CN110342926B - Zirconia powder cake, preparation method and application thereof, and method for adjusting shrinkage performance of zirconia powder cake - Google Patents

Zirconia powder cake, preparation method and application thereof, and method for adjusting shrinkage performance of zirconia powder cake Download PDF

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CN110342926B
CN110342926B CN201910570635.8A CN201910570635A CN110342926B CN 110342926 B CN110342926 B CN 110342926B CN 201910570635 A CN201910570635 A CN 201910570635A CN 110342926 B CN110342926 B CN 110342926B
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zirconia
yttrium
hydrothermal synthesis
powder
temperature
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CN110342926A (en
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宋锡滨
杨爱民
张巧云
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Shandong Sinocera Functional Material Co Ltd
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    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C11/00—Watch chains; Ornamental chains
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A44C5/0084—Bracelets in the form of a ring, band or tube of rigid material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/878—Zirconium oxide
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    • 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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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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Abstract

The invention provides a zirconia pressed powder, a preparation method and application thereof, and a method for adjusting the shrinkage performance of the zirconia pressed powder. The zirconia powder cake comprises at least two zirconia powder layers, wherein the yttrium contents of different zirconia powder layers are different, and the difference of TMA curve shrinkage starting temperatures of the different zirconia powder layers is less than or equal to 5 ℃; and the TMA curve shrinkage deviation of the different zirconia powder layers is less than or equal to 0.3 percent. The invention provides a zirconia compact, a preparation method and application thereof, wherein different zirconia powder layers of the zirconia compact have different yttrium contents and still have roughly consistent shrinkage behaviors, so that higher deformation stability is provided for a subsequent sintering process, and defects of deformation, cracking and the like caused by inconsistent shrinkage behaviors are effectively avoided.

Description

Zirconia powder cake, preparation method and application thereof, and method for adjusting shrinkage performance of zirconia powder cake
Technical Field
The invention belongs to the field of ceramic materials, and relates to a zirconia compact, a preparation method and application thereof, and a method for adjusting the shrinkage performance of the zirconia compact, in particular to a zirconia compact, a preparation method and application thereof, a zirconia sintered body prepared from the zirconia compact, a preparation method and application thereof, a denture prepared from the zirconia compact or the zirconia sintered body, a preparation method of the denture, a method for adjusting the initial shrinkage temperature of the zirconia sintered body, and a method for adjusting the shrinkage rate of the zirconia sintered body.
Background
The natural tooth has gradually changed light transmittance, and the layered zirconia false tooth can be made into a light transmittance gradually-changed false tooth which is closer to the appearance of the natural tooth. The light transmission gradual-change type artificial tooth has different Y2O3And (4) realizing the content. However, because of different components, the shrinkage behavior of various zirconia powders produced by the same process is different, and when two or more zirconia powders with different yttrium contents are pressed in a layered manner, internal stress can occur in the sintering process, which leads to the integral strengthReduce even cracking, and the finished product after sintering is deformed.
One of the prior art is by adjusting the sintering aid (e.g. Al)2O3Etc.) to achieve an adjustment of the shrinkage behaviour. The addition of the sintering aid can influence the growth state of crystal grains, thereby controlling the sintering activity of the zirconia. When sintering is carried out at the same temperature, different shrinkage behaviors can be obtained by adding different types or different contents of sintering aids. Although the sintering aid can effectively adjust the sintering shrinkage of zirconia, the addition of the sintering aid affects the permeability and color of the zirconia sintered body. For example, adding Al to zirconia2O3The sintered body permeability will decrease and the whiteness will increase. In order to avoid this defect, the yttrium content may be increased to improve the strength of the sintered body. Therefore, the adjustment of the shrinkage ratio by the component causes a problem of linkage, and the adjustment is troublesome.
In the prior art, the transition layer between different zirconia layers is arranged, so that the shrinkage performance difference is minimized, the zirconia layer with larger yttrium content difference has limited adjustment degree, and the adjustment method cannot be applied to the adjustment of the shrinkage consistency of the zirconia layer with larger yttrium content difference, and limits the gradual change range of the light transmittance.
There is a need in the art to develop a method for adjusting zirconia powders with different yttrium contents to have approximately the same shrinkage rate, which can enable the zirconia powders with different yttrium contents to have approximately the same shrinkage behavior during sintering, and has small deformation after sintering and is not easy to crack.
CN107108373A (2014) provides a zirconia sintered body in which occurrence of defects is suppressed and transparency is changed, wherein the sintered body contains 4 to 7 mol% of yttria as a stabilizer and a light-shielding material, and the light-shielding material is at least one selected from the group consisting of composite oxides of silica, alumina, titania, zirconium, and silicon. The content of the light-shielding material in the second region of the zirconia sintered body is higher than that in the first region, and the difference in the content of yttria between the two regions is 1 mol% or less.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a zirconia compact comprising at least two zirconia powder layers, wherein the different zirconia powder layers have different yttrium contents, and wherein the different zirconia powder layers have a TMA curve shrinkage onset temperature difference of 5 ℃ (e.g., 4 ℃, 3 ℃, 2 ℃, 1 ℃, etc.); the different zirconia powder layers have TMA curve shrinkage deviation less than or equal to 0.3% (e.g., 0.2%, 0.1%, etc.).
Tma (thermomechanical analysis), the name of chinese, is thermomechanical analysis, which refers to a method of measuring the relationship between deformation and temperature of a material at a programmed temperature. The zirconia compact provided by the invention has a plurality of zirconia powder layers, and each zirconia powder layer obtains different light transmittances after sintering by adjusting different yttrium contents, so that the gradual change of the light transmittance is realized. In the prior art, the shrinkage behaviors of zirconia powder with different yttrium contents are mostly inconsistent, and the problems of deformation, cracking and the like are caused in the subsequent sintering process. The zirconia powder provided by the invention has a multilayer structure, and each zirconia powder layer has different yttrium content, but the shrinkage behaviors can be kept approximately the same, and the problems of deformation, cracking and the like in the sintering process can be solved.
Preferably, the difference between the yttrium contents of different zirconia powder layers in the zirconia compact is greater than 1 mol% (e.g. 1.2 mol%, 2 mol%, 3mol%, 4mol%, 5mol%, 6 mol%, etc.), preferably 1-5 mol%.
It should be noted that, in the zirconia compact, the maximum difference of the yttrium contents of different zirconia powder layers > 1 mol% means: the zirconia compact provided by the invention has at least two zirconia powder layers, and the maximum difference value is more than 1 mol% in the set of all the differences of the yttrium contents of the zirconia powder layers. The difference is the difference in yttrium content of the optional zirconia powder layers of different layers.
Preferably, the yttrium content of the zirconia powder layer increases from bottom to top.
