CN116496082B - Zirconia ceramic and preparation method and application thereof - Google Patents
Zirconia ceramic and preparation method and application thereof Download PDFInfo
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- CN116496082B CN116496082B CN202310461532.4A CN202310461532A CN116496082B CN 116496082 B CN116496082 B CN 116496082B CN 202310461532 A CN202310461532 A CN 202310461532A CN 116496082 B CN116496082 B CN 116496082B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000000919 ceramic Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims description 57
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001238 wet grinding Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
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- 229960003943 hypromellose Drugs 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 14
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000009766 low-temperature sintering Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 238000000280 densification Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
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- 230000002349 favourable effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 3
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005324 grain boundary diffusion Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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Abstract
The invention relates to zirconia ceramic, a preparation method and application thereof, and belongs to the field of composite ceramic materials. The zirconia ceramics of the invention comprise the following crystalline phases: zr (1‑x)MgxO2、Mg2MnO4 and MgO, wherein x is more than 0 and less than or equal to 0.25. According to the invention, mg 2MnO4 is adopted as a light phase to be added into zirconia, part of Mg 2MnO4 is decomposed at high temperature, part of Mg ions are combined with oxygen to form MgO, and the other part of Mg ions enter into a zirconia crystal lattice to form three phases of solid solution Zr (1‑x)MgxO2、Mg2MnO4 and MgO, so that the density of the zirconia ceramic can be effectively reduced, the sintering densification of the zirconia ceramic can be effectively promoted, low-temperature sintering is realized, grains are refined, and the material strength is improved. Meanwhile, the zirconia ceramic provided by the invention is simple in preparation process and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the field of composite ceramic materials, and particularly relates to zirconia ceramic, a preparation method and application thereof.
Background
In recent years, zirconia-based ceramic materials have been widely used as functional ceramics and structural ceramics because of their excellent toughness, strength, oxidation resistance, corrosion resistance, wear resistance, and the like. With the advent of 5G, zirconia ceramics are increasingly widely applied to mobile phone back plates, and particularly with the improvement of color mixing technology, various colorful mobile phone back plates are favored by a large number of consumers. The zirconia has a self density of about 6.09g/cm 3, so that the problems of heavy weight, light weight and the like are avoided even if the thickness of the processed backboard can be controlled to be about 0.4 mm. Therefore, the use of low-density, high-strength lightweight zirconia as a back sheet has been a great deal of research. For example, patent CN108358628B adopts mullite as the light phase, and uses hot press sintering technology to prepare a high toughness and low density zirconia; patent CN108892526A also adopts mullite as a toughening phase, combines a hydrothermal method to prepare composite powder, and then carries out a sintering process to prepare the high-toughness and high-strength zirconia mobile phone backboard. The proposal reduces the density of zirconia to a certain extent, but the operation process is complex and the cost is high.
The patent CN112537957A prepares multiphase composite zirconia ceramic by adding Y, zr, zn, al, si, mg, nb, ta and other elements into zirconia slurry, effectively reduces the density to below 5.65g/cm 3, realizes the effect of light weight, but has the problem that the sintering temperature of a sample is 1350-1450 ℃, and the sintering temperature is too high. Similarly, patent CN113004033A adopts 10-25% cordierite as light phase, and adopts low-temperature sintering at 1280-1340 ℃ to prepare the light zirconia backboard with toughness of more than 6.5Mpa and density of less than 5.40g/cm 3, but the light zirconia backboard has high monoclinic phase content and low strength performance after calcination.
Therefore, development of a zirconia ceramic that can be sintered at low temperature and is lightweight is a technical problem that needs to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the zirconia ceramic which can be applied to low-temperature sintering and has simple preparation method, high strength and low density.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a zirconia ceramic comprising the following crystalline phases: zr (1-x)MgxO2、Mg2MnO4 and MgO, wherein x is more than 0 and less than or equal to 0.25.
According to the invention, a certain content of Mg 2MnO4 is added into zirconia as a light phase, and Mg 2MnO4 is partially decomposed under a certain sintering process condition to form Mg and Mn ions, wherein part of Mg ions enter a crystal lattice of the zirconia to form Zr (1-x)MgxO2 solid solution; part of the Mg ions are combined with oxygen to generate MgO. The theoretical densities of Zr (1-x)MgxO2、Mg2MnO4 and MgO are 5.75g/cm 3,3.83g/cm3 and 3.6g/cm 3, respectively, which are lower than that of zirconia, so that the density of zirconia ceramics can be effectively reduced. In addition, mn ions generated by Mg 2MnO4 decomposition are mainly dissolved in the grain boundary region of the zirconia, and because the radius difference of Mn ions and Zr ions is large, a large number of defects are caused at the grain boundary, the grain boundary diffusion in the sintering process can be effectively promoted, and the sintering temperature of the zirconia ceramic is greatly reduced. As the sintering temperature is reduced, the grain size of the zirconia can be obviously reduced, thereby realizing fine grain strengthening and improving the strength of the final sintered body.
