CN111377735A - Surface-modified nano zirconia ceramic powder and preparation method and application thereof - Google Patents
Surface-modified nano zirconia ceramic powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to surface-modified nano zirconia ceramic powder and a preparation method and application thereof, wherein the surface-modified nano zirconia ceramic powder consists of two parts, one part is doped zirconia ceramic powder with the size of less than 200nm, and the other part is organic functional groups or organic resin for surface modification of the zirconia ceramic powder. Compared with the prior art, the invention has the advantages of strong controllability of the preparation process, simple process, convenient operation, low cost, smaller controllable diameter size, good dispersibility and uniform granularity, and has good processability when being used for processing and preparing high-grade ceramic decorative materials and good application prospect in high-end decorative consumer products.
Description
Technical Field
The invention relates to the technical field of nano material preparation and application thereof, in particular to surface-modified nano zirconia ceramic powder and a preparation method and application thereof.
Background
The zirconia ceramic is a common ceramic material in daily life, and has good application performance due to the fact that zirconia is inactive in chemical property and has the properties of high melting point, high resistivity, high refractive index and low thermal expansion coefficient, and the mechanical performance and the thermal sintering performance of the zirconia ceramic can be improved by doping other elements, for example, after a certain amount of yttrium element is doped, the zirconia ceramic material can have very good mechanical performance and better toughness by virtue of a special phase change toughening mechanism of the zirconia ceramic material, and the problem that the ceramic material is common in brittleness is solved. The zirconia-based ceramic material has become the key point of research in the material field, has also become the ceramic decorative material with the fastest development, and has wide market prospect in applications such as high-grade dials, watch chains, artificial teeth, artificial joints, mobile phone shells and the like.
The zirconia ceramic powder is a raw material for processing various ceramic devices and is also the basis of ceramic application. Therefore, the preparation of the zirconia ceramic powder is the core of the zirconia ceramic application technology. In the application process, the purity, particle size, surface property, shape and other properties of the zirconia ceramic powder directly determine the yield and subsequent use performance of ceramic device processing. With the increasing demand of various high-grade ceramic decorative materials, higher performance requirements are put forward on the powder, the powder is required to have smaller particle size reaching the nanometer level, and the particles are uniformly dispersed. Therefore, the preparation of the high-quality zirconia nano ceramic powder is the current research hotspot and technical difficulty.
At present, a plurality of methods such as a precipitation method, a sol-gel method, a microemulsion method, a hydrothermal method and the like exist for preparing zirconia ceramic powder, but the particles of the ceramic powder prepared by the conventional methods for preparing zirconia ceramic powder are often large, even if the particle size can reach a nanometer level, the agglomeration is always serious or the crystal phase is not pure, so that the development and the application of the zirconia ceramic material are greatly limited. In addition, the zirconia ceramic powder after high-temperature roasting treatment has poor compatibility with high-molecular resin in the processing process because of the agglomeration and growth and no organic functional groups on the surface, so that the yield of the zirconia ceramic powder is greatly reduced. In conclusion, the preparation of high-quality nano-grade zirconia ceramic powder and the surface modification treatment thereof are key technical problems for determining the application of zirconia ceramic.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the surface-modified nano zirconia ceramic powder, and the preparation method and the application thereof.
The purpose of the invention can be realized by the following technical scheme:
the surface modified nanometer zirconia ceramic powder consists of two parts, one part is doped zirconia ceramic powder with the size smaller than 200nm, and the other part is organic functional group or organic resin for surface modification of the zirconia ceramic powder.
Furthermore, the doped zirconia ceramic powder has a spherical shape or an irregular shape, the particle diameter is 80-200nm, and the specific surface area is 5-15m2A/g, consisting of a crystalline phase of pure tetragonal phase.
Further, the content of the organic functional group or the organic resin modified on the surface in the nano zirconia ceramic powder modified on the surface is not more than 5 percent of the total mass of the whole nano zirconia ceramic powder modified on the surface;
wherein, the content of doping elements in the first part of doped zirconia ceramic powder is not more than 25 percent of the total mass of the whole ceramic nanometer powder.