The larger the yttrium content is, the better the light transmission is, and the multilayer zirconia powder cake with the sequentially increased yttrium content from bottom to top has gradually changed light transmission in appearance and is close to natural teeth.
Preferably, the zirconia powder body comprises 3 zirconia powder body layers, wherein the yttrium content is 2.6-3.4 mol%, 3.6-4.4 mol% and 4.6-5.4 mol% in sequence; it is further preferable that the yttrium content of the 3-layer zirconia powder layer is 3mol%, 4mol%, and 5mol% in this order.
Another object of the present invention is to provide a method for preparing zirconia pressed powder, comprising the following steps:
(1) mixing a zirconium source, an yttrium source and other functional element sources in a liquid phase, and carrying out hydrothermal synthesis; calcining and heat treating the product of liquid phase thermal synthesis to obtain zirconium oxide powder with different yttrium contents;
according to the yttrium content in the raw materials of the zirconia powder, selecting the hydrothermal synthesis temperature and the calcining heat treatment temperature in the preparation process of the zirconia powder according to the following formula:
ΔThydrothermal synthesis＝-k1ΔXYttrium saltFormula (I)
ΔTCalcination Heat treatment＝k2ΔXYttrium saltFormula (II)
Wherein, Delta THydrothermal synthesisThe difference value of the hydrothermal synthesis temperature in the preparation process of any two groups of zirconium oxide powder raw materials is calculated, and the unit is; delta TCalcination Heat treatmentThe difference value of the calcining heat treatment temperature in the preparation process of any two groups of zirconium oxide powder raw materials is measured in unit; Δ XYttrium saltThe difference value of the molar contents of yttrium in any two groups of zirconia powder raw materials is expressed in mol%; k is a radical of1The coefficient of hydrothermal synthesis is 8.3-8.7 (such as 8.4, 8.5, 8.6 and the like); k is a radical of2A coefficient of calcination heat treatment of 16.6 to 17.0 (e.g., 16.7, 16.8, 16.9, etc.);
(3) and stacking the zirconia powder with the yttrium content according to a preset sequence, and then carrying out dry pressing to obtain the zirconia powder cake.
In the prior art, the smaller the difference of yttrium content is, the easier the adjustment of shrinkage behavior is; when the difference in the yttrium content is 1 mol% or more, the adjustment of the shrinkage behavior becomes difficult. In the preparation method of the zirconium oxide powder cake provided by the invention, the shrinkage behavior is adjusted by adjusting the hydrothermal synthesis temperature and the calcining heat treatment temperature. As shown in the formula (I) and the formula (II), according to the difference of the yttrium content, the adjusting temperature of the hydrothermal synthesis temperature and the adjusting temperature of the calcination heat treatment can be obtained.
Preferably, the dry pressure is 5 to 100MPa (e.g., 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa, 100MPa, etc.) for 5 to 30s (e.g., 5s, 10s, 15s, 20s, 25s, etc.).
In the preparation method of the zirconia compact, the addition amount of other functional elements is more than or equal to 0, and 0 means that other functional elements are not added. The other functional element means other element compounds than the zirconium compound and the yttrium compound, and the selection of the other element compounds is not particularly limited and can be selected by those skilled in the art as needed. For example, the other functional element may be an element having a coloring function, such as iron, manganese, erbium, neodymium, praseodymium, cerium, aluminum, or the like.
Preferably, the other functional elements include any one or a combination of at least two of iron, manganese, erbium, neodymium, praseodymium, cerium, aluminum, and the like.
Preferably, the zirconia compact includes the zirconia compact of one of the purposes.
Preferably, the hydrothermal synthesis specifically comprises the following steps:
(2a) mixing a zirconium source, an yttrium source and other functional elements, dissolving in water, and adjusting the pH to 8-10 (8.5, 9.0, 9.5 and the like);
(2b) heating the reaction system for hydro-thermal synthesis;
(2c) and calcining and heat treating the hydrothermal synthesis product, grinding, dispersing and granulating to obtain the zirconium oxide powder.
Preferably, the zirconium source comprises a water soluble zirconium salt, preferably any one of zirconium nitrate, zirconium oxychloride, zirconium chloride or a combination of at least two thereof.
Combinations of at least two of the zirconium sources illustratively can include combinations of zirconium nitrate and zirconium oxychloride, zirconium nitrate and zirconium chloride, zirconium nitrate and zirconium oxychloride and zirconium chloride, and the like.
Preferably, the source of yttrium comprises a salt of yttrium, preferably yttrium nitrate.
Preferably, the pH adjustment is performed by adding ammonia.
Preferably, the hydrothermal synthesis temperature is 140-200 ℃ (e.g., 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃) and the time is 10-72 hours (e.g., 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, 60 hours, 70 hours and the like), and the hydrothermal synthesis temperature is preferably 140-170 ℃ and the time is 10-50 hours.
Preferably, the calcination heat treatment temperature is 800-1100 ℃ (such as 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, and the like), and the time is 1-5 h, preferably 900-1100 ℃, and the time is 2-4 h.
Preferably, alumina powder is added in the grinding process of the step (2 c).
Preferably, the hydrothermal synthesis product of step (2c) is washed and dried before being subjected to calcination heat treatment.
It is a further object of the present invention to provide a use of the zirconia compact according to one of the objects as a dental compact for processing a denture, a biscuit for processing a back plate, or a biscuit for processing a decoration.
The zirconia compact provided by the invention can be used as a baking block to obtain a denture after sintering, or a backboard of an electronic product, or used as an ornament (such as a bracelet, a necklace and the like). The zirconia compact provided by the invention has gradually changed light transmittance.
It is a fourth object of the present invention to provide a layered zirconia-based sintered body having at least two zirconia sintered layers, the zirconia sintered layers having different yttrium contents, and the zirconia sintered body having a deformation amount of 0.3% or less (e.g., 0.25%, 0.20%, 0.15%, 0.10%, etc.).
The deformation amount of the zirconia sintered body means a layered sample piece having a length of 100mm and a thickness of 10mm, and the ratio Δ d/d of the amount of end portion shift Δ d to the thickness d after sintering.
In the prior art, different zirconia sintering layers have different yttrium contents, and the shrinkage rate difference of each layer in the sintering process is large, so that the deformation is large. The deformation of the layered zirconia-based sintered body is less than or equal to 0.3%, so that the layered zirconia-based sintered body has good shape and size controllability, and is not easy to generate the problems of shape distortion, strength reduction, cracks, fracture and the like.
Preferably, the maximum difference in yttrium content of the different zirconia sintered layers is > 1 mol% (2 mol%, 3mol%, 4mol%, etc.), preferably 1-5 mol%.
