube, with its reflow treatment 6 hours in concentrated nitric acid, use deionized water wash then, dry.Immerse the ZrOCl of 0.008M after the 72mg acidification at the carbon pipe
28H
2In the O aqueous solution, be placed in 40 milliliters of autoclaves in ultra-sonic dispersion 15-60 minute,, naturally cool to room temperature then 200 ℃ of following hydro-thermal reactions 12 hours.The product that obtains respectively washs three times through water, dehydrated alcohol, promptly obtains the composite granule of nano zirconium dioxide parcel carbon nanotube after the oven dry.Fig. 1 (c) is the composite granule X-ray diffraction spectrogram of the zirconium dioxide parcel carbon nanotube of present embodiment preparation.As can be seen from the figure, except the main peak of carbon nanotube, other peak is corresponding to the diffraction peak of cubic phase zirconium dioxide.What therefore, obtain under these processing condition is cubic phase zirconium/carbon dioxide nanometer tube composite materials.Fig. 2 (a) and (b) be the transmission electron microscope photo of the composite granule of the zirconium dioxide original position parcel carbon nanotube of (different enlargement ratio) preparation under the processing condition for this reason.As seen from the figure, the zirconium dioxide nanoparticle is evenly distributed on the tube wall of carbon nanotube, also has small part to be filled in the carbon nanotubes lumen.Zirconium dioxide is spherical in shape, and particle size is 4-5nm.Do not realize full coating this moment to carbon nanotube.Content of carbon nanotubes is greater than 85wt%.
Claims (7)
1, the controlled zirconium/carbon dioxide nanometer composite powder of a kind of crystalline phase is characterized in that: when content of carbon nanotubes was less than 5wt%, zirconium dioxide existed mutually with monocline in the carbon nano-tube composite powder of the nanocrystalline parcel of original position zirconium dioxide of gained; When content of carbon nanotubes during greater than 85wt%, zirconium dioxide exists mutually with the four directions; When content of carbon nanotubes during between 5-85wt%, monocline coexists as in the composite granule with cubic zirconium dioxide mutually mutually.
2, by the described zirconium/carbon dioxide nanometer composite powder of claim 1, it is characterized in that zirconium dioxide is nanocrystalline spherical in shape.
3, by the described zirconium/carbon dioxide nanometer composite powder of claim 2, it is characterized in that zirconium dioxide nano-crystalline granule spherical in shape is of a size of 4-5nm.
4, by the described zirconium/carbon dioxide nanometer composite powder of claim 1, the zirconium dioxide nano-crystalline granule is evenly distributed on the tube wall of carbon nanotube when it is characterized in that content of carbon nanotubes greater than 85wt%, and is partially filled in carbon nanotubes lumen; Content of carbon nanotubes is during less than 85wt%, and then carbon nanotube is closely wrapped up by the zirconium dioxide nano-crystalline granule.
5, the method for preparation zirconium/carbon dioxide nanometer composite powder as claimed in claim 1 is characterized in that: with ZrOCl
28H
2O does the zirconium source, electrostatic attraction effect by carbon nanotube after its positively charged complexing ion that in water, forms and the acidification, that the surface is electronegative, the precursor in situ of zirconium is adsorbed in carbon nano tube surface, carrying out along with hydro-thermal reaction, in the carbon nano tube surface nucleation, and then original position generates ZrO to this complexing ion by esterification
2Nano particle is the composite granule of the carbon nanotube of parcel closely.
6, by the preparation method of the nanocrystalline parcel carbon nano-tube composite powder of the described zirconium dioxide of claim 5, it is characterized in that concrete steps are:
(a) with the multi-walled carbon nano-tubes oven dry, remove the moisture that it contains;
(b) dried carbon nano-tube with concentrated nitric acid in 140 ℃ of reflow treatment 6-8 hours carbon nano tube surface introducing-OH ,-COOH or-the CO active group, use deionized water repetitive scrubbing, oven dry then;
(c) with ZrOCl
28H
2O is dissolved into and is made into the solution that concentration is 0.3-0.009M in the water;
(d) the prepared carbon nano tube modified of step (b) is joined in the aqueous solution of step (c) preparation ultrasonic 15-60 minute;
(e) mixing solutions that step (d) is obtained is put into autoclave, at 150-200 ℃ of following hydro-thermal 12-24 hour, obtains ZrO
2The composite granule of nanoparticle original position parcel carbon nanotube.
(f) product respectively washs 3 times through water, dehydrated alcohol, promptly obtains the composite granule of the nanocrystalline parcel carbon nanotube of zirconium dioxide after the drying.
7,, it is characterized in that by regulating ZrOCl by the preparation method of claim 5 or the nanocrystalline parcel carbon nano-tube composite powder of 6 described zirconium dioxides
28H
2Thereby the O concentration of aqueous solution changes the mass percent of zirconium dioxide and carbon nanotube, obtains the zirconium/carbon dioxide nanometer composite powder of different crystalline phases.
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| CN100544823C (en) * | 2007-12-29 | 2009-09-30 | 中国科学院长春应用化学研究所 | A kind of preparation method of nanometer particle carbon nanotube compound catalyst |
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| CN102424430B (en) * | 2011-08-24 | 2013-08-14 | 郑州轻工业学院 | Preparation method for single crystal cobalt oxide nano-sphere/carbon nano-tube composite nano-material |
| CN103626179A (en) * | 2013-11-19 | 2014-03-12 | 陕西科技大学 | Method for preparing nanometer zirconium carbide powder |
| CN103626179B (en) * | 2013-11-19 | 2015-07-29 | 陕西科技大学 | A kind of method preparing nanometer zirconium carbide powder |
| CN105036099A (en) * | 2015-07-15 | 2015-11-11 | 李亚丰 | Tetragonal phase zirconium dioxide with carbon stability under normal temperature and pressure and preparation method |
| CN106669555A (en) * | 2016-12-06 | 2017-05-17 | 深圳市华星光电技术有限公司 | Preparation method of carbon nanotube conductive ball |
| CN109971420A (en) * | 2019-04-02 | 2019-07-05 | 安徽理工大学 | The preparation method and application of one-dimensional zirconium/carbon dioxide nano-tube nano composite material |
| CN113088957A (en) * | 2021-02-20 | 2021-07-09 | 南昌大学 | Method for preparing wear-resistant and high-temperature-resistant coating on titanium alloy surface through laser cladding |
| CN113088957B (en) * | 2021-02-20 | 2022-09-02 | 景德镇明兴航空锻压有限公司 | Method for preparing wear-resistant and high-temperature-resistant coating on surface of titanium alloy through laser cladding |
| CN114516754A (en) * | 2021-12-27 | 2022-05-20 | 湘潭顺络电子有限公司 | Ultrahigh-strength high-toughness low-density zirconia ceramic and preparation method and application thereof |
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