CN115259218B - Preparation method of tetragonal phase zirconium oxide nano powder - Google Patents
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 210000002381 plasma Anatomy 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 230000000171 quenching effect Effects 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 54
- 239000012295 chemical reaction liquid Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 16
- -1 zirconium ions Chemical class 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011858 nanopowder Substances 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 32
- 239000012071 phase Substances 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 13
- 238000005245 sintering Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 238000000498 ball milling Methods 0.000 abstract description 3
- 230000035882 stress Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000593 microemulsion method Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention discloses a preparation method of tetragonal phase zirconia nano powder, which is carried out at room temperature by adopting a liquid phase plasma method, so that complex technological treatment processes such as high-temperature sintering, ball milling and the like in the conventional powder preparation are avoided, the powder dispersibility is good, and the hard agglomeration phenomenon in the sintering process is avoided. In the implementation process, high-energy plasmas are formed between electrodes by adopting high-voltage pulse signals, and the tetragonal zirconia nano powder which can exist stably at room temperature is obtained by combining the rapid quenching effect of low-temperature solution, so that the structure and the performance of the powder are improved. The tetragonal phase zirconia nano powder synthesized based on the method has wide application prospect in the fields of advanced functional ceramic materials, devices and the like.
Description
Technical Field
The invention belongs to the technical field of advanced functional ceramic material preparation, and particularly relates to a preparation method of tetragonal zirconia nano powder.
Background
In the field of new material research, zirconia (ZrO 2) has become an important base material because of its excellent heat resistance, corrosion resistance and plasticity, and is widely used in refractory materials, ceramics, optical glass, zirconia fibers, catalyst supports, bioceramic materials, etc. Compared with monoclinic phase zirconium dioxide, tetragonal phase zirconium dioxide has higher hardness and elastic modulus, and nano powder with tetragonal phase structure is used as original powder, so that a sintered body with a superplastic structure can be obtained, and the service performance of the product is improved. Meanwhile, as the nano powder has small size and large specific surface area, the performance of a matrix can be improved when the nano powder is used as a ceramic material, the sintering temperature is reduced, the service life of a member is prolonged, the cost is reduced, the nano tetragonal zirconia has higher catalytic activity, the nano tetragonal zirconia can be used as a catalyst, the catalytic performance of the material is effectively improved, and the like.
Although tetragonal phase zirconium dioxide is widely used, it belongs to a high temperature phase and cannot exist stably at room temperature, so that the key of research is how to obtain a tetragonal phase structure which exists stably at room temperature. At present, the method for preparing the zirconium dioxide nano powder mainly comprises a microemulsion method, a sol-gel method, a hydrothermal method, a precipitation method and the like, but the method for synthesizing the zirconium dioxide nano powder has certain defects. The microemulsion method is an effective way to synthesize monodisperse nanoparticles, but the non-recyclability of organic solvents and high price limit the use of the microemulsion method. The sol-gel method has simple experimental conditions, convenient operation, low cost, easily controlled product components and good chemical uniformity, but the required raw materials are expensive, the reaction period is long, the hydrolysis conditions are difficult to control, the shrinkage is large when the gel is dried, and the product is easy to agglomerate; the hydrothermal method is a common method for preparing nanocrystalline zirconia, but the equipment investment is large and the technical requirement is high. Enterprises choose to produce nano zirconia powder by a precipitation method, however, avoiding powder agglomeration caused by impurity ions and hydrogen bonds in the drying and heat treatment processes, the need of multiple water washing and alcohol washing processes and the like are main problems puzzling the preparation of nano zirconia by almost all wet chemical methods including a precipitation method, a hydrothermal method and a sol-gel method. Therefore, how to solve the agglomeration problem of nanometer zirconia powder in the processes of precursor preparation, drying and heat treatment more efficiently and with low cost is a difficult problem to be solved in the urgent need of synthesizing high-quality zirconia powder.
Disclosure of Invention
The invention aims to provide a preparation method of tetragonal zirconia nano powder.