Preferably, the layered zirconia-based sintered body includes at least a zirconia sintered layer with a yttrium content of 3mol%, a zirconia sintered layer with a yttrium content of 4mol%, and a zirconia sintered layer with a yttrium content of 5mol%, and the amount of deformation of the zirconia sintered body is 0.3% or less.
The fifth object of the present invention is to provide a method for producing a layered zirconia-based sintered body according to the fourth object, the method comprising sintering the zirconia compact according to the first object to obtain a layered zirconia-based sintered body.
Preferably, the sintering temperature is 1400-1550 ℃, such as 1450 ℃, 1500 ℃ and the like, and the time is 1-3 h, such as 1.5h, 2.0h, 2.5h and the like.
The sixth object of the present invention is to provide a use of the layered zirconia-based sintered body according to the fourth object for producing a denture, a back sheet or a decoration.
A seventh object of the present invention is to provide a denture comprising the layered zirconia-based sintered body according to the fourth object;
or, the denture comprises a product prepared by the preparation method of the layered zirconia-based sintered body of the fifth aim;
alternatively, the denture is obtained by sintering the zirconia compact according to one of the purposes;
or the false tooth is obtained by sintering the zirconia compact prepared by the preparation method of the second aim.
For the sintering of zirconia compact, the shrinkage behavior can be classified into a shrinkage onset temperature and a shrinkage rate. The shrinkage starting temperature and the shrinkage rate were adjusted to be approximately the same, and it was considered that the shrinkage behavior of the zirconia compact was approximately the same.
An eighth object of the present invention is to provide a method for adjusting the initial shrinkage temperature of a zirconia sintered body, the method comprising the steps of:
(1) obtaining the hydrothermal synthesis temperature according to the formula (III) according to the predetermined yttrium content of the zirconia powder and the predetermined shrinkage starting temperature:
Thydrothermal synthesis＝k1XYttrium salt-TOnset of shrinkage+859 type (III)
Wherein, THydrothermal synthesisThe hydrothermal synthesis temperature in the preparation process of the zirconium oxide powder is the unit; xYttrium saltThe yttrium content of the zirconium oxide powder is preset, and the unit is mol%; t isOnset of shrinkageA predetermined shrinkage onset temperature in units of; k is a radical of1The coefficient of hydrothermal synthesis is 8.3-8.7;
(2) mixing a source of zirconium, a source of yttrium and a source of other functional elements in a liquid phase at THydrothermal synthesisCarrying out hydro-thermal synthesis at the temperature; and calcining and heat treating the product of the hydrothermal synthesis to obtain the zirconium oxide powder with a preset shrinkage starting temperature.
The other functional elements are understood as described above, for example, the addition amount of the other functional elements is not less than 0, and 0 means that no other functional elements are added. The other functional element means other element compounds than the zirconium compound and the yttrium compound, and the selection of the other element compounds is not particularly limited and can be selected by those skilled in the art as needed. For example, the other functional element may be an element having a coloring function, such as iron, manganese, or the like; erbium, neodymium, praseodymium, cerium, aluminum, etc. may be used.
The ninth purpose of the present invention is to provide a method for adjusting shrinkage of a zirconia sintered body, comprising the steps of:
(1) obtaining a calcination heat treatment temperature according to formula (IV) according to a predetermined yttrium content of the zirconia powder, a predetermined shrinkage rate, and a liquid phase thermal synthesis temperature:
Tcalcination Heat treatment＝(σ-0.0002608Y+0.0001168THydrothermal synthesis-0.2899)/0.00007426 formula (IV)
Wherein, THydrothermal synthesisThe hydrothermal synthesis temperature in the preparation process of the zirconium oxide powder is the unit; xYttrium saltThe yttrium content of the zirconium oxide powder is preset, and the unit is mol%; t isCalcination Heat treatmentThe calcining heat treatment temperature in the preparation process of the zirconium oxide powder is the unit; σ is shrinkage,%;
(2) mixing a zirconium source, an yttrium source and other additive element sources in a liquid phase at THydrothermal synthesisCarrying out hydro-thermal synthesis at the temperature; the product of the hydrothermal synthesis is at TCalcination Heat treatmentAnd carrying out calcination heat treatment at the temperature to obtain the zirconium oxide powder with the preset shrinkage starting temperature.
The other functional elements are understood as described above, for example, the addition amount of the other functional elements is not less than 0, and 0 means that no other functional elements are added. The other functional element means other element compounds than the zirconium compound and the yttrium compound, and the selection of the other element compounds is not particularly limited and can be selected by those skilled in the art as needed. For example, the other functional element may be an element having a coloring function, such as iron, manganese, or the like; erbium, neodymium, praseodymium, cerium, aluminum, etc. may be used.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a zirconia compact, a preparation method and application thereof, wherein different zirconia powder layers of the zirconia compact have different yttrium contents and still have approximately consistent shrinkage behaviors (the TMA curve shrinkage starting temperature difference is less than or equal to 5 ℃, and the TMA curve shrinkage rate deviation of the different zirconia powder layers is less than or equal to 0.3%), so that higher deformation stability is provided for a subsequent sintering process, and the defects of shape distortion, strength reduction, cracks, cracking and the like caused by inconsistent shrinkage behaviors are effectively avoided.
(2) The invention provides a layered zirconia-based sintered body, a preparation method and application thereof, wherein different light transmittances are obtained by selecting different yttrium contents of different zirconia sintered layers, and the layered zirconia-based sintered body with gradually changed light transmittances is obtained by selecting the arrangement sequence of the zirconia sintered layers with different light transmittances. The layered zirconia-based sintered body has a light transmittance that gradually changes, and thus can be used as a denture with a feeling closer to that of a natural tooth.
(3) The invention also provides a regulating method of the shrinkage behavior of the zirconia sintered body, which comprises a regulating method of the initial shrinkage temperature and the shrinkage rate, wherein the regulating method regulates the hydrothermal synthesis temperature and the calcination heat treatment temperature according to the regulating formula (I) and/or formula (II)) according to different yttrium contents, so that the purpose of controllably regulating the shrinkage behavior is realized.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of a plurality of groups of zirconia powders (A1, A2 and A3) with different yttrium contents is provided, wherein the A1 yttrium content of the zirconia powder is 3mol percent, the A2 yttrium content of the zirconia powder is 4mol percent, and the A3 yttrium content of the zirconia powder is 5mol percent, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder A1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 97:6, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder A1 (the yttrium content is 3 mol%);
(2) the preparation method of the zirconia powder A2 specifically comprises the following steps: (2a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe temperature of the hydrothermal synthesis of the zirconia powder A2 is 160-8.5 ℃ ═ 151.5 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × 1 ═ 16.8 ℃, that is, the calcination heat treatment temperature of the zirconia powder a2 is 950 ℃ +16.8 ℃ ═ 966.8 ℃; (2b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96:8, dissolving in water, and adjusting the pH value to 8-10; (2c) heating the reaction system to 151.5 DEG CCarrying out hydro-thermal synthesis; (2d) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 966.8 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder A2 (the content of yttrium is 4 mol%);
(3) the preparation method of the zirconia powder A3 specifically comprises the following steps: (3a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder A3 is 160-17 ℃ and 143 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × 2 ═ 33.6 ℃, that is, the calcination heat treatment temperature of the zirconia powder a3 is 950 ℃ +33.6 ℃ ═ 983.6 ℃; (3b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 95:10, dissolving in water, and adjusting the pH value to 8-10; (3c) heating the reaction system to 143 ℃ for hydro-thermal synthesis; (3d) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 983.6 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder A3 (the yttrium content is 5 mol%);
(4) stacking zirconia powder A1, zirconia powder A2 and zirconia powder A3 in the order from bottom to top, and then performing dry pressing at 20MPa to obtain zirconia powder cake X1.