As a preferred embodiment of the zirconia ceramic of the present invention, the x satisfies: x is more than or equal to 0.063 and less than or equal to 0.25.
The inventor of the present invention has found that by adding a specific Mg 2MnO4, the present invention can make the doping amount of Mg ions into the zirconia crystal lattice within the above range, and can make the zirconia ceramic achieve a lower density under the condition of having high strength, thereby making the zirconia ceramic have a better light-weight performance.
In a second aspect, the invention also provides a preparation method of the zirconia ceramic, which comprises the following steps:
S1, uniformly mixing Mg 2MnO4 powder, water and a dispersing agent A in proportion, and wet-grinding to obtain slurry A;
s2, uniformly mixing yttria-stabilized zirconia powder, water, a dispersing agent B and the slurry A in the step S1 according to a proportion, and wet-milling to obtain a slurry B;
s3, carrying out spray granulation, forming and sintering on the slurry B obtained in the step S2 to obtain the zirconia ceramic;
The mass percentage of the Mg 2MnO4 powder is 10-40% based on the total mass of the Mg 2MnO4 powder and the yttria-stabilized zirconia powder;
in the step S3, the sintering temperature is 1200-1300 ℃, and the sintering time is 1-4 h.
By adopting the specific sintering temperature and time range, the invention can better control the decomposition of Mg 2MnO4 and the generation of a small amount of free MgO, and can also effectively promote the sintering densification of zirconia ceramics, thereby realizing low-temperature sintering, refining grains and improving the strength of materials.
As a preferred embodiment of the preparation method of the present invention, the particle size of Mg 2MnO4 powder is 0.1-0.4 μm.
The inventor of the invention researches and discovers that the Mg 2MnO4 powder with the particle size range is favorable for more fully dispersing and mixing the slurry A and uniformly dispersing around zirconia, and can ensure that the generated Zr (1-x)MgxO2 crystal grains can uniformly grow up, so that the zirconia ceramic has more excellent strength performance. The larger grain size of Mg 2MnO4 powder reduces the dispersion performance, which can lead to uneven dispersion in the pulping process, thereby reducing the strength performance of zirconia ceramics; and the particle size of Mg 2MnO4 powder is smaller, agglomeration easily occurs, and the powder is difficult to disperse in the pulping process, so that the agglomeration phenomenon occurs in a ceramic sample, and the strength of zirconia ceramics is reduced.
As a preferred embodiment of the preparation method of the present invention, in the step S1, the mass ratio of Mg 2MnO4 powder, water and dispersant a is Mg 2MnO4 powder: water: dispersant a=100:100: (0.02-3).
The mass ratio of the Mg 2MnO4 powder to the water to the dispersing agent A is in the range, so that the Mg 2MnO4 powder can be uniformly dispersed, the subsequent sintering process is facilitated, and the compact zirconia ceramic is obtained.
As a more preferable embodiment of the preparation method of the invention, the mass percentage of the Mg 2MnO4 powder is 12-30% based on the total mass of the Mg 2MnO4 powder and the yttria-stabilized zirconia powder.
The inventor of the invention researches and discovers that when the mass percentage of Mg 2MnO4 powder is in the range of 12-30% of the total mass of Mg 2MnO4 powder and yttria-stabilized zirconia powder, the doping amount of Mg ions entering the zirconia crystal lattice can be better controlled, so that the formation of a main crystal phase Zr (1-x)MgxO2 is improved, and the zirconia ceramic has better strength and stability. The addition amount of the yttria-stabilized zirconia powder is small, and excessive Mg 2MnO4 can cause the prepared zirconia ceramic to form more MgO and Mg 2MnO4 crystalline phases, so that the strength performance of the zirconia ceramic material is reduced; when the added amount of the yttria-stabilized zirconia powder is large, the density of the zirconia ceramic is high due to the insufficient added amount of the Mg 2MnO4 light phase, so that the low density and the light weight cannot be realized, and meanwhile, the sintering performance is reduced due to the small generated amount of the MgO crystal phase, so that the low-temperature sintering cannot be realized.
As a preferred embodiment of the preparation method of the present invention, in the step S2, the mass ratio of the yttria-stabilized zirconia powder, the water and the dispersant B is that the yttria-stabilized zirconia powder comprises water, the dispersant b=100: (50-100): (0.02-3).
