CN114516754B - Ultrahigh-strength high-toughness low-density zirconia ceramic and preparation method and application thereof - Google Patents
Ultrahigh-strength high-toughness low-density zirconia ceramic and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a zirconium oxide ceramic with ultrahigh strength, high toughness and low density, which is prepared from a composite material and zirconium dioxide; the composite material is a composite material containing carbon nano tubes and zirconium dioxide. According to the invention, nano zirconia is sealed in the carbon nano tube, so that zirconium dioxide in the carbon nano tube is tightly combined with zirconium dioxide in a matrix, and the carbon nano tube is enhanced and toughened in the zirconium dioxide matrix through surface modification of the carbon nano tube and uniform dispersion of a high-pressure homogenizer, so that the carbon nano tube enhanced zirconia ceramic with high strength, high toughness, high thermal conductivity and low density is prepared; and then the problems that the zirconia ceramics are difficult to process, difficult to seal, difficult to combine, large in mass and the like in the intelligent wearing field are solved. The invention also provides a preparation method and application of the ultrahigh-strength high-toughness low-density zirconia ceramic.
Description
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to ultrahigh-strength high-toughness low-density zirconia ceramic and a preparation method and application thereof.
Background
The zirconia ceramics has excellent mechanical property, high temperature resistance and corrosion resistance; wherein the doping is 3% molY 2 O 3 The tetragonal zirconia ceramics of (1) can effectively release stress by phase transformation when subjected to an external force, and therefore have considerable high toughness, and are called "ceramic steels". In recent years, with the continuous maturity of zirconia powder and ceramic preparation technology, the application field of zirconia ceramic is greatly expanded. Many brand-new application scenes need that the zirconia ceramics simultaneously have the characteristics of high strength, high toughness, good heat conduction and the like, the severe requirements cannot be met only by depending on the physical properties of the zirconia ceramics, and the zirconia ceramics are extremely necessary to be modified or compounded by other materials. One of the most representative examples is a smart watch case made of zirconia, which has high strength, jade-like appearance and touch, and good biocompatibility, making it the best case of wearing products, but its high density, low conductivity, and difficult processingAnd difficult bonding with other organic materials, make it challenging. A great deal of research and application has been conducted over 20 years, and many results have been obtained, among which carbon nanotube-modified zirconia ceramics are particularly spotlighted.
The carbon nano tube has extremely excellent mechanical property and has good heat conduction and electric conduction performance. With the maturity of carbon nanotube preparation technology, a large amount of cheap high-performance carbon nanotubes are more and more easily obtained. The combination of the carbon nano tube and the zirconia has attractive prospect, and the application of the zirconia ceramic industry in a higher level is promoted.
The carbon nanotube modified nano zirconia ceramic mainly faces two main difficulties, one is uniform dispersion of the carbon nanotube in the zirconia matrix; secondly, the infiltration and high bonding strength of the carbon nano tube and the zirconia matrix; in particular, how to ensure high strength bonding of the carbon nanotubes to the zirconia matrix is a core problem because of the C and ZrO 2 The ZrC crystal phase with lower strength is easily formed on the bonding interface at high temperature, the bonding strength of the carbon nanotube and the zirconia is greatly reduced, the carbon nanotube is doped into the zirconia matrix and cannot achieve the corresponding enhancement effect, and the low-strength crystal phase and the defects are introduced instead, so that the failure of the carbon nanotube enhanced zirconia is caused.
Disclosure of Invention
In view of the above, the present invention aims to provide a zirconium oxide ceramic with ultra-high strength, high toughness and low density, and a preparation method and an application thereof.
The invention provides a zirconium oxide ceramic with ultrahigh strength, high toughness and low density, which is prepared from a composite material and zirconium dioxide; the composite material is a composite material containing carbon nano tubes and zirconium dioxide.
Preferably, the zirconium dioxide in the composite material is nano zirconium dioxide;
zirconium dioxide in the composite material is arranged inside and on the surface of the carbon nano tube in a crystallization precipitation mode;
the zirconium dioxide in the composite material is rare earth element doped zirconium dioxide.