Comparative example 1
The preparation method of a plurality of groups of zirconia powders (A1, A '2 and A' 3) with different yttrium contents is provided, the A1 yttrium content of the zirconia powder is 3mol%, the A '2 yttrium content of the zirconia powder is 4mol%, and the A' 3 yttrium content of the zirconia powder is 5mol%, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder A1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 97:6, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder A1 (the yttrium content is 3 mol%);
(2) the preparation method of the zirconia powder A' 2 specifically comprises the following steps: (2a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96:8, dissolving in water, and adjusting the pH value to 8-10; (2b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (2c) after washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder A' 2 (the yttrium content is 4 mol%);
(3) the preparation method of the zirconia powder A' 3 specifically comprises the following steps: (3a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 95:10, dissolving in water, and adjusting the pH value to 8-10; (3b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (3c) after washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder A' 3 (the yttrium content is 5 mol%);
(4) stacking the zirconia powder A '1, the zirconia powder A' 2 and the zirconia powder A '3 in sequence from bottom to top, and then carrying out dry pressing for 20MPa to obtain a zirconia powder cake X' 1.
And (3) performance testing:
(1) performing dry pressing on zirconium oxide powder A1, zirconium oxide powder A2, zirconium oxide powder A3, zirconium oxide powder A '2 and zirconium oxide powder A' 3 at 20MPa, performing isostatic pressing at 200MPa for 30s to obtain a green blank sample block, performing biscuit firing on the green blank sample block at 900 ℃ to obtain a test sample block, testing the test sample block by using TMA, and heating to 1600 ℃ at a heating rate of 1 ℃/min under an air atmosphere to obtain an initial shrinkage temperature and a shrinkage rate;
the three-point bending strength test method comprises the following steps: the biscuit firing sample block is cut, ground and sintered for 1h at 1500 ℃ to obtain sample strips of 4.0 multiplied by 1.0 multiplied by 20mm, after the surfaces of the sample strips are polished, the three-point bending strength is tested, the span is 16mm, the testing speed is 0.5mm/min, 10 sample strips are tested for each sample, and the average value is taken.
The permeability test method comprises the following steps: the biscuit firing sample block is cut, polished and sintered at 1500 ℃ for 1h to obtain a sample wafer with the thickness of 1.0mm, and after double-side polishing, a spectrophotometer is used for testing light transmittance data at the wavelength of 500 nm.
The test results are shown in table 1:
TABLE 1
Serial number A1 A2 A3 A’2 A’3
Shrinkage onset temperature/. degree.C 1043 1047 1045 1057 1064
Shrinkage ratio/% 20.14 20.13 20.13 20.18 20.23
strength/MPa 1205 868 563 886 547
Permeability/% 43.53 46.18 49.53 46.26 49.41
(2) Sintering zirconia powder cakes X1 and X' 1 at 1500 ℃ for 1h, monitoring deformation, wherein the test method comprises the steps of placing a sample block on a horizontal workbench, pressing one end of the sample block downwards to be seamless with the workbench, measuring the size delta d of the gap between the other end of the sample block and the workbench by using a feeler gauge, measuring the thickness d of a sample strip by using a caliper gauge, and calculating to obtain deformation data delta d/d, wherein the test results are shown in a table 2;
TABLE 2
Figure BDA0002110775540000131
Figure BDA0002110775540000141
As can be seen from tables 1 and 2, after the hydrothermal synthesis temperature and the calcination temperature are adjusted, the shrinkage rates (all between 20.13% and 20.14%) and the shrinkage initiation temperatures (all between 1043 ℃ and 1047 ℃) of different powders tend to be consistent, the strength and the permeability are not obviously affected, and the sintering deformation of the pressed powder is obviously reduced.
Example 2
The preparation method of multiple groups of zirconia powders (B1, B2 and B3) with different yttrium contents is provided, wherein the yttrium content of the zirconia powder B1 is 5mol percent, the yttrium content of the zirconia powder B2 is 4mol percent, and the yttrium content of the zirconia powder B3 is 3mol percent, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder B1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 95:10, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder B1 (the yttrium content is 5 mol%);
(2) the preparation method of the zirconia powder B2 specifically comprises the following steps: (2a) according to formula (I)) Calculating the hydrothermal synthesis temperature: delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder B2 is 160 ℃ +8.5 ℃ ═ 168.5 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × (-1) — 16.8 ℃, that is, the calcination heat treatment temperature of the zirconia powder B2 is 950 ℃ to 16.8 ℃ — (933.2 ℃; (2b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96:8, dissolving in water, and adjusting the pH value to 8-10; (2c) heating the reaction system to 168.5 ℃ for hydro-thermal synthesis; (2d) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 933.2 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder B2 (the content of yttrium is 4 mol%);
(3) the preparation method of the zirconia powder B3 specifically comprises the following steps: (3a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder B3 is 160 ℃ and 177 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × (-2) — 33.6 ℃, that is, the calcination heat treatment temperature of the zirconia powder B3 is 950 ℃ to 33.6 ℃ to 916.4 ℃; (3b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 97:6, dissolving in water, and adjusting the pH value to 8-10; (3c) heating the reaction system to 177 ℃ for hydro-thermal synthesis; (3d) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 914.6 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder B3 (the yttrium content is 3 mol%);
(4) stacking zirconia powder B3, zirconia powder B2 and zirconia powder B1 in the order from bottom to top, and then performing dry pressing at 20MPa to obtain zirconia powder cake X2.
