CN111253155B - Graphene toughened ceramic and preparation method thereof - Google Patents
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Abstract
The invention discloses a preparation method of graphene toughened ceramic, which comprises the following steps: mixing graphene oxide and zirconium oxychloride in a solvent to obtain a precursor mixed solution; adjusting the pH value of the precursor mixed solution to be more than 7; carrying out solid-liquid separation on the alkaline precursor mixed solution, and collecting to obtain a precipitate; carrying out hydrothermal reaction on the precipitate; and sintering the product after the hydrothermal reaction. The invention also discloses the graphene toughened ceramic.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to graphene toughened ceramic and a preparation method thereof.
Background
The ceramic is one of materials widely applied in life, has the characteristics of high melting point, high hardness, high wear resistance and oxidation resistance, is mostly used as a structural material, and the research on functional ceramics is gradually increased along with the rise of fine ceramics. The zirconia ceramics have higher strength and hardness, better wear resistance, chemical corrosion resistance and the like. When the zirconia ceramic is used as high-temperature ceramic, the crystal form of the zirconia ceramic can be changed from a monoclinic system to a tetragonal system and then to the cubic system along with the change of temperature, and the phenomenon of cracking and the like of the material can be caused due to the volume change generated in the phase change process in the process. Meanwhile, as a ceramic material, zirconia also has the common defect of insufficient toughness. The performance of the zirconia ceramics is difficult to meet the higher and higher requirements, and the toughening treatment of the zirconia ceramics becomes an effective way for solving the problem.
Graphene is a two-dimensional layered material, and after zirconia ceramic is added, the graphene can effectively toughen the zirconia ceramic, but the premise of the toughening effect is that the graphene can be uniformly distributed in a ceramic matrix.
Disclosure of Invention
Based on the above, there is a need for a method for preparing graphene toughened ceramic capable of uniformly distributing graphene in zirconia, and graphene toughened ceramic prepared by the method.
A preparation method of graphene toughened ceramic comprises the following steps:
mixing graphene oxide and zirconium oxychloride in a solvent to obtain a precursor mixed solution;
adjusting the pH value of the precursor mixed solution to be more than 7;
carrying out hydrothermal reaction on the alkaline precursor mixed solution;
carrying out solid-liquid separation on the product after the hydrothermal reaction, and collecting solid components;
sintering the solid component.
In one embodiment, the zirconium oxychloride is zirconium oxychloride with crystalline water.
In one embodiment, the zirconium oxychloride with crystal water is zirconium oxychloride octahydrate.
In one embodiment, in the step of adjusting the pH of the precursor mixed solution to be greater than 7, the pH value of the precursor mixed solution after adjustment is 8-10.
In one embodiment, the temperature of the hydrothermal reaction is 150 ℃ to 200 ℃.
In one embodiment, the hydrothermal reaction time is 10-30 h.
In one embodiment, the sintering temperature is 1700 ℃ to 2200 ℃.
In one embodiment, the sintering is hot-pressing sintering, and the pressure applied in the sintering is 20 MPa-30 MPa.
In one embodiment, the sintering time is 0.5-1.5 h.
In one embodiment, the mass ratio of the graphene oxide to the zirconium oxychloride in the precursor mixed solution is (1-5) to (9.4-47).
In one embodiment, the step of mixing graphene oxide and zirconium oxychloride in a solvent to obtain a precursor mixture includes:
dissolving zirconium oxychloride with crystallization water in water to obtain a zirconium oxychloride solution;
dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid; and
mixing the zirconium oxychloride solution with the graphene oxide dispersion liquid.
The graphene toughened ceramic is prepared by the preparation method of the graphene toughened ceramic.