Preferably, the mass of the carbon nano tube is 0.1-4% of that of the ultrahigh-strength high-toughness low-density zirconia ceramic.
The invention provides a preparation method of the ultrahigh-strength high-toughness low-density zirconia ceramic, which comprises the following steps:
and (3) forming powder formed by the composite material and the zirconium dioxide, and then sintering to obtain the ultrahigh-strength high-toughness low-density zirconium oxide ceramic.
Preferably, the preparation method of the composite material comprises the following steps:
crystallizing the mixed solution to obtain a composite material;
the mixed solution comprises: acid-modified carbon nanotubes and acid-complexed zirconium salt solution;
the ratio of the mass of the carbon nanotubes in the acid-modified carbon nanotubes to the mass of the effective zirconium dioxide of the zirconium salt in the acid-complexed zirconium salt solution is (5-50): (1-5);
the acid adopted by the acid modified carbon nano tube is reducing acid.
Preferably, the method of crystallization comprises:
heating and preserving heat for the mixed solution;
the heating temperature is 65-110 ℃;
the heat preservation time is 1 to 48 hours;
the electrical conductivity of the composite material is less than or equal to 300 mu S/cm.
Preferably, the method for preparing the acid-complexed zirconium salt solution comprises:
mixing the solution containing acid radical ions and the zirconium salt solution;
the ratio of the mole number of the acid radical ions in the solution containing the acid radical ions to the mole number of the zirconium salt in the zirconium salt solution is (1-10): (1-4);
the zirconium salt solution contains rare earth elements.
Preferably, the acid radical ion is an organic acid radical ion;
the organic acid radical ions are selected from one or more of acid radical ions of citric acid and derivatives thereof, acid radical ions of malic acid and derivatives thereof, and acid radical ions of fumaric acid and derivatives thereof.
The present invention provides a wearable device, including: the ultrahigh-strength high-toughness low-density zirconia ceramic in the technical scheme is prepared by the following steps of (1) preparing a high-strength high-toughness low-density zirconia ceramic; or the zirconia ceramics with high strength, high toughness and low density prepared by the method in the technical scheme;
the wearable equipment is intelligent wearable equipment;
the wearable device is a watch, and the watch is an intelligent watch.
The invention provides a mobile phone, comprising: the ultrahigh-strength high-toughness low-density zirconia ceramic in the technical scheme is prepared by the following steps of (1) preparing a high-strength high-toughness low-density zirconia ceramic; or the zirconia ceramics with high strength, high toughness and low density prepared by the method of the technical proposal.
According to the invention, nanometer zirconia is sealed in the carbon nano tube, so that zirconia in the carbon nano tube is tightly combined with zirconia in the matrix, and the effect of strengthening and toughening the carbon nano tube in the zirconia matrix is realized, thereby preparing the low-density zirconia ceramic combined with high strength, high toughness and high thermal conductivity; and further overcomes the defects of difficult processing, difficult sealing, difficult combination, large mass and the like of the zirconia ceramics in the field of intelligent wearing.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a zirconium oxide ceramic with ultrahigh strength, high toughness and low density, which is prepared from a composite material and zirconium dioxide; the composite material is a composite material containing carbon nanotubes and zirconium dioxide.
In the present invention, the zirconia in the composite material is preferably nano zirconia.
In the invention, the zirconium dioxide in the composite material is preferably arranged inside and on the surface of the carbon nano tube in a crystallization precipitation mode;
in the present invention, the zirconia in the composite material is preferably a rare earth element-doped zirconia; the rare earth element is preferably yttrium.
In the present invention, the mass of the carbon nanotube is preferably 0.1 to 4%, more preferably 0.5 to 3.5%, more preferably 1 to 3%, more preferably 1.5 to 2.5%, and most preferably 2% of the mass of the ultra-high strength, high toughness, and low density zirconia ceramic. It is known in the art that carbon nanotubes of suitable mass can be added to the ultra-high strength, high toughness and low density zirconia ceramic according to actual needs to obtain the desired ceramic properties.