Further, the doped zirconia ceramic powder comprises the following components in percentage by weight: 65-98 wt% of zirconium oxide, 0-5 wt% of yttrium oxide, 0-5 wt% of neodymium oxide, 0-5 wt% of cerium oxide, 0-5 wt% of thulium oxide, 0-5 wt% of erbium oxide, 0-5 wt% of samarium oxide, 0-5 wt% of iron oxide, 0-20 wt% of aluminum oxide and 0-5 wt% of silicon oxide.
Further, the organic functional group or the organic resin for surface modification of the zirconia ceramic powder is obtained by modifying the zirconia ceramic powder through a surface modifier, and the surface modifier is one or more of an organic silane coupling agent containing multiple organic functional groups, an organic zirconate coupling agent, an organic titanate coupling agent, an organic aluminum acid ester coupling agent, an organic silicon resin, an organic silicon rubber or an organic polymer.
Further, the surface modifier is one or more of an organosilane coupling agent containing an alkane chain group, an organosilane coupling agent containing an unsaturated bond, an organosilane coupling agent containing an epoxy chain segment, a titanate coupling agent containing an alkane chain group, an organic titanate coupling agent containing an epoxy chain segment, an aluminate coupling agent containing an alkane chain group, an organic aluminate coupling agent containing an epoxy chain segment, polyacrylic acid, polymethacrylic acid, polydopamine, polystyrene and polybutadiene.
Further, the organosilane coupling agent generally means an organosilicon compound having two different chemical property groups in a molecule, and may be, for example, an organosilicon compound having both an X group and a Y group, and may be, for example, YmSiXn(where 1. ltoreq. m.ltoreq.3, 1. ltoreq. n.ltoreq.3, m and n are integers, and m + n. ltoreq.4), the X group and the Y group may be two groups of different chemical properties, for example, the X group includes a group terminating in a chloro group, a fluoroalkyl group, a methoxy group, an ethoxy group, an acetoxy group, or the like, and the Y group includes a group terminating in a vinyl group, an amino group, an epoxy group, a methacryloxy group, a mercapto group, or a ureido; the organosilane coupling agent comprises one or more of a chloro-silane coupling agent, an amino-silane coupling agent, an epoxy-silane coupling agent, a fluorosilane coupling agent, a mercapto-silane coupling agent, a methoxy-silane coupling agent, an ethoxy-silane coupling agent, a methoxy-ethoxy composite silane coupling agent and an acetoxy-silane coupling agent.
A method for preparing nano zirconia ceramic powder with modified surface comprises the following steps,
(1) dissolving a surfactant into a mixed solvent of alcohol and water, and stirring to obtain a clear solution;
(2) adding a zirconium source and a doping element precursor into the clarified solution, and continuously stirring for 0.5-3h for dissolving to obtain a precursor solution; the mass fraction of the zirconium element in the precursor solution is 1-5%;
(3) slowly dripping a prepared precipitator solution into the precursor solution under stirring, continuously stirring for 12-24h to obtain gel precipitate, and drying and calcining after centrifugal separation and washing to obtain doped zirconia ceramic nano powder with the size of less than 200 nm;
(4) the doped zirconia ceramic nanometer powder is coated with surface modification by organic functional group precursor or organic resin. The specific modification method comprises the following steps: dispersing the doped zirconia ceramic powder in a mixed solvent of water and ethanol (V water: V ethanol is 10: 0.5-2), enabling the mass volume concentration of the doped zirconia ceramic powder to be 0.01-0.5 g/ml, then adding ammonia water (the mass fraction of the ammonia water in the whole solution is 1-5%) to obtain a suspension, adding an organic functional group precursor or an organic resin for reaction, then centrifugally separating a lotion and drying to obtain the surface-modified nano zirconia ceramic powder.
Further, the surfactant, the alcohol and the water in the step (1) are mixed according to a mass-to-volume ratio of 0-2 g: 0-50 ml: 200-300 ml;
the precipitator in the step (2) is ammonium oxalate or ammonia water, and the addition amount of the precipitator is 1-5% of the mass of the precursor solution; the zirconium source comprises zirconium oxychloride, zirconium nitrate or zirconium chloride, and the doped element precursor is soluble salt of a doped element, including nitrate or hydrochloride;
the centrifugal separation in the step (3) is performed for 1-10min at the rotating speed of 10000-; the washing is to wash twice by ethanol and then wash twice by water; the drying is drying for 8-16h at 50-80 ℃; the calcination is carried out in a muffle furnace at 800-1200 ℃ for 3-6 h.