According to the technical scheme, graphene oxide and zirconium oxychloride are used as initial precursors to prepare the graphene zirconia ceramic. Adjusting the precursor mixed solution to be alkaline, so that enough hydroxide exists in the mixed solution, and zirconium ions can react to generate hydrated zirconium hydroxide to generate a precipitate; meanwhile, because the mixed solution contains graphene oxide which is rich in oxygen-containing groups such as carboxyl, hydroxyl and the like, zirconium hydroxide preferentially nucleates on the surface of the graphene oxide, and hydrous zirconium hydroxide wraps the graphene oxide to form a precipitate, so that the zirconium hydroxide is directly deposited on the surface of the graphene oxide. The process of depositing zirconium hydroxide on the graphene oxide can be in solution, and the mixing uniformity of the two is ensured. And performing later hydrothermal reaction and sintering processes, performing thermal decomposition on zirconium hydroxide, and reducing graphene oxide to obtain a uniformly mixed graphene-zirconium oxide composite structure. According to the technical scheme, the graphene and zirconium oxide are mixed by a method of chemical reaction in the solution, and compared with the simple physical mixing of graphene and zirconium oxide powder, the mixing uniformity of graphene and zirconium oxide can be remarkably improved, so that the toughness of zirconium oxide ceramic can be better improved.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Zirconia ceramics have higher strength, toughness and corrosion and abrasion resistance than alumina, are widely applied to the fields of metallurgy, chemical industry, machinery, electronics, petroleum and the like, and are also called as tough ceramics due to the unique stress-induced martensite phase transformation toughening property. The zirconium oxide has extremely high chemical stability and thermal stability, is inert in physiological environment and has good biocompatibility. Pure zirconia has three allotypes and can undergo crystal transformation (phase transition) under certain conditions. When the steel plate is subjected to external force, the process of t-phase-to-m-phase transformation needs to absorb higher energy, so that the stress at the tip of a crack is relaxed, and the crack diffusion resistance is increased to toughen the steel plate, thereby having very high fracture toughness.
At normal temperature, zirconia only appears in monoclinic phase, and is heated to a certain temperature to be converted into tetragonal phase, and is heated to a higher temperature to be converted into cubic phase. Because the monoclinic phase can generate larger volume change when being converted to the tetragonal phase, and the monoclinic phase can generate larger volume change in the opposite direction when being cooled, the product is easy to crack, the application of pure zirconium oxide in the high-temperature field is limited, and the wear-resisting property of the pure zirconium oxide is general.
The graphene is a two-dimensional layered material, and the inventor finds that the graphene can firstly play a role in refining grains after the zirconia ceramic is added; secondly, the larger specific surface area determines that more physical bonds can be formed between the graphene and the zirconia ceramic, and more energy is needed when the bonding surfaces are damaged. Thus, graphene can effectively toughen zirconia ceramics, but this toughening effect is premised on the ability of graphene to be uniformly distributed in the ceramic matrix.
The application enhances the toughness and the wear resistance of the zirconia ceramic by adding graphene in the zirconia. The main problem to be solved is how to uniformly distribute graphene and zirconia, so that the graphene can better play a role in the zirconia.
The embodiment of the invention provides a preparation method of graphene toughened ceramic, which comprises the following steps:
s100, mixing graphene oxide and zirconium oxychloride in a solvent to obtain a precursor mixed solution;
s200, adjusting the pH value of the precursor mixed solution to be more than 7;
s300, carrying out hydrothermal reaction on the alkaline precursor mixed solution;
s400, performing solid-liquid separation on the product after the hydrothermal reaction, and collecting solid components; and
s500, sintering the solid component.