Comparative example 2
The preparation method of a plurality of groups of zirconia powders (B1, B '2 and B' 3) with different yttrium contents is provided, the yttrium content of the zirconia powder B1 is 5mol%, the yttrium content of the zirconia powder B '2 is 4mol%, and the yttrium content of the zirconia powder B' 3 is 3mol%, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder B1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 95:10, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying a hydrothermal synthesis product, calcining and heat treating the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder B1 (the yttrium content is 5 mol%);
(2) the preparation method of the zirconia powder B' 2 specifically comprises the following steps: (2a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96:8, dissolving in water, and adjusting the pH value to 8-10; (2b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (2c) after washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder B' 2 (the yttrium content is 4 mol%);
(3) the preparation method of the zirconia powder B' 3 specifically comprises the following steps: (3a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 97:6, dissolving in water, and adjusting the pH value to 8-10; (3b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (3c) after washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder B' 3 (the yttrium content is 3 mol%);
(4) stacking the zirconia powder B3, the zirconia powder B ' 2 and the zirconia powder B ' 1 in the order from bottom to top, and then carrying out dry pressing for 20MPa to obtain a zirconia powder cake X ' 2.
And (3) performance testing:
(1) performing dry pressing on zirconium oxide powder B1, zirconium oxide powder B2, zirconium oxide powder B3, zirconium oxide powder B '2 and zirconium oxide powder B' 3 at 20MPa, performing isostatic pressing at 200MPa for 30s to obtain a green blank sample block, performing biscuit firing on the green blank sample block at 900 ℃ to obtain a test sample block, testing the test sample block by using TMA, and heating to 1600 ℃ at a heating rate of 1 ℃/min under an air atmosphere to obtain an initial shrinkage temperature and a shrinkage rate;
the three-point bending strength test method comprises the following steps: the biscuit firing sample block is cut, ground and sintered for 1h at 1500 ℃ to obtain sample strips of 4.0 multiplied by 1.0 multiplied by 20mm, after the surfaces of the sample strips are polished, the three-point bending strength is tested, the span is 16mm, the testing speed is 0.5mm/min, 10 sample strips are tested for each sample, and the average value is taken.
The permeability test method comprises the following steps: the biscuit firing sample block is cut, polished and sintered at 1500 ℃ for 1h to obtain a sample wafer with the thickness of 1.0mm, and after double-side polishing, a spectrophotometer is used for testing light transmittance data at the wavelength of 500 nm.
The test results are shown in table 3:
TABLE 3
Serial number B1 B2 B3 B’2 B’3
Shrinkage onset temperature/. degree.C 1062 1060 1061 1053 1043
Shrinkage ratio/% 20.20 20.20 20.21 20.16 20.10
strength/MPa 547 893 1235 886 1205
Permeability/% 547 46.38 43.36 46.26 43.53
(2) Sintering zirconia pressed powders X2 and X' 2 at 1500 ℃ for 1h, monitoring the deformation quantity, wherein the test method comprises the steps of placing a sample block on a horizontal workbench, pressing one end of the sample block downwards to be seamless with the workbench, measuring the size delta d of the gap between the other end of the sample block and the workbench by using a feeler gauge, measuring the thickness d of a sample strip by using a caliper gauge, and calculating to obtain deformation data delta d/d, wherein the test results are shown in a table 4:
TABLE 4
Serial number Zirconia pressed powder X2 Zirconia pressed powder X' 2
Amount of deformation/%) 0.19 1.43
As can be seen from tables 3 and 4, after the hydrothermal synthesis temperature and the calcination temperature are adjusted, the shrinkage temperature (1060-1062 ℃) and the shrinkage rate (20.20-20.21%) of the powder are consistent, the strength and the permeability are not obviously affected, and the sintering deformation of the pressed powder is obviously reduced.
Example 3
The preparation method of multiple groups of zirconia powders (C1, C2 and C3) with different yttrium contents is provided, wherein the C1 yttrium content of the zirconia powder is 4mol percent, the C2 yttrium content of the zirconia powder is 6mol percent, and the C3 yttrium content of the zirconia powder is 2mol percent, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder C1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96:8, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder C1;
(2) the preparation method of the zirconia powder C2 specifically comprises the following steps: (2a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder C2 is 160-17 ℃ and 143 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × 2 ═ 33.6 ℃, that is, the calcination heat treatment temperature of the zirconia powder C2 is 950 ℃ +33.6 ℃ ═ 983.6 ℃; (2b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 94:12, dissolving in water, and adjusting the pH value to 8-10; (2c) heating the reaction system to 143 ℃ for hydro-thermal synthesis; (2d) washing and drying the hydrothermal synthesis product, calcining the powder at 983.6 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder C2;
(3) the preparation method of the zirconia powder C3 specifically comprises the following steps: (3a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder C3 is 160 ℃ and 177 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × (-2) — 33.6 ℃, namely the calcining heat treatment temperature of the zirconia powder C3 is 950 ℃ -33.6 ℃, — (916.4 ℃); (3b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 98:4, dissolving in water, and adjusting the pH value to 8-10; (3c) heating the reaction system to 177 ℃ for hydro-thermal synthesis; (3d) after the hydrothermal synthesis product is washed and dried, the powder is at 914.6 DEG CAfter calcining and heat treatment, grinding, dispersing and granulating to obtain zirconium oxide powder C3;
(4) stacking zirconia powder C3, zirconia powder C1 and zirconia powder C2 in the order from bottom to top, and then performing dry pressing at 20MPa to obtain zirconia powder cake X3.
Comparative example 3
The preparation method of a plurality of groups of zirconia powders (C1, C '2 and C' 3) with different yttrium contents is provided, wherein the yttrium content of the zirconia powder C1 is 4mol%, the yttrium content of the zirconia powder C '2 is 6 mol%, and the yttrium content of the zirconia powder C' 3 is 2 mol%, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder C1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96:8, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder C1;
(2) the preparation method of the zirconia powder C' 2 specifically comprises the following steps: (2a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 94:12, dissolving in water, and adjusting the pH value to 8-10; (2b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (2c) washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder C' 2;
(3) the preparation method of the zirconia powder C' 3 specifically comprises the following steps: (3a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 98:4, dissolving in water, and adjusting the pH value to 8-10; (3b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (3c) washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder C' 3;
(4) stacking the zirconia powder C ' 3, the zirconia powder C1 and the zirconia powder C ' 2 in the order from bottom to top, and then carrying out dry pressing for 20MPa to obtain a zirconia powder cake X ' 3.