The invention provides a preparation method of the ultrahigh-strength high-toughness low-density zirconia ceramic, which comprises the following steps:
and (3) forming powder formed by the composite material and the zirconium dioxide, and sintering to obtain the ultrahigh-strength high-toughness low-density zirconium oxide ceramic.
In the present invention, the method for preparing the powder preferably includes:
and mixing the composite material and the zirconium dioxide slurry, and granulating to obtain powder.
In the present invention, the preparation method of the composite material preferably includes:
crystallizing the mixed solution to obtain a composite material;
the mixed solution comprises: acid-modified carbon nanotubes and acid-complexed zirconium salt solution.
In the present invention, the acid used for the acid-modified carbon nanotube is preferably a reducing acid, and more preferably one or more selected from hydrochloric acid and acetic acid.
In the present invention, the method for preparing the acid-modified carbon nanotube preferably includes:
and immersing the carbon nano tube into an acid solution, and then standing and dispersing.
The carbon nanotubes used in the present invention are not particularly limited, and those known to those skilled in the art can be used and commercially available.
In the present invention, the solvent in the acid solution is preferably water; the concentration of the acid solution is preferably 2 to 5mol/L, more preferably 3 to 4mol/L, and most preferably 3.5mol/L.
In the present invention, the standing time is preferably 30 to 60min, more preferably 40 to 50min, and most preferably 45min. In the present invention, the dispersion method is preferably carried out by sufficiently dispersing with an ultra-high speed disperser.
In the invention, acid is adopted to remove metal impurities on the top end and the tube wall of the carbon nano tube, and after the impurities are removed, pore channels (commonly called as 'open ends' and 'windows') are left at the two ends and the tube wall of the carbon nano tube, so that zirconium ions can enter the carbon nano tube pipeline through diffusion.
In the present invention, the method for preparing the acid-complexed zirconium salt solution preferably comprises:
and mixing the solution containing acid radical ions and the zirconium salt solution.
In the present invention, the acid ion-containing solution is preferably an acid solution or an acid salt solution; the solvent in the solution containing acid radical ions is preferably water; the concentration of the solution containing the acid ion is preferably 1 to 6mol/L, more preferably 2 to 5mol/L, and most preferably 3 to 4mol/L.
In the invention, the acid radical ion is preferably an organic acid radical ion, and more preferably one or more selected from the acid radical ion of citric acid and derivatives thereof, the acid radical ion of malic acid and derivatives thereof, and the acid radical ion of fumaric acid and derivatives thereof; namely, the solution containing acid radical ions is preferably one or more of a solution of citric acid and derivatives thereof, a solution of malic acid and derivatives thereof and a solution of fumaric acid and derivatives thereof.
In the present invention, the zirconium salt solution preferably contains a rare earth element, i.e., a rare earth element-doped zirconium salt solution; the rare earth element is preferably yttrium.
In the present invention, the method for preparing the zirconium salt solution preferably includes:
and mixing and diluting the rare earth element-containing substance and the zirconium-containing substance solution to obtain a zirconium salt solution.
In the present invention, the rare earth element-containing substance is preferably a rare earth oxide and/or a rare earth salt; the rare earth element in the rare earth element-containing substance is preferably yttrium; the rare earth element-containing substance is preferably yttrium oxide and/or yttrium chloride.
In the present invention, the zirconium-containing substance is preferably a zirconium salt, more preferably one or more selected from the group consisting of zirconium oxychloride, zirconium chloride, zirconium nitrate, zirconium carbonate and zirconium sulfate; the solvent in the zirconium-containing substance solution is preferably water; the concentration of the zirconium-containing substance solution is preferably 2 to 3mol/L, more preferably 2.5mol/L.
In the present invention, the ratio of the number of moles of the rare earth element in the rare earth element-containing substance to the number of moles of zirconium in the rare earth element-containing substance is preferably (1 to 8): (92-99), more preferably (2-6): (94-98), more preferably (3-5): (95-97), most preferably 3:97.
in the present invention, the reagent used for the dilution is preferably water, and more preferably deionized water; the total concentration of rare earth and zirconium (the rare earth element content is low and can be ignored and can be directly regarded as the concentration of zirconium) in the zirconium salt solution obtained after dilution is preferably 0.05 to 0.5mol/L, more preferably 0.1 to 0.4mol/L, more preferably 0.2 to 0.4mol/L, more preferably 0.3 to 0.4mol/L, and most preferably 0.4mol/L.