As a preferred embodiment of the production method of the present invention, in the step S2, the D50 of the slurry B is 0.15 to 0.3. Mu.m.
The inventor of the present invention has found that slurry B of the present invention is wet-milled within the above particle size range, so that the D50 distribution of slurry B is narrow and small, which is favorable for uniform size of ceramic grains and higher strength. The grain size range of the slurry B after wet grinding is larger, so that grains with larger sizes are easy to phagocytize grains with small sizes in the sintering process, the grains are abnormally grown, defects appear in the prepared zirconia ceramic, and the strength of the zirconia ceramic is lower; and the particle size range of the slurry B after wet grinding is too small, and the increase of the specific surface area can generate agglomeration, so that a large number of defects are formed in the ceramic, and the strength of the material is reduced.
As a preferred embodiment of the preparation method of the present invention, in the step S2, the yttrium-stabilized zirconia has a mole percentage of yttrium of 0.01 to 8%.
In the yttrium oxide stabilized zirconia, the mole percentage of yttrium is in the range, and the yttrium content is small, so that the yttrium oxide stabilized zirconia is fully doped into a zirconia crystal lattice, and is represented as zirconia with tetragonal phase composition.
As a preferred embodiment of the preparation method of the present invention, in the step S3, the sintering temperature is 1230-1260 ℃ and the sintering time is 2-3 h.
The inventor of the invention researches and discovers that the sintering temperature and time are in the above range, so that the generation of Zr (1-x)MgxO2、Mg2MnO4 and MgO crystalline phases can be effectively controlled, and the prepared zirconia ceramic can keep higher strength under lower density. The sintering temperature is higher or the sintering time is too long, so that Mg 2MnO4 is easier to decompose, and a large amount of free Mg and Mn can quickly promote abnormal growth of crystal grains, thereby reducing the strength of the zirconia ceramic; the sintering temperature is lower or the sintering time is shorter, so that the sample is not sintered densely, the grains are not sufficiently grown and large, a large number of holes exist in the zirconia ceramic, the ceramic forming effect is poor, and the strength is also lower.
As a preferred embodiment of the preparation method of the present invention, the shaping in the step S3 is dry press shaping, and a binder is further added before wet milling in the step S2; the mass ratio of the binder to the yttria-stabilized zirconia powder is as follows: yttria stabilized zirconia powder= (3-6): 100.
The inventor of the present invention has found that a certain amount of binder needs to be added before wet grinding in step S2 before the dry press forming process is adopted, which is more favorable for subsequent sintering; and the injection or casting molding process can be adopted without adding adhesive.
As a more preferable embodiment of the preparation method of the present invention, the binder is at least one selected from polyvinyl alcohol, gelatin, and sodium alginate.
As a preferred embodiment of the preparation method of the present invention, the dispersing agent A and the dispersing agent B are at least one selected from hypromellose, sodium carboxymethyl cellulose, triethanolamine, polyethylene glycol (PEG), polyacrylic acid (PAA) and polystyrene acid.
In a third aspect, the invention also provides application of the zirconia ceramics in preparing a ceramic mobile phone backboard or preparing wearable intelligent equipment.
The zirconia ceramic with the light weight performance can be applied to the preparation of ceramic mobile phone back plates and wearable intelligent equipment, and has a good application prospect.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, mg 2MnO4 is adopted as a light phase to be added into zirconia, so that not only can the density of zirconia ceramic be effectively reduced, but also the sintering densification of the zirconia ceramic can be effectively promoted, thereby realizing low-temperature sintering, refining grains and improving the material strength;
(2) According to the invention, by controlling the addition amount of Mg 2MnO4, a proper amount of Mg ions enter the doping amount of the zirconia crystal lattice, so that the formation of a main crystal phase Zr (1-x)MgxO2 is improved, the zirconia ceramic has better strength and stability, and the generation of a proper amount of low-density MgO can be promoted; mn ions generated by Mg 2MnO4 decomposition are mainly dissolved in the grain boundary region of the zirconia, and because the radius difference of Mn ions and Zr ions is large, a large number of defects are caused at the grain boundary, the grain boundary diffusion in the sintering process can be effectively promoted, and the sintering temperature of the zirconia ceramic is greatly reduced. The grain size of the zirconia can be obviously reduced due to the reduction of the sintering temperature, so that fine grain strengthening is realized, and the strength of the final sintered body is improved;
(3) The zirconia ceramic provided by the invention can be sintered under a low-temperature condition, is simple in preparation process, is beneficial to industrial production, can be applied to preparation of ceramic mobile phone back plates and wearable intelligent equipment, and has a good application prospect.