And (3) performance testing:
(1) performing dry pressing on zirconium oxide powder C1, zirconium oxide powder C2, zirconium oxide powder C3, zirconium oxide powder C '2 and zirconium oxide powder C' 3 at 20MPa, performing isostatic pressing at 200MPa for 30s to obtain a green blank sample block, performing biscuit firing on the green blank sample block at 900 ℃ to obtain a test sample block, testing the test sample block by using TMA, and heating to 1600 ℃ at a heating rate of 1 ℃/min under an air atmosphere to obtain an initial shrinkage temperature and a shrinkage rate;
the three-point bending strength test method comprises the following steps: the biscuit firing sample block is cut, ground and sintered for 1h at 1500 ℃ to obtain sample strips of 4.0 multiplied by 1.0 multiplied by 20mm, after the surfaces of the sample strips are polished, the three-point bending strength is tested, the span is 16mm, the testing speed is 0.5mm/min, 10 sample strips are tested for each sample, and the average value is taken.
The permeability test method comprises the following steps: the biscuit firing sample block is cut, polished and sintered at 1500 ℃ for 1h to obtain a sample wafer with the thickness of 1.0mm, and after double-side polishing, a spectrophotometer is used for testing light transmittance data at the wavelength of 500 nm.
The test results are shown in table 5:
TABLE 5
Serial number C1 C2 C3 C’2 C’3
Shrinkage onset temperature/. degree.C 1053 1053 1054 1036 1070
Shrinkage ratio/% 20.17 20.17 20.19 20.12 20.22
strength/MPa 886 487 1308 492 1294
Permeability/% 46.26 49.09 32.56 49.05 32.60
(2) Sintering zirconia pressed powders X3 and X' 3 at 1500 ℃ for 1h, monitoring the deformation quantity, wherein the test method comprises the steps of placing a sample block on a horizontal workbench, pressing one end of the sample block downwards to be seamless with the workbench, measuring the size delta d of the gap between the other end of the sample block and the workbench by using a feeler gauge, measuring the thickness d of a sample strip by using a caliper gauge, and calculating to obtain deformation data delta d/d, wherein the test results are shown in Table 6:
TABLE 6
Serial number Zirconia pressed powder X3 Zirconia pressed powder X' 3
Amount of deformation/%) 0.28 1.62
As can be seen from tables 5 and 6, after the hydrothermal synthesis temperature and the calcination temperature are adjusted, the shrinkage rate (both 20.17-20.19%) and the shrinkage temperature (1053-1054 ℃) of the powder are consistent, the strength and the permeability are not obviously affected, and the sintering deformation of the pressed powder is obviously reduced.
Example 4
The preparation method of multiple groups of zirconia powders (D1, D2 and D3) with different yttrium contents is provided, wherein the D1 yttrium content of the zirconia powder is 2.6 mol%, the D2 yttrium content of the zirconia powder is 4.4mol%, and the D3 yttrium content of the zirconia powder is 4.6 mol%, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder D1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 97.4:5.2, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder D1;
(2) the preparation method of the zirconia powder D2 specifically comprises the following steps: (2a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder D2 is 160-15.3 ℃ ═ 144.7 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × 1.8 ═ 30.24 ℃, that is, the calcination heat treatment temperature of the zirconia powder D2 is 950 ℃ +30.24 ℃ ═ 980.24 ℃; (2b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 95.6:8.8, dissolving in water, and adjusting the pH value to 8-10; (2c) heating the reaction system to 144.7 DEG CCarrying out hydro-thermal synthesis; (2d) washing and drying the hydrothermal synthesis product, calcining the powder at 980.24 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder D2;
(3) the preparation method of the zirconia powder D3 specifically comprises the following steps: (3a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder B3 is 160-17 ℃ and 143 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × 2 ═ 33.6 ℃, that is, the calcination heat treatment temperature of the zirconia powder B3 was 950 ℃ +33.6 ℃ ═ 983.6 ℃; (3b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 95.4:9.2, dissolving in water, and adjusting the pH value to 8-10; (3c) heating the reaction system to 143 ℃ for hydro-thermal synthesis; (3d) washing and drying the hydrothermal synthesis product, calcining the powder at 983.6 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder D3;
(4) stacking zirconia powder D1, zirconia powder D2 and zirconia powder D3 in sequence from bottom to top, and then performing dry pressing under 20MPa to obtain a zirconia powder cake X4;
(5) sintering zirconia powder cake X4 at 1400 ℃ for 1h, and monitoring the deformation amount thereof, wherein the test method comprises the steps of placing a sample block on a horizontal workbench, pressing one end of the sample block downwards to form no gap with the workbench, measuring the size delta d of the gap between the other end of the sample block and the workbench by using a feeler gauge, measuring the thickness d of the sample strip by using a caliper gauge, and calculating to obtain deformation data delta d/d of 0.25.
And (3) performance testing:
(1) performing dry pressing on zirconium oxide powder D1, zirconium oxide powder D2 and zirconium oxide powder D3 at 20MPa for forming, performing isostatic pressing at 200MPa for 30s to obtain a green blank sample block, performing biscuit firing on the green blank sample block at 900 ℃ to obtain a test sample block, testing the test sample block by using TMA, and heating to 1600 ℃ at a heating rate of 1 ℃/min under an air atmosphere to obtain an initial shrinkage temperature and a shrinkage rate;
the three-point bending strength test method comprises the following steps: the biscuit firing sample block is cut, ground and sintered for 1h at 1500 ℃ to obtain sample strips of 4.0 multiplied by 1.0 multiplied by 20mm, after the surfaces of the sample strips are polished, the three-point bending strength is tested, the span is 16mm, the testing speed is 0.5mm/min, 10 sample strips are tested for each sample, and the average value is taken.
The permeability test method comprises the following steps: the biscuit firing sample block is cut, polished and sintered at 1500 ℃ for 1h to obtain a sample wafer with the thickness of 1.0mm, and after double-side polishing, a spectrophotometer is used for testing light transmittance data at the wavelength of 500 nm.
The test results are shown in table 7:
TABLE 7
Serial number D1 D2 D3
Shrinkage onset temperature/. degree.C 1041 1041 1040
Shrinkage ratio/% 20.13 20.14 20.14
strength/MPa 1315 887 853
Permeability/% 37.85 46.26 47.31
(2) As can be seen from the performance test results, after the hydrothermal synthesis temperature and the calcination temperature are adjusted, the shrinkage rate (both 20.13-20.14%) and the initial shrinkage temperature (1040-.