According to the technical scheme, graphene oxide and zirconium oxychloride are used as initial precursors to prepare the graphene zirconia ceramic. Adjusting the precursor mixed solution to be alkaline, so that enough hydroxide exists in the mixed solution, and zirconium ions can react to generate hydrated zirconium hydroxide to generate a precipitate; meanwhile, because the mixed solution contains graphene oxide which is rich in oxygen-containing groups such as carboxyl, hydroxyl and the like, zirconium hydroxide preferentially nucleates on the surface of the graphene oxide, and hydrous zirconium hydroxide wraps the graphene oxide to form a precipitate, so that the zirconium hydroxide is directly deposited on the surface of the graphene oxide. The process of depositing zirconium hydroxide on the graphene oxide can be in solution, and the mixing uniformity of the two is ensured. And performing later hydrothermal reaction and sintering processes, performing thermal decomposition on zirconium hydroxide, and reducing graphene oxide to obtain a uniformly mixed graphene-zirconium oxide composite structure. According to the technical scheme, the graphene and zirconium oxide are mixed by a method of chemical reaction in the solution, and compared with the simple physical mixing of graphene and zirconium oxide powder, the mixing uniformity of graphene and zirconium oxide can be remarkably improved, so that the toughness of zirconium oxide ceramic can be better improved.
The graphene is a two-dimensional layered material, and can firstly play a role in refining grains after being added with the zirconia ceramic; secondly, the larger specific surface area of the graphene determines that the graphene can form more physical bonds with the zirconia ceramic, and more energy is needed when the bonding surface is damaged. Therefore, the graphene can effectively toughen the zirconia ceramic. According to the invention, the toughening effect of graphene in the zirconia ceramic is enhanced by improving the uniform distribution of graphene and zirconia.
In step S100, preferably, graphene oxide and zirconium oxychloride are respectively prepared into a solution and then mixed, so that it can be avoided that graphene oxide is agglomerated or zirconium oxychloride is agglomerated when the graphene oxide and the zirconium oxychloride are directly mixed, and graphene oxide and zirconium oxychloride are not easily dispersed uniformly in the mixed solution.
In an embodiment, the step of mixing graphene oxide and zirconium oxychloride in a solvent to obtain a precursor mixture includes:
dissolving zirconium oxychloride in water to obtain a zirconium oxychloride solution;
dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid; and
mixing the zirconium oxychloride solution with the graphene dispersion liquid.
In one embodiment, the zirconium oxychloride is zirconium oxychloride with crystalline water. Zirconium oxychloride with crystal water.
In one embodiment, the zirconium oxychloride with crystal water is zirconium oxychloride octahydrate. In one embodiment, the concentration of the zirconium oxychloride in the zirconium oxychloride solution is (0.1-0.5) g/800 ml.
In an embodiment, the graphene oxide is easy to agglomerate, and may include a step of subjecting the graphene oxide dispersion liquid to ultrasound, so that the agglomerated graphene oxide is more uniformly dispersed in water by the ultrasound. In one embodiment, the temperature of the ultrasound may be 25 ℃ to 40 ℃. In one embodiment, the time of the ultrasonic treatment can be 3-10 h.
In one embodiment, the concentration of the graphene oxide in the graphene oxide dispersion liquid may be (0.01-0.05) g/200 ml.
In one embodiment, the uniform mixing of the graphene oxide and the zirconium oxychloride can be accelerated by stirring. In one embodiment, the stirring speed may be 100rpm to 500 rpm. In one embodiment, the stirring time may be 2 to 12 hours.
In one embodiment, the mass ratio of the graphene oxide to the zirconium oxychloride in the precursor mixed solution is (1-5): 9.4-47. Within the concentration range, the two components are easier to be uniformly mixed, and the obtained ceramic product has better wear resistance and stronger toughness.
In step S200, the pH is adjusted so that sufficient hydroxyl groups are present in the mixed solution to react the zirconium ions to form hydrous zirconium hydroxide and thereby form a precipitate. Meanwhile, due to the existence of graphene oxide in the mixed solution, the graphene oxide carries a large number of oxygen-containing groups, such as hydroxyl, carboxyl and the like, the existence of hydroxyl enables hydrated zirconium hydroxide to nucleate preferentially on the surface of the graphene oxide, the hydrated zirconium hydroxide wraps the graphene oxide and becomes precipitate, and equivalently, an additional driving force is provided through the transformation of the compound form of zirconium, so that the difference of density is broken, the zirconium element is more easily combined with the graphene oxide, and the difficulty in uniform dispersion of the zirconium hydroxide and the graphene oxide is reduced.