The technical scheme for solving the technical problems is as follows:
a preparation method of tetragonal phase zirconia nano powder comprises the following steps:
pre-establishing a reaction environment, taking a double-layer glass beaker, pouring reaction liquid, and then introducing circulating cooling water into an interlayer of the double-layer glass beaker;
liquid stirring, namely placing the reaction environment and the built double-layer glass beaker on a magnetic stirring device, and stirring the reaction liquid through a magnetic stirring rotor;
fixing electrodes, namely, selecting a group of two high-purity zirconium bars as electrodes, fixing the electrodes on an electrode station, and penetrating the electrodes into a double-layer glass beaker and placing the electrodes in a reaction liquid;
generating a high-energy plasma environment, introducing high-voltage pulses to the two electrodes, and controlling the interval between the two electrodes through an electrode station, so that the reaction liquid between the two electrodes is broken down and discharged to form high-energy plasma with strong oxidizing property;
the method comprises the steps that zirconium ions are obtained, two electrodes are arranged in a package of high-energy plasmas, active zirconium atoms are formed on the surfaces of the electrodes through evaporation, and the zirconium atoms emit electrons under the action of a strong electric field and are converted into charged zirconium ions with high energy;
the nano powder is prepared by carrying out oxidation reaction on zirconium ions and high-energy plasmas to generate hot zirconia clusters, accumulating and growing up, and then quenching by surrounding low-temperature reaction liquid, so that the growth is stopped and tetragonal zirconia nano powder is formed.
The invention has the following beneficial effects: the technology is carried out at room temperature, avoids complex technological treatment processes such as high-temperature sintering, ball milling and the like in the conventional powder preparation, has good powder dispersibility and does not have hard agglomeration phenomenon in the sintering process. In the implementation process, a high-voltage pulse power supply is adopted to form high-energy plasmas between electrodes, and the rapid quenching effect of a low-temperature solution is combined, so that the combined stress in the nano particles cannot be fully released, a large amount of residual stress is generated in the particles, the nano zirconia powder is wrapped by strong stress, the stability of tetragonal phases is enhanced (the conclusion in the aspect is reported in literature), and therefore tetragonal phase zirconia powder which exists stably at room temperature is obtained, and the structure and the performance of the powder are improved. The tetragonal phase zirconia nano powder synthesized based on the method has wide application prospect in the fields of advanced functional ceramic materials, devices and the like.
Drawings
FIG. 1 is an XRD pattern of the powder prepared according to the present invention.
Fig. 2 is an SEM image of the powder prepared according to the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
Examples:
the preparation method of tetragonal phase zirconia nano powder in the embodiment of the invention adopts a liquid phase plasma method to synthesize the powder, and comprises the following steps:
pre-establishing a reaction environment, taking a double-layer glass beaker, pouring reaction liquid, and then introducing circulating cooling water into an interlayer of the double-layer glass beaker; the reaction liquid is purified water, the double-layer glass beaker is placed in a room temperature environment, and the diameter of the high-purity zirconium bar is 1-10mm. The circulating cooling water is adopted to cool the double-layer glass beaker in real time, so that the lower temperature of the periphery of the reaction liquid is ensured, and the reaction liquid with low temperature can form a quenching effect on the hot zirconia clusters in the reaction.
Liquid stirring, namely placing the reaction environment and the built double-layer glass beaker on a magnetic stirring device, and stirring the reaction liquid through a magnetic stirring rotor; the magnetic stirring device stirs the reaction liquid to enable the liquid to form moving rotation, so that certain stress is formed on powder generated in the reaction liquid, and the accumulation and growth of the thermal zirconia clusters are promoted.
Fixing electrodes, namely, selecting a group of two high-purity zirconium bars as electrodes, fixing the electrodes on an electrode station, and penetrating the electrodes into a double-layer glass beaker and placing the electrodes in a reaction liquid; the electrode is preferably immersed in the reaction liquid except for the portion to be connected to the power supply and the portion to be fixed, so that the reaction effect is improved.
