CN102502780B - Preparation method of lanthanum-doped zinc oxide microsphere with wave absorbing performance - Google Patents
Preparation method of lanthanum-doped zinc oxide microsphere with wave absorbing performance Download PDFInfo
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- CN102502780B CN102502780B CN 201110305092 CN201110305092A CN102502780B CN 102502780 B CN102502780 B CN 102502780B CN 201110305092 CN201110305092 CN 201110305092 CN 201110305092 A CN201110305092 A CN 201110305092A CN 102502780 B CN102502780 B CN 102502780B
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Abstract
The invention relates to a preparation method of lanthanum-doped zinc oxide microsphere with wave absorbing performance. The invention has the advantages that: firstly, the lanthanum-doped zinc oxide microsphere with perfect sphere shape and appearance is prepared innovatively by controlling the doping concentration, the reaction time, the reaction temperature, the solution alkalinity and the like; secondly, the lanthanum-doped zinc oxide microsphere has excellent performance and particularly has good wave absorbing performance as well as wide application prospect and important strategic significance as novel wave absorbing material; and thirdly, the raw materials for preparing the lanthanum-doped zinc oxide microsphere are conventional raw materials and readily available, the preparation method is simple and practical, and the preparation parameters are convenient to control.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide, especially a kind of lanthanum of mixing with absorbing property is received micron zinc oxide microballoon and preparation method thereof.
Background technology
In recent years, ZnO because of the energy gap of its 3.37eV and bigger exciton bind energy (up to 60meV), has caused that people more and more pay close attention to as the direct wide bandgap semiconductor oxide material of a kind of important II-VI family.And the ZnO of nanostructure is because its distinctive surface effects, volume effect, quantum effect and dielectric confinement effect etc. are subjected to broad research in technical fields such as catalysis, optics.
The ZnO of nanostructure is studied as a kind of novel absorbing material, and relevant report is less relatively.The ZnO of nanostructure has very strong receptivity at electromagnetic wave band, visible light wave range and infrared band, can reach the effect of escaping radar, infrared stealth; Simultaneously, nano-ZnO has very high chemical stability and high-temperature stability, can enough satisfy weapons system to the requirement of stealth material rigorous environment.We can say, the ZnO of nanostructure relies on that quality is light, thin thickness, of light color, advantage such as wave-sucking performance is strong, as a kind of rising New Type Military radar wave absorbing agent, can absorb the incident radar wave effectively and can make the functional materials of its scatter attenuation, have important and far-reaching meaning for the development of China's national defense technology.
Though the ZnO of nanostructure has numerous unique advantages as absorbing material, single ZnO material still is difficult to reach multiband, wide band assimilation effect, is one of effective way of widening frequency band, increase frequency range and mix.Rare earth element is described as the treasure-house of novel material because have unique character at aspects such as light, electricity, magnetic, and electricity, magnetic, the light property of rare earth element uniqueness is widely used in the absorbing material, is expected to significantly improve the performance of absorbing material.
In addition, numerous studies show that, the appearance structure of nano-ZnO has material impact for its various performances, and the nano-ZnO that particularly has high symmetry, globosity often has than such as more excellent performances such as nano wire, nano belt, nanometer sheet, is the preparation focus of nano ZnO material always.
Yet, mainly concentrate on air-sensitive and aspect such as pressure-sensitive for the nano ZnO material of doped with rare-earth elements and research with nano ZnO material of globosity, and the applied research of above-mentioned materials aspect absorbing material rarely has report, particularly with the two combination, namely doped with rare-earth elements does not appear in the newspapers especially as yet in high symmetry Nano microsphere ZnO.And the objective of the invention is to rare-earth elements of lanthanum is mixed the ZnO microballoon, by rare earth doped and morphology control, improve the absorbing property of ZnO, obtain a kind of high performance lanthanum zinc oxide microballoon absorbing material of mixing.
Summary of the invention
The objective of the invention is to provides a kind of high performance lanthanum zinc oxide microballoon absorbing material and preparation method thereof of mixing by reaction conditionss such as controlled doping concentration, reaction times, temperature of reaction, solution basicity.