In one embodiment, the pH of the precursor mixture is adjusted to be greater than 7 by adding a base solution to the precursor mixture. In one embodiment, the alkali solution may be selected from ammonia. In one embodiment, the concentration of the ammonia water may be 0.1mol/L to 2 mol/L. In one embodiment, the method of adding the precursor mixture to the alkali solution is to add ammonia water dropwise to the precursor mixture.
In one embodiment, in the step of adjusting the pH of the precursor mixed solution to be greater than 7, the pH of the precursor mixed solution after adjustment is 8 to 10. Specifically, the pH value can be 8-8.5, 8.5-9, 9-9.5 or 9.5-10.
In step S300, the hydrated zirconium hydroxide is dehydrated to form zirconium oxide under hydrothermal reaction, and meanwhile, the hydroxyl carboxyl group in the graphene oxide wrapped inside is thermally decomposed, so that the graphene oxide is substantially completely reduced to reduced graphene oxide, and the whole reduction is completed in the later molding process,
hydrothermal reaction is also called hydrothermal reaction and belongs to the category of liquid phase chemical method. Refers to a chemical reaction that is carried out in a sealed pressure vessel under conditions of high temperature and high pressure.
When the hydrothermal temperature is too low, the decomposition temperature of zirconium hydroxide cannot be reached, and zirconium oxide cannot be generated; when the hydrothermal temperature is too high, the crystal grains of the produced zirconia become large, which is disadvantageous to the compactness and strength of the ceramic. In one embodiment, the temperature of the hydrothermal reaction is 150 ℃ to 200 ℃. Specifically, the temperature of the hydrothermal reaction can be 150-160 ℃, 160-170 ℃, 170-180 ℃, 180-190 ℃ or 190-200 ℃.
In one embodiment, the hydrothermal reaction time may be 10 hours to 30 hours. In the scheme, a product obtained after hydrothermal reaction is a uniform doped body of reduced graphene oxide and zirconium oxide. After the majority of oxidized functional groups of graphene oxide uniformly dispersed in the precursor are removed through a thorough hydrothermal reaction, micropores formed in the material due to gas generated by decomposition of the oxidized functional groups in the subsequent forming process are avoided, the density of the final product can be improved to a certain extent, and the performance of the material is further improved.
In step S400, collection of the solid component is completed by solid-liquid separation.
In one embodiment, the method of solid-liquid separation may be centrifugal separation. Preferably, the centrifugation rate is not too high due to the existence of precipitates, and the centrifugation rate can be 500rpm to 800 rpm.
In one embodiment, step S300 further includes: the collected solid fraction was washed with water to remove excess ions. The supernatant can be added with silver nitrate solution to determine whether the excess ions are washed clean. When the supernatant is taken and added with silver nitrate solution, no white precipitate (silver chloride) is generated, which indicates that impurity ions such as chloride ions in the solution are cleaned. In an embodiment, the method may further include: the washed product was dried. Preferably, in order to avoid product contamination, the drying is performed by vacuum freeze drying. In one embodiment, the drying temperature is-60 ℃ to 80 ℃.
In step S500, all of the zirconium hydroxide is sintered to form zirconium oxide, and graphene is oxidized to form graphene. And the obtained mixed powder is molded by sintering to obtain the blocky ceramic material.
In one embodiment, the sintering temperature may be 1700 ℃ to 2200 ℃. Specifically, the sintering temperature can be 1700-1800 ℃, 1800-1900 ℃, 1900-2000 ℃, 2000-2100 ℃ or 2100-2200 ℃.