And generating a high-energy plasma environment, and introducing high-voltage pulses to the two electrodes, wherein the high-voltage pulses are provided by a high-voltage pulse power supply with the voltage controlled at 0.5-20kv, the frequency of the high-voltage pulse power supply is controlled at 200-8000 Hz, and the pulse width is controlled at 20-5000 ns. Within this range, appropriate adjustment can be made to control the reaction rate. In the adjusting process, the needed pulse voltage is selected, and then the adjusting frequency and the pulse width are matched with the pulse voltage. When the pulse voltage is low, the reaction rate is slow, and as the pulse voltage increases, the reaction rate becomes fast. Under a certain pulse voltage, the effect of adjusting the reaction rate can be achieved by adjusting the frequency and the pulse width, and the reaction rate is faster when the frequency is higher and the pulse width is narrower. Within the scope provided in the present invention, the powders to be obtained in the present invention can be obtained, with the only difference in the obtaining rate.
The distance between the two electrodes is controlled through the electrode station, so that the reaction liquid between the two electrodes is broken down and discharged to form high-energy plasma with strong oxidizing property, and the electrode distance of the broken down reaction liquid is smaller than 5mm; the reaction liquid forms the high-energy plasma in high-voltage pulse electrolysis, wherein the high-energy plasma is formed by aggregation of strong oxides, and the strong oxides comprise superoxide, hydrogen peroxide and hydroxyl.
The electrolytic reaction process is as follows,
H 2 O——→H + +OH -
4H 2 O——→2O 2 - +2H + +3H 2
2O 2 - +H 2 ——→2OH - +O 2
2O 2 - +2H 2 O+2H + ——→3H 2 O 2 。
zirconium ions are obtained, two electrodes are in the package of high-energy plasmas, and the surfaces of the electrodes are evaporated to form active zirconium atoms; zirconium atoms are converted into charged zirconium ions with high energy after emitting electrons under the action of a strong electric field, and the zirconium ions comprise Zr + 、Zr 2+ Zr (Zr) 4+ All of which can be produced by reactionOxidized bright.
The preparation of nano powder, namely, performing oxidation reaction on zirconium ions and high-energy plasma to generate hot zirconia clusters, accumulating and growing, and then quenching by surrounding low-temperature reaction liquid, so that the growth is stopped and tetragonal zirconia nano powder is formed, wherein the diameter of the tetragonal zirconia nano powder is smaller than 200nm.
The oxidation reaction of zirconium ions with high-energy plasma proceeds as follows,
Zr + +O 2 - ——→ZrO 2 ↓
2Zr + +3H 2 O 2 ——→2ZrO 2 ↓+2H 2 O+2H +
Zr 2+ +H 2 O 2 ——→(ZrO) 2+ +H 2 O
(ZrO) 2+ +2OH - ——→ZrO 2 ↓+H 2 O
3Zr 2+ +2O 2 - +2H 2 O——→3ZrO 2 ↓+4H +
Zr 4+ +4OH - ——→ZrO 2 ↓+2H 2 O。
in the embodiment, the method for synthesizing the tetragonal phase zirconia powder by adopting the high-voltage pulse liquid phase plasma technology is different from the existing preparation method, mainly uses space breakdown under high voltage to form high-energy plasma, and is subjected to rapid quenching action of surrounding low-temperature solution in the plasma combining process, so that residual stress is generated in particles due to rapid shrinkage and nucleation, and the stability of the tetragonal phase zirconia powder is improved. Experiments prove that the synthesis of the tetragonal zirconia powder at room temperature can be realized by adopting the embodiment, and the size of the tetragonal zirconia powder is increased while the stability of the tetragonal zirconia powder is enhanced, as shown in figures 1-2.
As can be seen from the above embodiments, the present invention has the following advantages:
1. the liquid phase plasma technology adopts a high-voltage pulse power supply to discharge in a solution to form a plasma region, so that the plasma energy is high, the combination property is good, and nano powder is easier to obtain.
2. The low-temperature quenching effect of the liquid around the plasma is utilized to enable the high-energy plasma to be quickly condensed and converted into nano particles, prevent the particles from further growing up, and form a stress effect in the particles, so that the zirconia powder is subjected to monoclinic phase to tetragonal phase conversion, and the stability of the tetragonal phase zirconia powder is improved.
3. Pure water and pure metal are mainly adopted for preparation in the synthesis, so that the method is pollution-free and environment-friendly. The technology is carried out at room temperature, has simple process and lower cost, avoids complex technological treatment processes such as high-temperature sintering, ball milling and the like in the conventional powder preparation, does not have hard agglomeration phenomenon in the sintering process, and improves the dispersibility and stability of the powder.