Drawings
FIG. 1 is an elemental distribution diagram of zirconia ceramics according to example 1 of the present invention, wherein: (a) is an elemental Mg profile; (b) is Mn element distribution map; (c) is a Zr element distribution map; (d) is a Y element profile.
Detailed Description
The technical scheme of the invention is further described below by referring to examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The methods or operations used in the examples, unless specifically indicated, are conventional methods or conventional operations in the art.
Examples 1 to 20 and comparative examples 1 to 10
Examples 1 to 20 and comparative examples 1 to 10 are zirconia ceramics according to the present invention.
The zirconia ceramics of examples 1 to 20 and comparative examples 1 to 10 were produced by the following processes:
S1, uniformly mixing Mg 2MnO4 powder, water and a dispersing agent A in proportion, and wet-grinding to obtain slurry A; wherein, the mass ratio of Mg 2MnO4 powder, water and dispersant A is Mg 2MnO4 powder: water: dispersant a=100: 100:2.2, the dispersant A is triethanolamine;
S2, uniformly mixing yttria-stabilized zirconia powder, water, a dispersing agent B, a binder and the slurry A in the step S1 in proportion, and wet-milling to obtain slurry B; wherein the mole percentage of yttrium in the yttria-stabilized zirconia is 2%, the dispersing agent B is PEG, the binder is polyvinyl alcohol, and the mass ratio of the binder to the yttria-stabilized zirconia powder is: yttria stabilized zirconia powder = 4.5:100;
And S3, carrying out spray granulation, dry press forming and sintering on the slurry B obtained in the step S2 to obtain the zirconia ceramic.
The process parameters of the methods for producing zirconia ceramics of examples 1 to 20 and comparative examples 1 to 10 are shown in the following table 1. In step S2 of the method for producing zirconia ceramics of examples 1 to 18 and comparative examples 1 to 10: the mass ratio of the yttria-stabilized zirconia powder to the water to the dispersant B is that the yttria-stabilized zirconia powder comprises the following components: 100:0.05; in step S2 of the method for producing zirconia ceramics of example 19: the mass ratio of the yttria-stabilized zirconia powder to the water to the dispersant B is that the yttria-stabilized zirconia powder comprises the following components: 50:0.02; in step S2 of the method for producing zirconia ceramics of example 20: the mass ratio of the yttria-stabilized zirconia powder to the water to the dispersant B is that the yttria-stabilized zirconia powder comprises the following components: 80:3.
TABLE 1
Effect example
The zirconia ceramics of examples 1 to 20 and comparative examples 1 to 10 were subjected to phase analysis and element distribution while measuring the density and three-point bending strength, and the specific test methods are as follows:
(1) Element distribution: the zirconia ceramic sample of example 1 was analyzed for its Mg, mn, zr, Y element distribution by transmission electron microscopy;
(2) And (3) phase analysis: carrying out phase analysis on the sample by XRD;
(3) Density: using density samples to measure, wherein the number of the samples is 5, and the average value of 5 measurement results is used as the density of the sample;
(4) Three-point bending strength: the test is carried out by adopting a three-point bending method, and particularly the method for testing the bending strength of the fine ceramic according to GB/T6569-2006.
The test results are shown in fig. 1 and table 2 below.
TABLE 2
As can be seen from fig. 1, the zirconia ceramic of example 1 was sintered at 1250 ℃ for 2 hours, mg 2MnO4 crystal was partially decomposed at high temperature, and free Mg and Mn elements were able to enter into ZrO 2 lattice, so that the zirconia ceramic formed Mg-doped ZrO 2 composite, free MgO and Mg 2MnO4 which was not completely decomposed.
As can be seen from Table 2, by adopting the preparation method of the invention, the density of the zirconia ceramics prepared in examples 1 to 20 can be maintained between 4.9 and 5.7g/cm 3, and the three-point bending strength is between 900 and 1200Mpa, so that the material has lower density while ensuring the strength.
As is clear from the comparison between the examples 1 and the comparative examples 1-2, the zirconia ceramics of the comparative example 1 have the defects in the zirconia ceramics increased and the mechanical properties thereof decreased due to the increase of the content of the impurity phase and the free MgO, as well as the decrease of the content of the zirconia which plays a main role of toughening, although the density of the material can be reduced to 4.70g/cm 3 due to the excessively high content of Mg 2MnO4; while the zirconia ceramic of comparative example 2 has too low Mg 2MnO4 content, although it can improve the three-point bending strength of the material, the ceramic density of the sample increases to 5.78g/cm 3 due to the low content of the light phase, which is not beneficial to the realization of light weight.