Example 5
The preparation method of a plurality of groups of zirconia powders (E1, E2 and E3) with different yttrium contents is provided, wherein the yttrium content of the zirconia powder E1 is 3.4mol percent, the yttrium content of the zirconia powder E2 is 3.6mol percent, and the yttrium content of the zirconia powder E3 is 5.4mol percent, and the preparation method comprises the following steps:
(1) the preparation method of the zirconia powder E1 specifically comprises the following steps: (1a) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96.6:6.8, dissolving in water, and adjusting the pH value to 8-10; (1b) heating the reaction system to 160 ℃ for hydro-thermal synthesis; (1c) washing and drying the hydrothermal synthesis product, calcining the powder at 950 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder E1;
(2) the preparation method of the zirconia powder E2 specifically comprises the following steps: (2a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder E2 is 160-1.7 ℃ ═ 158.3 ℃; calculating the calcination heat treatment temperature according to formula (II): delta TCalcination Heat treatment16.8 × 0.2 ═ 3.36 ℃, that is, the calcination heat treatment temperature of the zirconia powder E2 is 950 ℃ +3.36 ℃ ═ 953.6 ℃; (2b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 96.4:7.2, dissolving in water, and adjusting the pH value to 8-10; (2c) heating the reaction system to 158.3 ℃ for hydro-thermal synthesis; (2d) washing and drying the hydrothermal synthesis product, calcining the powder at 953.6 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder E2;
(3) the preparation method of the zirconia powder E3 specifically comprises the following steps: (3a) calculating the hydrothermal synthesis temperature according to formula (I): delta THydrothermal synthesisThe hydrothermal synthesis temperature of the zirconia powder E3 is 160-17 ℃ and 143 ℃; calculating the calcination Heat treatment according to formula (II)Temperature: delta TCalcination Heat treatment16.8 × 2 ═ 33.6 ℃, that is, the calcination heat treatment temperature of the zirconia powder E3 was 950 ℃ +33.6 ℃ ═ 983.6 ℃; (3b) mixing zirconium nitrate and yttrium nitrate according to a molar ratio of 94.6:10.8, dissolving in water, and adjusting the pH value to 8-10; (3c) heating the reaction system to 143 ℃ for hydro-thermal synthesis; (3d) washing and drying the hydrothermal synthesis product, calcining the powder at 983.6 ℃, grinding, dispersing and granulating to obtain zirconium oxide powder E3;
(4) stacking zirconia powder E3, zirconia powder E2 and zirconia powder E1 in sequence from bottom to top, and then performing dry pressing at 20MPa to obtain a zirconia powder cake X5;
(5) sintering zirconia powder cake X5 at 1550 deg.C for 1h, monitoring its deformation amount, and measuring by placing sample block on horizontal workbench, pressing one end of the sample block without gap, measuring gap Δ d between the other end of the sample block and the workbench by feeler gauge, measuring sample strip thickness d by caliper gauge, and calculating to obtain deformation amount data Δ d/d of 0.21.
And (3) performance testing:
(1) performing dry pressing on zirconium oxide powder E1, zirconium oxide powder E2 and zirconium oxide powder E3 at 20MPa for forming, performing isostatic pressing at 200MPa for 30s to obtain a green blank sample block, performing biscuit firing on the green blank sample block at 900 ℃ to obtain a test sample block, testing the test sample block by using TMA, and heating to 1600 ℃ at a heating rate of 1 ℃/min under an air atmosphere to obtain an initial shrinkage temperature and a shrinkage rate;
the three-point bending strength test method comprises the following steps: the biscuit firing sample block is cut, ground and sintered for 1h at 1500 ℃ to obtain sample strips of 4.0 multiplied by 1.0 multiplied by 20mm, after the surfaces of the sample strips are polished, the three-point bending strength is tested, the span is 16mm, the testing speed is 0.5mm/min, 10 sample strips are tested for each sample, and the average value is taken.
The permeability test method comprises the following steps: the biscuit firing sample block is cut, polished and sintered at 1500 ℃ for 1h to obtain a sample wafer with the thickness of 1.0mm, and after double-side polishing, a spectrophotometer is used for testing light transmittance data at the wavelength of 500 nm.
The test results are shown in table 7:
TABLE 7
Serial number E1 E2 E3
Shrinkage onset temperature/. degree.C 1048 1047 1048
Shrinkage ratio/% 20.16 20.15 20.16
strength/MPa 1132 1028 532
The performance test results show that after the hydrothermal synthesis temperature and the calcination temperature are adjusted, the shrinkage rate (both 20.15-20.16%) and the shrinkage temperature (1047-1048 ℃) of the powder are consistent, the strength and the permeability are not obviously affected, and the sintering deformation of the powder cake is obviously reduced.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (14)

1. The zirconia powder cake is characterized by comprising at least two zirconia powder layers, wherein the yttrium contents of different zirconia powder layers are different, and the difference between the shrinkage starting temperatures of TMA curves of the different zirconia powder layers is less than or equal to 5 ℃; the TMA curve shrinkage rate deviation of the different zirconia powder layers is less than or equal to 0.3 percent;
the preparation method of the zirconia pressed powder comprises the following steps:
(1) mixing a zirconium source, an yttrium source and other functional element sources in a liquid phase, and carrying out hydrothermal synthesis; calcining and heat treating the product of liquid phase thermal synthesis to obtain zirconium oxide powder with different yttrium contents;
according to the yttrium content in the raw materials of the zirconia powder, selecting the hydrothermal synthesis temperature and the calcining heat treatment temperature in the preparation process of the zirconia powder according to the following formula:
ΔThydrothermal synthesis=-k1ΔXYttrium saltFormula (I)
ΔTCalcination Heat treatment=k2ΔXYttrium saltFormula (II)
Wherein, Delta THydrothermal synthesisThe difference value of the hydrothermal synthesis temperature in the preparation process of any two groups of zirconium oxide powder raw materials is calculated, and the unit is; delta TCalcination Heat treatmentThe difference value of the calcining heat treatment temperature in the preparation process of any two groups of zirconium oxide powder raw materials is measured in unit; Δ XYttrium saltThe difference value of the molar contents of yttrium in any two groups of zirconia powder raw materials is expressed in mol%; k is a radical of1The coefficient of hydrothermal synthesis is 8.3-8.7; k is a radical of2The coefficient of the calcination heat treatment is 16.6-17.0;
(3) stacking the zirconia powder with yttrium content according to a preset sequence, and then carrying out dry pressing to obtain zirconia powder cake;
the pressure of the dry pressure is 5-100 MPa, and the time is 5-30 s;
the other functional elements comprise any one or the combination of at least two of iron, manganese, erbium, neodymium, praseodymium, cerium and aluminum.
2. The zirconia compact of claim 1, wherein the zirconia powder layer has an increasing yttrium content from bottom to top;
the zirconia powder comprises 3 zirconia powder layers, wherein the yttrium content is 2.6-3.4 mol%, 3.6-4.4 mol% and 4.6-5.4 mol% in sequence.
3. The zirconia compact of claim 2, wherein the 3-layer zirconia powder layer has a yttrium content of 3mol%, 4mol%, and 5mol%, in that order.
