CN110342926A - The adjusting method of zirconium oxide muffin, Preparation method and use and its shrinkage - Google Patents

The adjusting method of zirconium oxide muffin, Preparation method and use and its shrinkage Download PDF

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CN110342926A
CN110342926A CN201910570635.8A CN201910570635A CN110342926A CN 110342926 A CN110342926 A CN 110342926A CN 201910570635 A CN201910570635 A CN 201910570635A CN 110342926 A CN110342926 A CN 110342926A
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zirconium
yttrium
powder
hydrothermal synthesis
temperature
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CN110342926B (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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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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    • 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
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Abstract

The present invention provides the adjusting methods of a kind of zirconium oxide muffin, Preparation method and use and its shrinkage.The zirconium oxide muffin includes at least two layers of Zirconium powder layer, and the yttrium content of different Zirconium powder layers is different, and the different Zirconium powder layers, TMA curve shrinkage initial temperature difference≤5 DEG C；The difference Zirconium powder layer, TMA curve shrinkage rate deviation≤0.3%.The present invention provides a kind of zirconium oxide muffins, Preparation method and use, there is different yttrium contents in the different Zirconium powder layers of the zirconium oxide muffin, but still there is Shrinkage behavior unanimous on the whole, to provide higher deformation stability for subsequent sintering process, effectively avoid because of the defects of deforming, cracking caused by Shrinkage behavior is inconsistent.