In the present invention, the ratio of the number of moles of acid ions in the solution containing root ions to the number of moles of zirconium salt in the zirconium salt solution is preferably (1 to 10): (1 to 4), more preferably (2 to 8): (2 to 3), most preferably (3 to 6): 2.5; the zirconium salt solution contains rare earth elements, the mol number of the zirconium salt in the zirconium salt solution is the total mol number of the rare earth elements and the zirconium, and the mol number of the zirconium salt can be regarded as the mol number of the zirconium due to the lower content of the rare earth elements.
In the present invention, the method for mixing the acid ion-containing solution and the zirconium salt solution preferably comprises:
the solution containing the acid ions is added dropwise to the zirconium salt solution.
In the invention, acid radical ions can form sufficient complexation with zirconium and rare earth elements in the zirconium salt solution.
In the present invention, the ratio of the mass of the carbon nanotubes in the acid-modified carbon nanotubes to the mass of the zirconium salt in the acid-complexed zirconium salt solution is preferably (5 to 50): (1 to 5), more preferably (10 to 40): (2 to 4), more preferably (20 to 30): (2.5 to 3.5), most preferably 25:3; the zirconium salt contains rare earth substances, the mass of the zirconium salt is the total mass of the rare earth substances and the effective zirconium dioxide in the zirconium-containing substances, and the mass of the zirconium salt can be regarded as the mass of the effective zirconium dioxide in the zirconium-containing substances due to the lower content of the rare earth substances, and the effective zirconium dioxide content is required to be more than 35.5 percent if zirconium oxychloride is used.
In the present invention, the method for preparing the mixed solution preferably includes:
the acid-modified carbon nanotubes are mixed with an acid-complexed zirconium salt solution.
In the present invention, the method for mixing the acid-modified carbon nanotubes and the acid-complexed zirconium salt solution is preferably ultrasonic treatment, and the time of the ultrasonic treatment is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 1.5 to 2 hours, so that the zirconium yttrium ions after complexing are sufficiently diffused into the carbon nanotubes.
In the present invention, the crystallization method preferably includes:
and heating and preserving heat of the mixed solution to obtain the composite material.
In the present invention, the heating is preferably performed in a heating kettle, and the rare earth element-doped zirconium salt solution is simultaneously crystallized inside and outside the carbon nanotubes by heating, thereby precipitating the crystalline nano zirconium dioxide (containing the doped rare earth element).
In the present invention, the heating temperature is preferably 65 to 110 ℃, more preferably 85 to 105 ℃, more preferably 95 to 105 ℃, and most preferably 96 ℃; the time for the heat-retention is preferably 1 to 48 hours, more preferably 1.0 to 12 hours.
In the present invention, it is preferable that the product after the heat-retention is cooled.
In the invention, the composite material is preferably cleaned and separated to obtain rare earth (yttrium) stable nano zirconia slurry compounded by carbon nano tubes; the electrical conductivity of the washed composite material is preferably 300. Mu.S/cm or less, more preferably 50 to 100. Mu.S/cm, more preferably 60 to 90. Mu.S/cm, and most preferably 70 to 80. Mu.S/cm.
In the invention, a hydrolysis crystallization method is adopted to simultaneously crystallize zirconia (containing rare earth elements) precursors in the carbon nano tube and outside the carbon nano tube, and the zirconia crystallized in the carbon nano tube and the zirconia crystallized outside the carbon nano tube are connected at high strength at low temperature, so that the generation of low-strength zirconium carbide at an interface under the high-temperature condition is avoided, which is one of the key conditions of the carbon nano tube reinforced and toughened zirconia.
In the present invention, the zirconia slurry is preferably a sanded zirconia slurry; the invention is not limited to the particular size of the sand, and the person skilled in the art can sand the slurry to obtain the zirconia slurry with the appropriate size according to the actual needs.
In the present invention, the zirconium dioxide slurry preferably includes:
zirconium dioxide and water.