The surface-modified nano zirconia ceramic powder can be added into various high-molecular resins to prepare various high-grade ceramic decorative materials.
Further, the polymer resin comprises one or more of bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, alicyclic epoxy resin, phenol-novolac epoxy resin, resorcinol epoxy resin, glycol epoxy resin, trifunctional epoxy resin and bismaleimide resin;
the ceramic high-grade decorative material comprises a ceramic mobile phone shell, a ceramic dial, a ceramic knife, ceramic teeth and ceramic joints.
Compared with the prior art, the invention has the advantages of strong controllability of the preparation process, simple process, convenient operation, low cost, smaller controllable diameter size, various shapes, good dispersibility, uniform granularity, good compatibility with various polymer resins, and capability of being compounded with various polymer resins for processing and forming, thereby preparing various practical ceramic ornament devices. Has good application prospect in the fields of biological medicine, electronics, communication and the like.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the surface-modified nano zirconia ceramic powder prepared in example 1;
fig. 2 is an X-ray diffraction (XRD) pattern of the surface-modified nano zirconia ceramic powder prepared in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Preparation of doped nano zirconia ceramic powder with surface modification size smaller than 200nm
The inventor coats and modifies a plurality of organic functional groups or organic resins on the surface of zirconia ceramic nano powder particles with the size of less than 200nm, and then adds the organic functional groups or the organic resins into high polymer resin, thereby providing a precursor material for processing high-grade ceramic decorative materials with low cost, uniform integral structure, small size and good compatibility, and completing the invention on the basis.
The invention provides an organic functional group or organic resin surface modified zirconia ceramic nano powder with the size less than 200nm, wherein the ceramic powder material mainly comprises two parts, one part is doped nano zirconia ceramic powder with the size less than 200nm, and the other part is a modified organic functional group or organic resin for surface modification treatment. Wherein the doped nano zirconia ceramic powder with the size less than 200nm can be in a spherical shape or a random shape, and the diameter size is 20nm-200 nm. Such surface modification may be dense and/or uniform and may be formed by mechanisms such as chemical bonding, electrostatic interaction, adsorbed layer mediation, and the like.
The surface modification provided by the invention can be one or any combination of organosilane coupling agents containing various organic functional groups, organic titanate coupling agents, organic zirconate coupling agents, organic aluminate coupling agents, organic silicon rubber, organic macromolecules and the like, and more specifically can be one or any combination of organosilane coupling agents containing alkane chain groups, organic silane coupling agents containing unsaturated bonds, organic silane coupling agents containing epoxy chain segments, titanate coupling agents containing alkane chain groups, organic titanate coupling agents containing epoxy chain segments, aluminate coupling agents containing alkane chain groups, organic aluminate coupling agents containing epoxy chain segments, polyacrylic acid, polymethacrylic acid, polydopamine, polystyrene and polybutadiene. Organosilane coupling agents are commonly used. The organosilane coupling agent generally refers to an organosilicon compound containing two groups of different chemical properties in a molecule, and may be, for example, an organosilicon compound containing both X and Y groups, e.g., YmSiXn(wherein 1. ltoreq. m.ltoreq.4, 1. ltoreq. n.ltoreq.4, m and n are integers, and m + n. ltoreq.4), the X group and the Y group may be two different chemical property groups, for example, examples of the X group include, but are not limited to, a chloro group, a fluoroalkyl group, a methoxy group, an ethoxy group, an acetoxy group, or the like at the terminal, examples of the Y group include, but are not limited to, a vinyl group, an amino group, an epoxy group, a methacryloxy group, a mercapto group, or a ureido group at the terminal, and more specifically, examples of the organosilicon functional group precursor include, butAn agent (a silane coupling agent containing a group having a chloro group at the end), an amino silane coupling agent (a silane coupling agent containing a group having an amino group at the end), an epoxy silane coupling agent (a silane coupling agent containing a group having an epoxy group at the end), a fluorosilane coupling agent (a silane coupling agent containing a group having a fluoroalkyl group at the end), a mercaptosilane coupling agent (a silane coupling agent containing a group having a mercapto group at the end), a methoxy silane coupling agent (a silane coupling agent containing a methoxy group at the end), an ethoxy silane coupling agent (a silane coupling agent containing an ethoxy group at the end), a methoxyethoxy complex silane coupling agent (a silane coupling agent containing a methoxy and ethoxy group at the end), an acetoxy silane coupling agent (a silane coupling agent containing an acetoxy group at the end), and the like, or any combination thereof.