The technical solution adopted in the present invention is as follows: a kind of lanthanum of mixing is received micron preparation method of zinc oxide microballoon, it comprises the steps: step 1,0.5～1mol/L zinc acetate and 4-6mol/L sodium hydroxide solution equal-volume are mixed after, ultrasonic concussion 10min, be prepared into precursor, the distilled water that adds 10 times of lanthanum nitrate and precursor volumes then, and the element mol ratio of lanthanum and zinc is La/Zn=0.3-0.7, subsequently ultrasonic concussion 10min again; Step 2, the suspension of gained injected have the teflon-lined stainless steel cauldron, put into thermostatic drying chamber, under 165-170 ℃ of temperature, carry out hydrothermal crystallizing, after 18-21h is carried out in reaction, from reactor, take out the room temperature cooling; Step 3, remove the supernatant liquor in the reactor, with the liquid-solid mixture centrifugation, with deionized water and each washed twice of dehydrated alcohol, will wash the back powder and pour in the watch-glass, placing vacuum tightness is that the vacuum drying oven of 0.04-0.08MPa obtains dry powder in 90-100 ℃ of dry 2-4h; Step 4, with dry powder 680-720 ℃ the calcining 3-5h, obtain mixing the zinc oxide microballoon of lanthanum nanostructure at last.
Concentration sodium hydroxide is received the influence that micron zinc oxide microballoon forms for mixing lanthanum, be mainly reflected in the system speed of response and form two aspects of polar growth of zinc oxide microballoon branch: the one, the raising of basicity is beneficial to carrying out fast of reaction, thereby avoids the reaction times long and globosity that cause disintegrates; The 2nd, the raising of basicity makes the zincite crystal growth tend to polar growth, is unfavorable for the formation of globosity.As seen, there is certain contradiction in naoh concentration for the influence of mixing the formation of lanthanum zinc oxide microballoon, and is excessive too small all improper.The applicant thinks that through lot of experiments when concentration sodium hydroxide was 4-6mol/L, reaction effect was better, and particularly preferably being concentration sodium hydroxide is 5mol/L.
Reaction times is received the influence that micron zinc oxide microballoon forms for mixing lanthanum, mainly be to need the certain reaction time to carry out to react fully and form mixing lanthanum and receiving a micron zinc oxide microballoon, but the reaction times is unsuitable long again, and the long reaction times can make the zinc oxide with polar growth tendency take place to disintegrate and destroy the microballoon pattern.The applicant thinks that through lot of experiments the reaction times, reaction effect was better when being 18-21h, and particularly preferably being the reaction times is 19h.
Temperature of reaction is received the influence that micron zinc oxide microballoon forms and is similar to basicity for mixing lanthanum, be presented as that mainly temperature is for the influence of speed of response and two aspects of polar growth: the raising of temperature is beneficial to carrying out fast of reaction on the one hand, thereby the microballoon that generates perfect pattern within a short period of time avoids the reaction times long and globosity that cause disintegrates; The raising that is temperature has on the other hand aggravated polar growth trend, is unfavorable for the formation of globosity.As seen, temperature of reaction also is excessive too small all improper.The applicant thinks that through lot of experiments when temperature of reaction was 165-170 ℃, reaction effect was better, and particularly preferably being temperature of reaction is 168 ℃.
The lanthanum doping content is received the influence that micron zinc oxide microballoon forms for mixing lanthanum, and its effect is single, i.e. La
3+Doping content more low, influence for zinc oxide microballoon pattern is more little, otherwise doping content is more high, destroy more serious to pattern, when the atomic ratio of the doping content of La and Zn reaches 0.8 left and right sides, the zinc oxide microballoon occur to disintegrate, and reaches at 1.0 o'clock, microballoon pattern havoc and become bar-shaped monomer.Yet, in order to satisfy the requirement that improves the zinc oxide absorbing property, must make the doping of La reach finite concentration.The applicant thinks that through lot of experiments when the doping content of La was the element mol ratio La/Zn=0.3-0.7 of lanthanum and zinc, reaction effect and performance were all better, particularly preferably is the element mol ratio La/Zn=0.5 of lanthanum and zinc.
Foregoing as can be known, in preparation process, above parameter exists for the influence of reaction and closely connects each other, can be described as the result of these parametric synthesis effects, the applicant for the sake of clarity explains separately at each parameter.
The invention has the beneficial effects as follows, at first, by reaction conditionss such as controlled doping concentration, reaction times, temperature of reaction, solution basicity, prepared innovatively and have nanostructured zinc oxide microballoon perfect spherical morphology, that mix lanthanum; The second, mix lanthanum nanostructured zinc oxide microballoon excellent performance, particularly have good absorbing property, be with a wide range of applications and the important strategic meaning as novel wave-absorbing material; The 3rd, preparation raw material routine is easy to get, and the preparation method is simple, and preparation parameter is convenient to control.