In the present invention, the zirconia slurry has a mass concentration of preferably 30 to 50%, more preferably 35 to 45%, and most preferably 40%.
In the present invention, the mass of the carbon nanotubes in the composite material is preferably 0.1 to 4%, more preferably 0.5 to 3.5%, more preferably 1 to 3%, more preferably 1.5 to 2.5%, and most preferably 2% of the mass of zirconia in the zirconia slurry.
In the present invention, the method of mixing the composite material and the zirconia slurry preferably includes:
pre-dispersing and then performing reinforced dispersing.
In the present invention, the pre-dispersion is preferably performed in a high-speed dispersion apparatus, and the pre-dispersion time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours, so that the carbon nanotubes of the composite zirconia and the zirconia slurry are sufficiently dispersed; the strengthening dispersion is preferably carried out in a high-pressure homogenizer to ensure the uniform dispersion of the carbon nano tubes, the particles (composite material) of the co-crystallization of the carbon nano tubes and the zirconia are uniformly dispersed in the zirconia slurry by adopting the high-pressure homogenizer, and the density of the carbon nano tubes is close to that of the zirconia after the co-crystallization and the composite of the carbon nano tubes and the zirconia, so that the carbon nano tubes can be uniformly dispersed in the zirconia slurry, and the uniform dispersion of the carbon nano tubes in the zirconia ceramic is ensured.
In the present invention, after mixing the composite material and the zirconia slurry, the composite material preferably further comprises:
mixing the obtained mixture with an auxiliary agent, and granulating to obtain powder.
In the present invention, the auxiliary agent is preferably selected from a binder, a lubricant, a release agent, and the like, more preferably a binder; the binder is preferably a polyacrylic resin.
In the present invention, the mass of the auxiliary is preferably 0.3 to 8%, more preferably 0.5 to 7%, more preferably 1 to 6%, more preferably 2 to 5%, and most preferably 3 to 4% of the mass of zirconia in the zirconia slurry.
In the present invention, the mixing of the mixture and the auxiliary is preferably performed under stirring; the stirring time is preferably 30 to 180min, more preferably 45 to 120min, and most preferably 60min.
In the present invention, the forming method is preferably one or more of dry pressing, cold isostatic pressing or hot isostatic pressing.
In the present invention, the sintering temperature is preferably 1400 to 1550 ℃, more preferably 1430 to 1470 ℃, and most preferably 1460 ℃.
The present invention provides a wearable device, including: the ultrahigh-strength high-toughness low-density zirconia ceramic in the technical scheme is prepared by the following steps of (1) preparing a high-strength high-toughness low-density zirconia ceramic; or the zirconia ceramics with high strength, high toughness and low density prepared by the method of the technical proposal.
In the invention, the wearable device is preferably an intelligent wearable device; the wearable device is preferably a shell of the wearable device; the wearable device is preferably a watch, more preferably a smart watch, most preferably a smart watch case.
The invention provides a mobile phone, comprising: the ultrahigh-strength high-toughness low-density zirconia ceramic in the technical scheme is prepared by the following steps of (1) preparing a high-strength high-toughness low-density zirconia ceramic; or the zirconia ceramics with high strength, high toughness and low density prepared by the method of the technical proposal.
The invention organically combines the high strength and the high toughness of the carbon nano tube with the high strength and the high toughness of the zirconia, and the four-point bending strength and the maximum value of the fracture toughness of the prepared composite ceramic can reach 1500MPa and 18 MPa.m 1/2 Thus, the thickness of the product can be greatly reduced, and the weight of the watch case is reduced; and the density of the single-walled carbon nanotube is only 1.2g/cm 3 Density of the tetragonal phase of zirconia is 6.1g/cm 3 The carbon nano tube is much lower, and the product density is also reduced by adding the carbon nano tube, so that the weight reduction effect is achieved; the addition of the carbon nano tube can ensure that the non-conductive zirconia ceramic has good conductivity and the resistivity can reach 10 -4 Omega cm, thus being used as a conductive electrode material to be fused with the height of the watch case; the addition of the carbon nano tube greatly improves the performance of a connection interface between the ceramic surface and an organic matter, and improves the sealing property of the watch case; the addition of the carbon nano tube reduces the processing difficulty of the watchcase, and is beneficial to controlling the size of the watchcase and improving the yield.