4. A method for preparing the zirconia compact of any of claims 1 to 3, comprising the steps of:
(1) mixing a zirconium source, an yttrium source and other functional element sources in a liquid phase, and carrying out hydrothermal synthesis; calcining and heat treating the product of liquid phase thermal synthesis to obtain zirconium oxide powder with different yttrium contents;
according to the yttrium content in the raw materials of the zirconia powder, selecting the hydrothermal synthesis temperature and the calcining heat treatment temperature in the preparation process of the zirconia powder according to the following formula:
ΔThydrothermal synthesis=-k1ΔXYttrium saltFormula (I)
ΔTCalcination Heat treatment=k2ΔXYttrium saltFormula (II)
Wherein, Delta THydrothermal synthesisThe difference value of the hydrothermal synthesis temperature in the preparation process of any two groups of zirconium oxide powder raw materials is calculated, and the unit is; delta TCalcination Heat treatmentThe difference value of the calcining heat treatment temperature in the preparation process of any two groups of zirconium oxide powder raw materials is measured in unit; Δ XYttrium saltThe difference value of the molar contents of yttrium in any two groups of zirconia powder raw materials is expressed in mol%; k is a radical of1The coefficient of hydrothermal synthesis is 8.3-8.7; k is a radical of2The coefficient of the calcination heat treatment is 16.6-17.0；
(3) Stacking the zirconia powder with yttrium content according to a preset sequence, and then carrying out dry pressing to obtain zirconia powder cake;
the pressure of the dry pressure is 5-100 MPa, and the time is 5-30 s;
the other functional elements comprise any one or the combination of at least two of iron, manganese, erbium, neodymium, praseodymium, cerium and aluminum.
5. The preparation method according to claim 4, wherein the hydrothermal synthesis comprises the following steps:
(2a) mixing a zirconium source, an yttrium source and other functional elements, dissolving in water, and adjusting the pH to 8-10;
(2b) heating the reaction system for hydro-thermal synthesis;
(2c) calcining and heat treating the hydrothermal synthesis product, grinding, dispersing and granulating to obtain zirconium oxide powder;
the zirconium source comprises a water soluble zirconium salt;
the source of yttrium comprises a salt of yttrium;
the pH value is adjusted by adding ammonia water;
the hydrothermal synthesis temperature is 140-200 ℃, and the time is 10-72 h;
the calcination heat treatment temperature is 800-1100 ℃, and the time is 1-5 h;
and (3) washing and drying the hydrothermal synthesis product in the step (2c) before calcining and heat treating.
6. The method according to claim 5, wherein the water-soluble zirconium salt is any one of zirconium nitrate, zirconium oxychloride, zirconium chloride, or a combination of at least two thereof;
the yttrium salt is yttrium nitrate;
the hydrothermal synthesis temperature is 140-170 ℃, and the time is 10-50 h;
the calcining heat treatment temperature is 900-1100 ℃, and the time is 2-4 h.
7. Use of the zirconia compact according to any one of claims 1 to 3 as a dental compact for the manufacture of dentures, a biscuit for the manufacture of back plates or a biscuit for the manufacture of ornaments.
8. A layered zirconia-based sintered body, characterized in that the layered zirconia-based sintered body has at least two zirconia sintered layers, the yttrium content of different zirconia sintered layers is different, and the deformation of the zirconia sintered body is less than or equal to 0.3%;
a method for producing a layered zirconia-based sintered body, comprising sintering the zirconia compact according to any one of claims 1 to 3.
9. The layered zirconia-based sintered body according to claim 8, wherein the layered zirconia-based sintered body comprises at least a zirconia sintered layer having a yttrium content of 3mol%, a zirconia sintered layer having a yttrium content of 4mol%, and a zirconia sintered layer having a yttrium content of 5mol%, and the amount of deformation of the zirconia sintered body is 0.3% or less.
10. A method for producing the layered zirconia-based sintered body according to any one of claims 8 to 9, comprising sintering the zirconia compact according to any one of claims 1 to 3 to obtain a layered zirconia-based sintered body;
the sintering temperature is 1400-1550 ℃, and the time is 1-3 h.
11. Use of the layered zirconia-based sintered body according to any one of claims 8 to 9 for producing a denture, a back plate or a decoration.
12. A denture comprising the layered zirconia-based sintered body according to any one of claims 8 to 9;
alternatively, the denture comprises a product produced by the method for producing a layered zirconia-based sintered body according to claim 10;
alternatively, the denture is obtained by sintering the zirconia compact according to any one of claims 1 to 3;
alternatively, the denture is obtained by sintering the zirconia compact prepared by the preparation method according to any one of claims 4 to 6.
13. A method for adjusting a shrinkage starting temperature of a zirconia sintered body, characterized by comprising the steps of:
(1) obtaining the hydrothermal synthesis temperature according to the formula (III) according to the predetermined yttrium content of the zirconia powder and the predetermined shrinkage starting temperature:
Thydrothermal synthesis=k1XYttrium salt-TOnset of shrinkage+859 type (III)
Wherein, THydrothermal synthesisThe hydrothermal synthesis temperature in the preparation process of the zirconium oxide powder is the unit; xYttrium saltThe yttrium content of the zirconium oxide powder is preset, and the unit is mol%; t isOnset of shrinkageA predetermined shrinkage onset temperature in units of; k is a radical of1The coefficient of hydrothermal synthesis is 8.3-8.7;
(2) mixing a source of zirconium, a source of yttrium and a source of other functional elements in a liquid phase at THydrothermal synthesisCarrying out hydro-thermal synthesis at the temperature; and calcining and heat treating the product of the hydrothermal synthesis to obtain the zirconium oxide powder with a preset shrinkage starting temperature.
14. A method for adjusting shrinkage rate of a zirconia sintered body, which is characterized by comprising the following steps:
(1) obtaining a calcination heat treatment temperature according to formula (IV) according to a predetermined yttrium content of the zirconia powder, a predetermined shrinkage rate, and a liquid phase thermal synthesis temperature:
Tcalcination Heat treatment=（σ-0.0002608XYttrium salt+0.0001168THydrothermal synthesis-0.2899）/0.00007426
Formula (IV)
Wherein, THydrothermal synthesisThe hydrothermal synthesis temperature in the preparation process of the zirconium oxide powder is the unit; xYttrium saltThe predetermined yttrium content of the zirconia powder is as followsmol%；TCalcination Heat treatmentThe calcining heat treatment temperature in the preparation process of the zirconium oxide powder is the unit; σ is shrinkage,%;
(2) mixing a zirconium source, an yttrium source and other additive element sources in a liquid phase at THydrothermal synthesisCarrying out hydro-thermal synthesis at the temperature; the product of the hydrothermal synthesis is at TCalcination Heat treatmentAnd carrying out calcination heat treatment at the temperature to obtain the zirconium oxide powder with the preset shrinkage starting temperature.
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