As is clear from the comparison between the example 1 and the comparative examples 3 to 4, the lower sintering temperature of the comparative example 3 leads to the condition that the sample is not burned well, so that the grains of the zirconia ceramic prepared are not sufficiently grown up, and the three-point bending strength of the zirconia ceramic is reduced; in contrast, in comparative example 4, too high sintering temperature causes Mg 2MnO4 to decompose excessive MgO to be free, resulting in abnormal growth of grains, and thus the three-point bending strength of zirconia ceramic is also lowered.
As is clear from comparative examples 1 and comparative examples 5 to 6, comparative example 5 has a short sintering time, and the grain growth is incomplete, resulting in a decrease in the three-point bending strength of the zirconia ceramic; whereas comparative example 6 caused abnormal growth of crystal grains due to the excessively long calcination time, the three-point bending strength of the zirconia ceramic was lowered.
As is clear from comparative examples 1 and comparative examples 7 to 8, in the preparation process of the zirconia ceramic of comparative example 7, since the D50 of the slurry B after wet milling is small, the specific surface of the slurry B is increased, agglomeration easily occurs, dispersion is difficult in the pulping process, and the agglomeration phenomenon occurs in the porcelain-forming sample, resulting in a decrease in the strength of the zirconia ceramic. In contrast, in the preparation process of the zirconia ceramic of comparative example 8, since the D50 of the slurry B after wet milling is large, large grains are easy to phagocytize small grains in the sintering process, so that the grains are abnormally grown, defects are easy to occur in the interior, and the strength is obviously reduced.
As is clear from the comparison between the example 1 and the comparative examples 9 to 10, the zirconia ceramic of the comparative example 9 has the advantages that the particle size of the added Mg 2MnO4 powder is smaller, the powder is easy to agglomerate, the powder is difficult to disperse in the pulping process, and the agglomeration phenomenon occurs in the ceramic-forming sample, so that the strength is reduced to 785MPa; the zirconia ceramic of comparative example 10 has uneven distribution, poor dispersibility, and abnormal growth of local crystal grains due to the larger particle size of the added Mg 2MnO4 powder, thereby affecting the strength performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A method for preparing zirconia ceramics, which is characterized by comprising the following steps:
S1, uniformly mixing Mg 2MnO4 powder, water and a dispersing agent A in proportion, and wet-grinding to obtain slurry A;
s2, uniformly mixing yttria-stabilized zirconia powder, water, a dispersing agent B and the slurry A in the step S1 according to a proportion, and wet-milling to obtain a slurry B;
s3, carrying out spray granulation, forming and sintering on the slurry B obtained in the step S2 to obtain the zirconia ceramic;
The mass percentage of the Mg 2MnO4 powder is 10-40% based on the total mass of the Mg 2MnO4 powder and the yttria-stabilized zirconia powder;
In the step S1, the particle size of Mg 2MnO4 powder is 0.1-0.4 mu m, and the mass ratio of Mg 2MnO4 powder, water and dispersant A is Mg 2MnO4 powder: water: dispersant a=100:100: (0.02-3);
in the step S2, the D50 of the slurry B is 0.15-0.3 mu m;
In the step S3, the sintering temperature is 1200-1300 ℃, and the sintering time is 1-4 hours;
The dispersing agent A and the dispersing agent B are at least one selected from hypromellose, sodium carboxymethyl cellulose, triethanolamine, polyethylene glycol and polyacrylic acid.
2. The method according to claim 1, wherein the Mg 2MnO4 powder is 12 to 30% by mass based on the total mass of the Mg 2MnO4 powder and the yttria-stabilized zirconia powder.
3. The method according to claim 1, wherein in the step S2, the yttrium is 0.01 to 8% by mole of the yttria-stabilized zirconia powder.
4. The method according to claim 1, wherein in the step S3, the sintering temperature is 1230-1260 ℃ and the sintering time is 2-3 hours.
5. The method according to claim 1, wherein the shaping in the step S3 is dry press shaping, and a binder is further added before wet milling in the step S2; the mass ratio of the binder to the yttria-stabilized zirconia powder is as follows: yttria stabilized zirconia powder= (3-6): 100.
6. Zirconia ceramic prepared by the preparation method according to any one of claims 1 to 5, characterized by comprising the following crystalline phases: zr (1-x)MgxO2、Mg2MnO4 and MgO, wherein x is more than 0.063 and less than or equal to 0.25.
7. The use of the zirconia ceramic according to claim 6 for the preparation of a ceramic handset back sheet or for the preparation of a wearable smart device.
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