The carbon nanotubes used in the following examples of the present invention are the FT9000 model product from tiannai technologies.
Example 1
Soaking 500g of carbon nano tube into 3mol/L hydrochloric acid aqueous solution, standing for 60min, and fully dispersing by using an ultrahigh-speed dispersion machine;
1500g of ZrOCl were taken 2 ·8H 2 Dissolving O in deionized water to prepare 2.5mol/L zirconium oxychloride solution;
will Y 2 O 3 Is dissolved in ZrOCl 2 ·8H 2 In the O solution, a Y-doped zirconium oxychloride solution is formed, the doping ratio of yttrium is generally 3% 2 O 3 In a mole number of Y 2 O 3 And ZrOCl 2 Proportion in total mole number is 3%); then, deionized water is continuously added for dilution to obtain 0.2mol/L Y-doped ZrOCl 2 Mixed solution (abbreviated as Y-ZrOCl) 2 The total concentration of Y and Zr is 0.2mol/L, and Y is negligible);
dissolving fumaric acid in waterThe Y-ZrOCl was slowly injected with a solution (concentration 3 mol/L) 2 Fully stirring the mixed solution to fully complex the zirconium ions and the organic acid radicals to obtain a mixed solution of organic acid complex; the mole number of fumaric acid in the fumaric acid solution and Y-ZrOCl 2 Y-ZrOCl in mixed solution 2 The ratio of the number of moles of (Y to the total number of moles of Zr, the number of moles of Y being negligible) is 2:1.
fully mixing the organic acid complexed mixed solution with the carbon nano tube solution after the acid treatment to obtain a mixed solution; to make Y-ZrOCl 2 The mixed solution can enter the carbon nano tube, ultrasonic treatment is adopted for 1h in the mixing process, and the organic acid is complexed with the mixed solution Y-ZrOCl 2 Intermediate effective ZrO 2 Mass (Y) 2 O 3 ) Negligible mass) and the mass of the carbon nanotubes in the carbon nanotube solution after acid treatment was 1:1.
transferring the mixed solution after ultrasonic treatment into a heating kettle, heating to 96 ℃, preserving heat for 2 hours, carrying out hydrolytic crystallization on organic acid complex zirconium ions, and simultaneously precipitating Y-doped nano zirconia in and on the surface of a carbon nano tube to obtain carbon nano tube composite Y-doped zirconia slurry;
cleaning and filtering the carbon nano tube composite Y-doped zirconia slurry, wherein the conductivity of the cleaned slurry reaches 100 mu S/cm;
adding the cleaned carbon nano tube composite Y-doped zirconia slurry into the sanded zirconia slurry (the zirconia slurry comprises zirconia and water, the mass concentration of the zirconia slurry is 40%), wherein the mass of the carbon nano tube is 0.6% of that of the zirconia in the zirconia slurry, and pre-dispersing by adopting high-speed dispersion equipment; then further homogenizing and dispersing by adopting a high-pressure homogenizer to ensure that the carbon nano tubes are uniformly dispersed into the zirconium dioxide slurry to obtain a mixture;
adding a polyacrylic resin binder into the mixture under the stirring condition, wherein the mass of the polyacrylic resin is 5% of that of zirconium dioxide in the zirconium dioxide slurry, stirring for 40min, and granulating to obtain carbon nanotube composite zirconium oxide powder;
and (3) dry-pressing the powder, and sintering at 1400 ℃ to obtain the ultrahigh-strength high-toughness ceramic.
The conductivity, the strength and the toughness of the ceramic prepared in the embodiment 1 of the invention are detected, wherein the conductivity is tested by adopting a four-electrode method; the four-point bending strength test is detected according to the GB/T6569-2006 Fine ceramic bending strength test method standard; the fracture toughness test is carried out according to the GB/T23806-2009 'test method for fracture toughness of fine ceramics-unilateral pre-crack method' standard; the detection result is as follows: the resistivity is 8-10K omega cm, the four-point bending strength is 1420MPa, and the toughness is 14MPa m 1/2 。
Example 2
An ultra-high strength and high toughness ceramic was prepared according to the method of example 1, except that the mass of the carbon nanotubes was 2% of the mass of zirconia in the zirconia slurry, from example 1.