Description of drawings
Fig. 1 is the SEM typical image of mixing lanthanum nanostructured zinc oxide microballoon in the specific embodiment of the invention;
Fig. 2 is the XRD diffracting spectrum of mixing lanthanum nanostructured zinc oxide microballoon in the specific embodiment of the invention;
Fig. 3 is frequency-reflectance curve of mixing lanthanum nanostructured zinc oxide microballoon in the specific embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing 1-3 and concrete embodiment the present invention is done and to describe in further detail:
A kind of preparation method who mixes lanthanum nanostructured zinc oxide microballoon, it comprises the steps: step 1,1mol/L zinc acetate and 6mol/L sodium hydroxide solution equal-volume are mixed after, the distilled water that adds 10 times liquor capacity again, ultrasonic concussion 10min, add lanthanum nitrate then, the element mol ratio of lanthanum and zinc is La/Zn=0.5, subsequently ultrasonic concussion 10min again; Step 2, the suspension of gained injected have the teflon-lined stainless steel cauldron, put into thermostatic drying chamber, under 168 ℃ of temperature, carry out hydrothermal crystallizing, after 19h is carried out in reaction, from reactor, take out; After step 3, the cooling at room temperature, remove supernatant liquor, with the pressed powder centrifugation, with deionized water wash three times, will wash afterwards powder and pour in the watch-glass, placing vacuum tightness is that the vacuum drying oven of 0.06MPa obtains dry powder in 98 ℃ of dry 3h; Step 4, with dry powder at 700 ℃ of calcining 4h, the lanthanum of mixing with perfect spherical morphology that obtains is at last as shown in Figure 1 received a micron zinc oxide microballoon.
Fig. 2 is pure ZnO and the XRD stack collection of illustrative plates of mixing lanthanum nanostructured zinc oxide microballoon.Contrast as can be known with standard diagram, sample is the hexagonal system wurtzite structure.Do not occur the diffraction peak of rare earth oxide on the stack spectrogram, diffraction peak is comparatively sharp-pointed, shows La
3+Entered in the lattice defect of ZnO, formed sosoloid, the well-crystallized, mixing does not influence crystal configuration.
The reflectivity of mixing lanthanum nanostructured zinc oxide microballoon with the curve of change of frequency as shown in Figure 3, in measuring range of frequency, there is extreme value in reflectivity, and minimum is-20dB, all less than-10dB, absorbing frequency range less than-10dB is 2.5GHz from 9.1GHz to the 11.6GHz reflectivity.
Claims (6)
1. preparation method who mixes lanthanum nanostructured zinc oxide microballoon, it comprises the steps: step 1,1mol/L zinc acetate and 6mol/L sodium hydroxide solution equal-volume are mixed after, the distilled water that adds 10 times liquor capacity again, ultrasonic concussion 10min, add lanthanum nitrate then, the element mol ratio of lanthanum and zinc is La/Zn=0.5, subsequently ultrasonic concussion 10min again; Step 2, the suspension of gained injected have the teflon-lined stainless steel cauldron, put into thermostatic drying chamber, under 168 ℃ of temperature, carry out hydrothermal crystallizing, after 19h is carried out in reaction, from reactor, take out; After step 3, the cooling at room temperature, remove supernatant liquor, with the pressed powder centrifugation, with deionized water wash three times, will wash afterwards powder and pour in the watch-glass, placing vacuum tightness is that the vacuum drying oven of 0.06MPa obtains dry powder in 98 ℃ of dry 3h; Step 4, with dry powder 700 ℃ the calcining 4h, obtain mixing the zinc oxide microballoon of lanthanum nanostructure at last.
2. a kind of lanthanum zinc oxide microballoon of mixing of making of preparation method according to claim 1.
3. the described a kind of application of lanthanum zinc oxide microballoon in absorbing material of mixing of claim 2.
4. absorbing material, it mainly is made of the described lanthanum zinc oxide microballoon of mixing of claim 2.
5. a kind of absorbing material according to claim 4 is characterized in that: inhale the ripple frequency range when 9.1GHz to 11.6GHz, reflectivity is all less than-10dB.
6. a kind of absorbing material according to claim 5 is characterized in that: inhale the ripple frequency range when being 8-12GHz, its electromagnetic wave attenuation is 20dB to the maximum.
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