In one embodiment, the sintering is hot-pressing sintering, and pressure is applied to the ceramic material during sintering to improve the compactness of the sintered product. In one embodiment, the pressure applied to the product after the hydrothermal reaction in the sintering process may be 20MPa to 30 MPa.
In one embodiment, the sintering time is 0.5 h to 1.5 h.
The density of the zirconia was 5.85g/cm3The density of the graphene is less than 2 g/cm3The difference in density between the two results in difficulty in truly mixing uniformly. The preparation method of the invention completes mixing on the zirconium ion layer, and has more uniformity compared with powder mixing; and the zirconium element is in the form of precursor hydrated zirconium hydroxide, and the graphene is in the form of graphene oxide, so that when the precursor hydrated zirconium hydroxide is generated by reacting by taking the surface of the graphene oxide as a substrate, the density difference is weakened due to the change of the form of the element, and the graphene oxide can be uniformly mixed with a zirconium compound, thereby fundamentally solving the problem of segregation of the graphene caused by the density difference between the zirconium oxide and the graphene powder in the mixing process. Compared with the traditional method of directly and physically mixing the powder, the method adopts the zirconium oxychloride and the graphene oxide in the solutionThe mixing mode of reaction realizes higher mixing uniformity, and the additive capable of introducing impurities is not added, so that the impurity component pollution caused by the additive can be avoided.
The embodiment of the invention also provides the graphene toughened ceramic prepared by the preparation method of the graphene toughened ceramic in any embodiment.
The following are specific examples.
Example 1
(1) Weighing 0.1g of zirconium oxychloride octahydrate powder, and dissolving the zirconium oxychloride powder in 800ml of deionized water to obtain a zirconium oxychloride solution;
(2) weighing 0.05g of graphene oxide, and dispersing the graphene oxide in 200ml of deionized water by an ultrasonic method for 10 hours to obtain a graphene oxide dispersion liquid;
(3) mixing the two solutions, and stirring at 100-500rpm for 2-12h for mixing;
(4) gradually dripping ammonia water solution with the concentration of 0.1-2mol/L into the solution to ensure that the final pH value is 8;
(5) carrying out hydrothermal reaction on the mixed solution at 150 ℃ for 15 h;
(6) collecting the obtained precipitate by centrifugation at a centrifugation speed of 800rpm, washing with deionized water for multiple times to remove excessive ions, and drying to obtain mixed powder;
(7) the forming process of the graphene/zirconia ceramic is completed through hot-pressing sintering, the hot-pressing temperature is 2200 ℃, the pressure is 20-30MPa, and the heat preservation time is 0.5-1.5 h.
Example 2
(1) Weighing 0.5g of zirconium oxychloride octahydrate powder, and dissolving the zirconium oxychloride powder in 800ml of deionized water to obtain a zirconium oxychloride solution;
(2) weighing 0.01g of graphene oxide, and dispersing the graphene oxide in 200ml of deionized water by an ultrasonic method for 3 hours to obtain a graphene oxide dispersion liquid;
(3) mixing the two solutions, and stirring at 100-500rpm for 2-12h for mixing;
(4) gradually dripping ammonia water solution with the concentration of 0.1-2mol/L into the solution to ensure that the final PH value is 8;
(5) carrying out hydrothermal reaction on the mixed solution at 180 ℃ for 30 h;
(6) collecting the obtained precipitate by centrifugation, washing the precipitate with deionized water for multiple times to remove redundant ions, and drying the precipitate to obtain mixed powder;
(7) the forming process of the graphene/zirconia ceramic is completed through hot-pressing sintering, the hot-pressing temperature is 1700 ℃, the pressure is 20-30MPa, and the heat preservation time is 0.5-1.5 h.