The ceramic prepared in example 2 of the present invention was measured for properties according to the method of example 1, and as a result, the resistivity was 10 -3 Omega cm, four-point bending strength of 1320MPa, toughness of 17MPa m 1/2 。
Example 3
An ultra-high strength and high toughness ceramic was prepared according to the method of example 1, except that the mass of the carbon nanotubes was 3% of the mass of zirconia in the zirconia slurry, from example 1.
The ceramic prepared in example 3 of the present invention was measured for properties according to the method of example 1, and as a result, the resistivity was 10 -4 Omega cm, four-point bending strength of 1250MPa, toughness of 18MPa m 1/2 。
According to the invention, nanometer zirconia is sealed in the carbon nano tube, so that the zirconia in the carbon nano tube is tightly combined with the zirconia in the matrix, and the effect of strengthening and toughening the carbon nano tube in the zirconia matrix is realized, thereby preparing the low-density zirconia ceramic with high strength, high toughness, high conductivity and high thermal conductivity; and further overcomes the defects of difficult processing, difficult sealing, difficult combination, large mass and the like of the zirconia ceramics in the field of intelligent wearing.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes may be made to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application without departing from the true spirit and scope of the invention as defined by the appended claims. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (5)
1. A preparation method of ultrahigh-strength high-toughness low-density zirconia ceramic comprises the following steps:
the ultrahigh-strength high-toughness low-density zirconia ceramic is prepared from a composite material and zirconium dioxide; the composite material is a composite material containing carbon nanotubes and zirconium dioxide;
forming powder formed by materials containing composite materials and zirconium dioxide, and sintering to obtain the ultrahigh-strength high-toughness low-density zirconium oxide ceramic;
the preparation method of the composite material comprises the following steps:
crystallizing the mixed solution to obtain a composite material;
the mixed solution comprises: acid-modified carbon nanotubes and acid-complexed zirconium salt solution;
the ratio of the mass of the carbon nano tube in the acid-modified carbon nano tube to the mass of the effective zirconia content in the acid complex zirconium salt solution is (5-50): (1~5);
the acid adopted by the acid-modified carbon nano tube is reducing acid;
the zirconium dioxide in the composite material is nano zirconium dioxide;
the zirconium dioxide in the composite material is arranged inside and on the surface of the carbon nanotube in a crystallization precipitation mode;
the zirconium dioxide in the composite material is rare earth element doped zirconium dioxide;
the mass of the carbon nano tube is 0.1 to 4 percent of the mass of the ultrahigh-strength high-toughness low-density zirconia ceramic;
the method for crystallizing comprises the following steps:
heating and preserving heat for the mixed solution;
the heating temperature is 65 to 110 ℃;
the heat preservation time is 1 to 48 hours;
the electrical conductivity of the composite material is less than or equal to 300 mu S/cm.
2. The method of claim 1, wherein the acid-complexed zirconium salt solution is prepared by a method comprising:
mixing the solution containing acid radical ions and the zirconium salt solution;
the ratio of the mole number of the acid radical ions in the solution containing the acid radical ions to the mole number of the zirconium salt in the zirconium salt solution is (1 to 10): (1~4);
the zirconium salt solution contains rare earth elements.
3. The method of claim 2, wherein the acid ion is an organic acid ion;
the organic acid radical ions are selected from one or more of acid radical ions of citric acid and derivatives thereof, acid radical ions of malic acid and derivatives thereof, and acid radical ions of fumaric acid and derivatives thereof.
4. A wearable device, comprising: the ultra-high strength, high toughness and low density zirconia ceramic prepared by the method of claim 1;
the wearing equipment is a smart watch.
5. A handset, comprising:
the ultra-high strength, high toughness and low density zirconia ceramic prepared by the method of claim 1.
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