Application of doped nano zirconia ceramic powder with surface modification size smaller than 200nm
The invention also provides application of the doped nano zirconia ceramic powder with the surface modification size smaller than 200nm, in particular application in preparing high-grade ceramic decorative materials.
The doped nano zirconia ceramic powder with the surface modification size smaller than 200nm provided by the invention has the characteristics of low cost, uniform integral structure, small size and good high polymer compatibility, and can be used for preparing high-grade ceramic decorative materials. The high-grade ceramic decorative material, more specifically beautiful ceramic decorative material, may be, for example, applied ceramic material including but not limited to ceramic mobile phone shell, ceramic dial, ceramic knife, ceramic tooth, ceramic joint, etc.
Preparation method of high-grade ceramic decorative material
The invention also provides a preparation method of the high-grade ceramic decorative material, which comprises the following steps: adding a certain curing agent into the doped nano zirconia ceramic powder with the surface modification size smaller than 200nm, molding high polymer resin, stirring, shearing, molding, curing and sintering to obtain the ceramic material. In the preparation method of the high-grade ceramic decorative material provided by the invention, a person skilled in the art can select corresponding curing, forming and sintering conditions according to the types of the high-molecular resins, and the curing conditions corresponding to the resins are known to the person skilled in the art.
The invention provides doped nano zirconia ceramic powder with the surface modification size smaller than 200nm, which has the advantages of low cost, uniform integral structure, small size and good high molecular compatibility, and a preparation method and application thereof. The invention innovatively prepares the zirconia ceramic nano powder with the particle size less than 200nm, and then the zirconia ceramic nano powder can obtain good compatibility with high polymer resin through surface modification treatment, thereby being used for processing and preparing high-grade ceramic decorative materials and having very important significance for the development of ceramic materials. The doped nano zirconia ceramic powder material with the surface modification size smaller than 100nm has the advantages of strong controllability of the preparation process, simple process, convenient operation, low cost, smaller controllable diameter size, good dispersibility and uniform granularity, and has good processability when being used for processing and preparing high-grade ceramic decorative materials and good application prospect in high-end decorative consumer products.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content. In the invention, the mechanical property, density and porosity of the ceramic sample processed and sintered are tested.
Example 1
1.0g of surfactant is added into a mixed solution of 50ml of organic alcohol and 300ml of water for dissolution, 3g of zirconium oxychloride and 0.03g of yttrium nitrate are added after dissolution, stirring is continued for half an hour, and then 20ml of a precipitant ammonium oxalate solution (the mass fraction of ammonium oxalate is 2%) is added into the solution. After stirring for 12-24 hours. And centrifuging the generated gel solution product at the rotating speed of 12000rpm for 5 minutes to separate gel, then washing the gel twice by using ethanol, washing the gel twice by using water, drying the gel in the air at 60 ℃ for 12 hours, and calcining the gel at 1000 ℃ for 4 hours to obtain the doped nano zirconia ceramic powder with the diameter and the size of 80 nm. The morphology and characteristics are shown in fig. 1-2. The prepared doped nano zirconia ceramic powder has irregular morphology, and the diameter size of the sphere is about 80 nm. Dispersing the prepared doped nano zirconia ceramic powder with irregular morphology in 150ml of mixed solvent of water and ethanol, adding 5ml of ammonia water, then adding 5ml of epoxy silane coupling agent (product name KH-560, Nanjing Bisuiciding chemical Co., Ltd.) into the solution, continuously stirring for 10hr, centrifugally separating the lotion and drying to obtain a powder sample, mixing the sample with 5.0g of resin, molding and sintering to obtain the ceramic sample.