Example 3
(1) Weighing 0.4g of zirconium oxychloride octahydrate powder, and dissolving the zirconium oxychloride powder in 800ml of deionized water to obtain a zirconium oxychloride solution;
(2) weighing 0.02g of graphene oxide, and dispersing the graphene oxide in 200ml of deionized water by an ultrasonic method for 3-10h to obtain a graphene oxide dispersion liquid;
(3) mixing the two solutions, and stirring at 100-500rpm for 2-12h for mixing;
(4) gradually dripping ammonia water solution with the concentration of 0.1-2mol/L into the solution to ensure that the final PH value is 10;
(5) carrying out hydrothermal reaction on the mixed solution at 200 ℃ for 20 h;
(6) collecting the obtained precipitate by centrifugation, washing the precipitate with deionized water for multiple times to remove redundant ions, and drying the precipitate to obtain mixed powder;
(7) the forming process of the graphene/zirconia ceramic is completed through hot-pressing sintering, the hot-pressing temperature is 2000 ℃, the pressure is 20-30MPa, and the heat preservation time is 0.5-1.5 h.
Example 4
(1) Weighing 1.5g of zirconium oxychloride octahydrate powder, and dissolving the zirconium oxychloride powder in 800ml of deionized water to obtain a zirconium oxychloride solution;
(2) weighing 0.01g of graphene oxide, and dispersing the graphene oxide in 200ml of deionized water by an ultrasonic method for 3-10h to obtain a graphene oxide dispersion liquid;
(3) mixing the two solutions, and stirring at 100-500rpm for 2-12h for mixing;
(4) gradually dripping ammonia water solution with the concentration of 0.1-2mol/L into the solution to ensure that the final PH value is 10;
(5) carrying out hydrothermal reaction on the mixed solution at 100 ℃ for 25 h;
(6) collecting the obtained precipitate by centrifugation at 2000rpm, washing with deionized water for several times to remove excessive ions, and drying to obtain mixed powder;
(7) the forming process of the graphene/zirconia ceramic is completed through hot-pressing sintering, the hot-pressing temperature is 1800 ℃, the pressure is 20-30MPa, and the heat preservation time is 0.5-1.5 h.
Example 5
(1) Weighing 0.1g of zirconium oxychloride octahydrate powder, and dissolving the zirconium oxychloride powder in 800ml of deionized water to obtain a zirconium oxychloride solution;
(2) weighing 0.5g of graphene oxide, and dispersing the graphene oxide in 200ml of deionized water by an ultrasonic method for 3-10h to obtain a graphene oxide dispersion liquid;
(3) mixing the two solutions, and stirring at 100-500rpm for 2-12h for mixing;
(4) gradually dripping ammonia water solution with the concentration of 0.1-2mol/L into the solution to ensure that the final PH value is 8;
(5) carrying out hydrothermal reaction on the mixed solution at 350 ℃ for 30 h;
(6) collecting the obtained precipitate by centrifugation, washing the precipitate with deionized water for multiple times to remove redundant ions, and drying the precipitate to obtain mixed powder;
(7) the forming process of the graphene/zirconia ceramic is completed through hot-pressing sintering, the hot-pressing temperature is 2100 ℃, the pressure is 20-30MPa, and the heat preservation time is 0.5-1.5 h.
Comparative example 1
(1) 0.1g of zirconium oxide powder and 0.0.5g of graphene oxide were weighed and dispersed in 1000ml of deionized water by means of sonication for 3-10 h. Stirring for 2-12h at 100-500rpm for mixing;
(2) gradually dripping ammonia water solution with the concentration of 0.1-2mol/L into the solution to ensure that the final PH value is 9;
(3) carrying out hydrothermal reaction on the mixed solution at 200 ℃ for 30 h;
(4) collecting the obtained precipitate by centrifugation, washing with deionized water for multiple times to remove redundant ions, and drying to obtain mixed powder;
(5) the forming process of the graphene/zirconia ceramic is completed through hot-pressing sintering, the hot-pressing temperature is 2200 ℃, the pressure is 20-30MPa, and the heat preservation time is 0.5-1.5 h.