In addition to the embodiments described above, other embodiments of the invention are possible. For example, the solution can be an acidic solution or an alkaline solution, and the synthesis of the tetragonal zirconia powder is basically not influenced by the pH value of the solution due to the existence of stress in the powder. The invention is based on the fact that the crystal structure of the nano zirconia powder is easy to be influenced by external force, the crystal structure of the powder is easy to be subjected to monoclinic phase to tetragonal phase transformation under the action of external stress, the size of tetragonal phase zirconia which is stable at room temperature is enlarged, and the stability of tetragonal phase zirconia powder with smaller size is enhanced. Experiments show that when the liquid phase plasma method is adopted for synthesis, the aqueous solution between the two electrodes is broken down in space under high potential to form high-energy plasma, and the energy can evaporate, melt and activate the metal forming the electrodes and ions in the solution to enable the metal and the ions to form high-energy plasma and react with each other. Meanwhile, the low-temperature solution around the plasma can rapidly quench the growth of particles, so that the particles shrink and nucleate rapidly to form nano particles, and a certain stress effect is formed in the particles, thereby being beneficial to the synthesis of tetragonal zirconia nano powder
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (6)
1. The preparation method of the tetragonal zirconia nano powder is characterized by comprising the following steps:
pre-establishing a reaction environment, taking a double-layer glass beaker, pouring reaction liquid which is purified water into the double-layer glass beaker, and then introducing circulating cooling water into an interlayer of the double-layer glass beaker;
liquid stirring, namely placing a double-layer glass beaker with a pre-established reaction environment on a magnetic stirring device, and stirring the reaction liquid through a magnetic stirring rotor;
fixing electrodes, namely, selecting a group of two high-purity zirconium bars as electrodes, fixing the electrodes on an electrode station, and penetrating the electrodes into a double-layer glass beaker and placing the electrodes in a reaction liquid;
generating a high-energy plasma environment, introducing high-voltage pulses to the two electrodes, controlling the interval between the two electrodes through an electrode station, and enabling reaction liquid between the two electrodes to be broken down and discharged to form high-energy plasma with strong oxidizing property, wherein the high-voltage pulses are provided by a high-voltage pulse power supply with the voltage controlled at 0.5-20kv, the frequency of the high-voltage pulse power supply is controlled at 200-5000 Hz, and the pulse width is controlled at 20-5000 ns;
the method comprises the steps that zirconium ions are obtained, two electrodes are arranged in a package of high-energy plasmas, active zirconium atoms are formed on the surfaces of the electrodes through evaporation, and the zirconium atoms emit electrons under the action of a strong electric field and are converted into charged zirconium ions with high energy;
the preparation of nano powder, namely, performing oxidation reaction on zirconium ions and high-energy plasma to generate hot zirconia clusters, accumulating and growing, and then quenching by surrounding low-temperature reaction liquid, so that the growth is stopped and tetragonal zirconia nano powder is formed, wherein the diameter of the tetragonal zirconia nano powder is smaller than 200nm.
2. The method for preparing tetragonal zirconia nano-powder according to claim 1, wherein: the high-energy plasma is formed by gathering strong oxides, wherein the strong oxides comprise superoxide, hydrogen peroxide and hydroxyl.
3. The method for preparing tetragonal zirconia nano-powder according to claim 2, wherein: the reaction liquid forms the high-energy plasma in the high-voltage pulse electrolysis, the electrolytic reaction process is as follows,
，/>，/>，。
4. the method for preparing tetragonal zirconia nano-powder according to claim 3, wherein: in the preparation process of the nano powder, the reaction process of the oxidation reaction of zirconium ions and high-energy plasmas is as follows,
，/>，，/>，，/>。
5. the method for preparing tetragonal zirconia nano-powder according to any one of claims 1 to 4, wherein: the double-layer glass beaker is placed in a room temperature environment, and the diameter of the high-purity zirconium bar is 1-10mm.
6. The method for preparing tetragonal zirconia nano-powder according to claim 5, wherein: in the high-energy plasma environment generation step, the electrode spacing of the breakdown reaction liquid is smaller than 5mm.
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