Example 2
3g of zirconium oxychloride and 0.03g of yttrium nitrate are dissolved in a mixed solution of 50ml of organic alcohol and 300ml of water, stirring is continued for half an hour, and then 20ml of a precipitant ammonium oxalate solution (ammonium oxalate mass fraction is 3%) is added to the above solution. After stirring for 12-24 hours. And centrifuging the generated gel solution product at the rotating speed of 12000rpm for 5 minutes to separate gel, then washing the gel twice by using ethanol, then washing the gel twice by using water, drying the gel in the air at 60 ℃ for 12 hours, and calcining the gel at 1000 ℃ for 4 hours to obtain the uniform doped nano zirconia ceramic powder. The prepared doped nano zirconia ceramic powder has irregular morphology, and the diameter size of the sphere is about 110 nm. Dispersing the prepared doped nano zirconia ceramic powder with irregular morphology in 150ml of mixed solvent of water and ethanol, adding 5ml of ammonia water, then adding 5ml of epoxy silane coupling agent (product name KH-560, Nanjing Bisuiciding chemical Co., Ltd.) into the solution, continuously stirring for 10hr, centrifugally separating the lotion and drying to obtain a powder sample, mixing the sample with 5.0g of resin, molding and sintering to obtain the ceramic sample.
Example 3
1.0g of surfactant is added into 300ml of water mixed solution for dissolution, then 3g of zirconium oxychloride and 0.03g of yttrium nitrate are added after dissolution, stirring is continued for half an hour, and then 20ml of precipitator ammonium oxalate solution (the mass fraction of ammonium oxalate is 5%) is added into the solution. After stirring for 12-24 hours. And centrifuging the generated gel solution product at the rotating speed of 12000rpm for 5 minutes to separate gel, then washing the gel twice by using ethanol, washing the gel twice by using water, drying the gel in the air at 60 ℃ for 12 hours, and calcining the gel at 1000 ℃ for 4 hours to obtain the doped nano zirconia ceramic powder with the diameter and the size of 80 nm. The prepared doped nano zirconia ceramic powder has irregular morphology, and the diameter size of the sphere is about 80 nm. Dispersing the prepared doped nano zirconia ceramic powder with irregular morphology in 150ml of mixed solvent of water and ethanol, adding 5ml of ammonia water, then adding 5ml of epoxy silane coupling agent (product name KH-560, Nanjing Bisuiciding chemical Co., Ltd.) into the solution, continuing stirring for 10h, then centrifugally separating and drying the lotion to obtain a powder sample, mixing the sample with 5.0g of resin, molding and sintering to obtain the ceramic sample.
Example 4
1.0g of surfactant is added into 300ml of water mixed solution for dissolution, then 3g of zirconium oxychloride and 0.03g of yttrium nitrate are added after dissolution, stirring is continued for half an hour, and then 20ml of precipitator ammonia water solution (ammonium oxalate mass fraction is 5%) is added into the solution. After stirring for 12-24 hours. And centrifuging the generated gel solution product at the rotating speed of 12000rpm for 5 minutes to separate gel, then washing the gel twice by using ethanol, washing the gel twice by using water, drying the gel in the air at 60 ℃ for 12 hours, and calcining the gel at 1000 ℃ for 4 hours to obtain the doped nano zirconia ceramic powder with the diameter and the size of 200 nm. The prepared doped nano zirconia ceramic powder has irregular morphology, and the diameter size of the sphere is about 200 nm. Dispersing the prepared doped nano zirconia ceramic powder with irregular morphology in 150ml of mixed solvent of water and ethanol, adding 5ml of ammonia water, then adding 5ml of epoxy silane coupling agent (product name KH-560, Nanjing Bisuiciding chemical Co., Ltd.) into the solution, continuing stirring for 10h, then centrifugally separating and drying the lotion to obtain a powder sample, mixing the sample with 5.0g of resin, molding and sintering to obtain the ceramic sample.
Example 5
(1) Dissolving a surfactant into a mixed solvent of alcohol and water, and stirring to obtain a clear solution; the mass volume ratio of the surfactant to the alcohol to the water is 2 g: 50 ml: 300 ml;
(2) then adding zirconium nitrate and neodymium nitrate into the clarified solution, and continuously stirring for 0.5h to dissolve to obtain a precursor solution; the mass fraction of the zirconium element in the precursor solution is 5 percent;
(3) slowly dripping an ammonium oxalate solution (the mass fraction of ammonium oxalate is 3%) into the precursor solution under stirring, and continuously stirring for 12 hours to obtain a gel precipitate;
(4) centrifuging the gel precipitate at 10000rpm for 10min to obtain gel;
(5) and then washing the gel twice by using ethanol, washing twice by using water, drying for 16h at 50 ℃, and calcining for 6h at 800 ℃ to obtain the doped zirconia ceramic powder with the average particle size of 80 nm. In the neodymium-doped zirconia ceramic powder, the content of neodymium oxide is 2 wt%, and the content of zirconia is 98 wt%;
(6) dispersing the doped zirconia ceramic powder in a mixed solvent of water and ethanol (V water: V ethanol is 10:0.5) to ensure that the mass volume concentration of the doped zirconia ceramic powder is 0.01g/ml, and then adding ammonia water (the mass fraction of the ammonia water in the whole solution is 1%) to obtain a suspension;
(7) and adding polyacrylic acid into the suspension, continuously stirring for 8 hours, then carrying out centrifugal separation, cleaning and drying to obtain a powder sample, wherein the content of the polyacrylic acid in the powder sample is 5% of the total mass of the whole ceramic nano powder.