The zirconia ceramics obtained in examples 1 to 5 and comparative example 1 were subjected to the performance measurement by the same test method. The results are shown in Table 1.
TABLE 1 comparison of the Properties of different ceramics
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The preparation method of the graphene toughened ceramic is characterized by comprising the following steps:
mixing graphene oxide and zirconium oxychloride in a solvent to obtain a precursor mixed solution, wherein the mass ratio of the graphene oxide to the zirconium oxychloride in the precursor mixed solution is (1-5) to (9.4-47);
adjusting the pH value of the precursor mixed solution to 8-10;
carrying out hydrothermal reaction on the alkaline precursor mixed solution, wherein the temperature of the hydrothermal reaction is 150-200 ℃, and the time of the hydrothermal reaction is 10-30 h;
carrying out solid-liquid separation on the product after the hydrothermal reaction, and collecting solid components;
sintering the solid component, wherein the sintering is hot-pressing sintering, the pressure applied in the sintering is 20-30MPa, and the sintering temperature is 1700-2200 ℃.
2. The method for preparing graphene toughened ceramic according to claim 1, wherein the zirconium oxychloride is zirconium oxychloride with crystal water.
3. The method for preparing graphene toughened ceramic according to claim 2, wherein the zirconium oxychloride with crystal water is zirconium oxychloride octahydrate.
4. The preparation method of the graphene toughened ceramic according to claim 1, wherein the sintering time is 0.5-1.5 h.
5. The method for preparing graphene toughened ceramic according to claim 1, wherein the step of mixing graphene oxide and zirconium oxychloride in a solvent to obtain a precursor mixture comprises:
dissolving zirconium oxychloride with crystallization water in water to obtain a zirconium oxychloride solution;
dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid; and
mixing the zirconium oxychloride solution with the graphene oxide dispersion liquid.
6. The method for preparing graphene toughened ceramic according to claim 1, wherein the pH value of the precursor mixed solution after adjustment is 8 to 8.5, 8.5 to 9, 9 to 9.5 or 9.5 to 10.
7. The preparation method of the graphene toughened ceramic according to claim 1, wherein the temperature of the hydrothermal reaction is 150-160 ℃, 160-170 ℃, 170-180 ℃, 180-190 ℃ or 190-200 ℃.
8. The graphene toughened ceramic prepared by the preparation method of the graphene toughened ceramic according to any one of claims 1 to 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106000297A (en) * | 2016-05-10 | 2016-10-12 | 郑州大学 | Graphene loaded zirconium oxide composite material, preparing method thereof, and application thereof as desulfurizer adsorbent |
| CN106045504A (en) * | 2016-06-01 | 2016-10-26 | 曲靖焜南科技有限公司 | Preparation method for enhancing performance of zirconia ceramic through graphene |
| RU2651524C1 (en) * | 2016-12-27 | 2018-04-20 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВО "МГТУ "СТАНКИН") | Method for the production of a product from black ceramic |
| CN109369179A (en) * | 2018-11-19 | 2019-02-22 | 安徽巨盛石油钻采配件有限公司 | A kind of research of graphene enhancing zirconia ceramics preparation process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000297A (en) * | 2016-05-10 | 2016-10-12 | 郑州大学 | Graphene loaded zirconium oxide composite material, preparing method thereof, and application thereof as desulfurizer adsorbent |
| CN106045504A (en) * | 2016-06-01 | 2016-10-26 | 曲靖焜南科技有限公司 | Preparation method for enhancing performance of zirconia ceramic through graphene |
| RU2651524C1 (en) * | 2016-12-27 | 2018-04-20 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВО "МГТУ "СТАНКИН") | Method for the production of a product from black ceramic |
| CN109369179A (en) * | 2018-11-19 | 2019-02-22 | 安徽巨盛石油钻采配件有限公司 | A kind of research of graphene enhancing zirconia ceramics preparation process |
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