(8) Mixing the powder sample with naphthalene epoxy resin, molding and sintering to obtain the surface-modified nano zirconia ceramic powder which can be used for manufacturing ceramic mobile phone shells.
Example 6
(1) Dissolving a surfactant into a mixed solvent of alcohol and water, and stirring to obtain a clear solution; the mass volume ratio of the surfactant to the alcohol to the water is 1 g: 25 ml: 200 ml;
(2) adding zirconium oxychloride, yttrium nitrate, neodymium nitrate, cerium nitrate, thulium nitrate, erbium nitrate, samarium nitrate, ferric nitrate, aluminum nitrate and silicon nitrate into the clear solution, and continuously stirring for 3 hours to dissolve the zirconium oxychloride and the yttrium nitrate, the neodymium nitrate, the cerium nitrate, the thulium nitrate, the erbium nitrate, the samarium nitrate, the ferric nitrate, the aluminum nitrate and the silicon nitrate to obtain a precursor solution; the mass fraction of the zirconium element in the precursor solution is 1 percent
(3) Slowly dripping an ammonium oxalate solution (the mass fraction of ammonium oxalate is 3%) into the precursor solution under stirring, and continuously stirring for 24 hours to obtain a gel precipitate;
(4) centrifuging the gel precipitate at 15000rpm for 1min to obtain gel;
(5) then washing the gel twice by ethanol, washing twice by water, drying for 8h at 80 ℃, and calcining for 3h at 1200 ℃ to obtain doped zirconia ceramic powder with the average particle size of 200 nm; in the doped zirconia ceramic powder, the content of zirconia is 65 wt%; the amount of cerium oxide was 5 wt%, the amount of thulium oxide was 5 wt%, the amount of erbium oxide was 5 wt%, the amount of samarium oxide was 5 wt%, the amount of iron oxide was 5 wt%, the amount of aluminum oxide was 5 wt%, and the amount of silicon oxide was 5 wt%.
(6) Dispersing the doped zirconia ceramic powder in a mixed solvent of water and ethanol (V water: V ethanol is 10:2) to ensure that the mass volume concentration of the doped zirconia ceramic powder is 0.5g/ml, and then adding ammonia water (the mass fraction of the ammonia water in the whole solution is 5%) to obtain a suspension;
(7) and then adding polystyrene into the suspension, continuously stirring for 12h, then carrying out centrifugal separation, cleaning and drying to obtain a powder sample, wherein the polystyrene content in the powder sample is 1% of the total mass of the whole ceramic nano powder.
(8) And mixing, molding and sintering the powder sample and bismaleimide resin to obtain the surface-modified nano zirconia ceramic powder which can be used for manufacturing ceramic knives.
The above embodiments are merely illustrative of the technical solutions of the present invention, and not restrictive, and those skilled in the art may make changes, substitutions, modifications, and simplifications in the spirit of the present invention and equivalent changes without departing from the spirit of the present invention, and shall fall within the protection scope of the claims of the present invention.
Claims (10)
1. The surface-modified nano zirconia ceramic powder is characterized by comprising two parts, wherein one part is doped zirconia ceramic powder with the size of less than 200nm, and the other part is organic functional groups or organic resin for surface modification of the zirconia ceramic powder.
2. The surface-modified nano zirconia ceramic powder as claimed in claim 1, wherein the doped zirconia ceramic powder has a spherical morphology or an irregular morphology, a particle diameter of 80 to 200nm, and a specific surface area of 5 to 15m2A/g, consisting of a crystalline phase of pure tetragonal phase.
3. The surface-modified nano zirconia ceramic powder of claim 1, wherein the content of the surface-modified organic functional groups or organic resins in the surface-modified nano zirconia ceramic powder is not more than 5% of the total mass of the surface-modified nano zirconia ceramic powder;
wherein, the content of doping elements in the first part of doped zirconia ceramic powder is not more than 25 percent of the total mass of the whole ceramic nanometer powder.
4. The surface-modified nano zirconia ceramic powder of claim 1, wherein the doped zirconia ceramic powder comprises the following components in percentage by weight: 65-98 wt% of zirconium oxide, 0-5 wt% of yttrium oxide, 0-5 wt% of neodymium oxide, 0-5 wt% of cerium oxide, 0-5 wt% of thulium oxide, 0-5 wt% of erbium oxide, 0-5 wt% of samarium oxide, 0-5 wt% of iron oxide, 0-20 wt% of aluminum oxide and 0-5 wt% of silicon oxide.
5. The surface-modified nano zirconia ceramic powder of claim 1, wherein the organic functional group or organic resin for surface modification of the zirconia ceramic powder is obtained by treating the zirconia ceramic powder with a surface modifier, and the surface modifier is one or more of an organic silane coupling agent containing multiple organic functional groups, an organic zirconate coupling agent, an organic titanate coupling agent, an organic aluminum acid ester coupling agent, an organic silicon resin, an organic silicon rubber or an organic macromolecule.
6. The surface-modified nano zirconia ceramic powder of claim 5, wherein the surface modifier is one or more of an organosilane coupling agent containing an alkane chain group, an organosilane coupling agent containing an unsaturated bond, an organosilane coupling agent containing an epoxy group chain segment, a titanate coupling agent containing an alkane chain group, an organotitanate coupling agent containing an epoxy group chain segment, an aluminate coupling agent containing an alkane chain group, an organoaluminum ester coupling agent containing an epoxy group chain segment, polyacrylic acid, polymethacrylic acid, polydopamine, polystyrene and polybutadiene.
7. A method for preparing the surface-modified nano zirconia ceramic powder according to any one of claims 1 to 6, comprising the steps of,
(1) dissolving a surfactant into a mixed solvent of alcohol and water, and stirring to obtain a clear solution;
(2) adding a zirconium source and a doping element precursor into the clarified solution, and continuously stirring for 0.5-3h for dissolving to obtain a precursor solution;
(3) slowly dripping a prepared precipitator solution into the precursor solution under stirring, continuously stirring for 12-24h to obtain gel precipitate, and drying and calcining after centrifugal separation and washing to obtain doped zirconia ceramic nano powder with the size of less than 200 nm;
(4) the doped zirconia ceramic nanometer powder is coated with surface modification by organic functional group precursor or organic resin.
Dispersing the doped zirconia ceramic powder in a mixture of water and ethanol, adding ammonia water to obtain a suspension, and adding a surface modifier to react to obtain the surface-modified nano zirconia ceramic powder.
8. The method for preparing surface-modified nano zirconia ceramic powder according to claim 7, wherein the surfactant, the alcohol and the water in the step (1) are mixed in a mass-to-volume ratio of 0 to 2 g: 0-50 ml: 200-300 ml;
the precipitator in the step (2) is ammonium oxalate or ammonia water, and the addition amount of the precipitator is 1-5% of the total mass of the precursor solution;
the centrifugal separation in the step (3) is performed for 1-10min at the rotating speed of 10000-; the washing is to wash twice by ethanol and then wash twice by water; the drying is drying for 8-16h at 50-80 ℃; the calcination is carried out in a muffle furnace at 800-1200 ℃ for 3-6 h.
9. The use of the surface-modified nano zirconia ceramic powder according to claim 1, wherein the surface-modified nano zirconia ceramic powder can be added into various polymer resins to prepare various ceramic high-grade decorative materials.
10. The use of the surface-modified nano zirconia ceramic powder according to claim 9, wherein the polymer resin comprises one or more of bisphenol a epoxy resin, brominated bisphenol a epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, alicyclic epoxy resin, phenol-novolac epoxy resin, resorcinol epoxy resin, ethylene glycol epoxy resin, trifunctional epoxy resin and bismaleimide resin;
the ceramic high-grade decorative material comprises a ceramic mobile phone shell, a ceramic dial, a ceramic knife, ceramic teeth and ceramic joints.
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