Description

The adjusting method of zirconium oxide muffin, Preparation method and use and its shrinkage
Technical field
The invention belongs to ceramic material field, it is related to a kind of zirconium oxide muffin, Preparation method and use and its shrinkage Adjusting method, and in particular to a kind of zirconium oxide muffin, preparation method and the usage, and prepared by the zirconium oxide muffin Obtained zirconia sintered body, Preparation method and use, and be prepared into using the zirconium oxide muffin or zirconia sintered body The artificial tooth that arrives, and preparation method thereof and a kind of zirconia sintered body starting shrinkage temperature adjusting method and a kind of zirconium oxide The adjusting method of sintered body shrinking percentage.
Background technique
Natural toilet article have the translucency of gradual change, and layering zirconium oxide artificial tooth can be made and the closer light transmission of natural tooth appearance Property gradation type artificial tooth.Translucency gradation type artificial tooth passes through with different Y2O3Content is realized.But because of ingredient difference, in same process The various Zirconium powders of lower production, Shrinkage behavior is different, when the Zirconium powder layering of two or more different yttrium contents It after compacting, will appear internal stress during the sintering process, cause integral strength to reduce and even crack, sintered finished product becomes Shape.
The prior art adjusts sintering aid (such as Al first is that passing through2O3Deng) content, realize the adjustment of Shrinkage behavior.It burns The addition for tying auxiliary agent, can influence the growth conditions of crystal grain, to control the sintering activity of zirconium oxide.It is sintered at the same temperature When, the sintering aid for adding variety classes or different content can obtain out different Shrinkage behaviors.Although sintering aid can have Effect adjusts Zirconium oxide sintering shrinking percentage, but sintering aid be added can permeability to zirconia sintered body and color have an impact. For example, adding Al in zirconium oxide2O3, sintered body permeability will reduce, and whiteness will increase.In order to avoid this defect, can be improved Yttrium content is improved, but the raising of yttrium content can bring the reduction of sintered body intensity.Therefore, pass through constituent adjustment shrinking percentage meeting Linksystem problem is brought, regulating measures are cumbersome.
The prior art is also the transition zone by being arranged between different zirconium oxide layers, is realized to shrinkage difference most Smallization, for the biggish zirconium oxide layer of yttrium content difference, regulating degree is limited, can not be suitable for the biggish oxidation of yttrium content difference The adjusting of the contraction consistency of zirconium layer limits the gradual change range of translucency gradual change.
This field, which needs to develop one kind, to be adjusted to the receipts for having roughly the same for the Zirconium powder of different yttrium contents The method of shrinkage, this method can make have roughly the same receipts in the Zirconium powder sintering process with different yttrium contents Indention is that deflection is small after sintering, not easy to crack.
The generation for inhibiting defect and the transparent zirconia sintered body that can change are provided for CN107108373A (2014), burnt Contain the yttrium oxide of 4~7mol% in knot body as stabilizer and light screening material, light screening material is selected from comprising silica, oxidation At least one of aluminium, titanium oxide, zirconium and group of composite oxides of silicon.Light screening material in the second area of zirconia sintered body Containing ratio it is higher than first area, the difference of the containing ratio of the yttrium oxide in two regions is 1mol% or less.
Summary of the invention
In view of the deficiencies of the prior art, an object of the present invention is to provide a kind of zirconium oxide muffin, the zirconia powder Cake includes at least two layers of Zirconium powder layer, and the yttrium content of different Zirconium powder layers is different, and the different Zirconium powders Layer, TMA curve shrinkage initial temperature difference≤5 DEG C (such as 4 DEG C, 3 DEG C, 2 DEG C, 1 DEG C etc.)；The difference Zirconium powder layer, TMA curve shrinkage rate deviation≤0.3% (such as 0.2%, 0.1% etc.).
TMA (thermomechanical analysis), Chinese is thermo-mechanical analysis, is referred in process control temperature Spend the method for the relationship of lower measurement of species deformation and temperature.Zirconium oxide muffin provided by the invention has multilayer Zirconium powder Layer, every layer of Zirconium powder layer obtain sintered different translucency, realize translucency gradually by adjusting the difference of yttrium content Become.In the prior art, the Zirconium powder Shrinkage behavior of different yttrium contents mostly shows inconsistent, in subsequent sintering process In, the problems such as causing deformation, crack.Zirconium powder provided by the invention has multilayered structure, and every layer of Zirconium powder layer Yttrium content is different, but its Shrinkage behavior is able to maintain roughly the same, is able to solve in sintering process be deformed, crack etc. and ask Topic.
Preferably, in the zirconium oxide muffin, the yttrium content maximum difference > 1mol% of different Zirconium powder layers (such as 1.2mol%, 2mol%, 3mol%, 4mol%, 5mol%, 6mol% etc.), preferably 1~5mol%.
It should be noted that in the zirconium oxide muffin, the yttrium content maximum difference > of different Zirconium powder layers 1mol% means: in zirconium oxide muffin provided by the invention, having at least two layers of Zirconium powder layer, in all zirconia powders In the set of body layer yttrium content difference, maximum difference > 1mol%.The difference is optional different layers Zirconium powder layer The difference of yttrium content.
Preferably, yttrium content is sequentially increased the Zirconium powder layer from the bottom to top.
Yttrium content is bigger, and translucency is better, the multilayer zirconia powder cake that yttrium content is sequentially increased from the bottom to top, and appearance is presented Gradual change translucency, it is close with natural tooth.
Preferably, the Zirconium powder includes 3 layers of Zirconium powder layer, wherein yttrium content be followed successively by 2.6~ 3.4mol%, 3.6~4.4mol% and 4.6~5.4mol%；The yttrium content of further preferred 3 layers of Zirconium powder layer according to Secondary is 3mol%, 4mol% and 5mol%.
The second object of the present invention is to providing a kind of preparation method of zirconium oxide muffin, the preparation method includes following step It is rapid:
(1) zirconium source, yttrium source and other function element source are mixed in liquid phase, carry out hydrothermal synthesis；Liquid phase thermal synthesis Product carry out calcining heat treatment, obtain the Zirconium powder with different yttrium contents；
According to the yttrium content in Zirconium powder raw material, according to the water in following formula selective oxidation zirconium powder production procedure Thermal synthesis temperature and calcining heat treatment temperature:
ΔTHydrothermal synthesis=-k1ΔXYttriumFormula (I)
ΔTCalcining heat treatment=k2ΔXYttriumFormula (II)
Wherein, Δ THydrothermal synthesisFor the difference of hydrothermal synthesis temperature in any two groups of Zirconium powder stock preparation process, unit For DEG C；ΔTCalcining heat treatmentFor the difference for calcining heat treatment temperature in any two groups of Zirconium powder stock preparation process, unit is DEG C； ΔXYttriumFor the difference of yttrium molar content in any two groups of Zirconium powder raw materials, unit mol%；k1For the coefficient of hydrothermal synthesis 8.3~8.7 (such as 8.4,8.5,8.6 etc.)；k2For the coefficient 16.6~17.0 (such as 16.7,16.8,16.9 of calcining heat treatment Deng)；
(3) Zirconium powder with yttrium content is stacked in a predetermined order, then carries out dry-pressing, obtain zirconia powder Cake.
In the prior art, yttrium content difference is smaller, and the adjustment of Shrinkage behavior is easier；When yttrium content difference is in 1mol% When above, Shrinkage behavior adjustment encounters difficulties.In the preparation method of zirconium oxide muffin provided by the invention, by adjusting hydro-thermal Synthesis temperature and calcining heat treatment temperature realize the adjustment to Shrinkage behavior.As shown in formula (I) and formula (II), according to yttrium content Difference can both obtain the adjustment temperature of hydrothermal synthesis temperature and the adjustment temperature of calcining heat treatment.
Preferably, the pressure of the dry-pressing be 5~100MPa (such as 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa, 100MPa etc.), the time is 5~30s (such as 5s, 10s, 15s, 20s, 25s etc.).
In the preparation method of the zirconium oxide muffin, additive amount >=0,0 of other function element means to be added without Other function element.Mean the other elements chemical combination other than zirconium compounds and yttrium compound for other function element The selection of object, the other elements compound is not especially limited, and those skilled in the art can select according to demand.Example If the other function element can be the element with colouring function, such as iron, manganese, erbium, neodymium, praseodymium, cerium, aluminium.
Preferably, the other function element include in iron, manganese, erbium, neodymium, praseodymium, cerium, aluminium etc. any one or at least Two kinds of combination.
Preferably, the zirconium oxide muffin includes zirconium oxide muffin described in the first purpose.
Preferably, the hydrothermal synthesis specifically comprises the following steps:
(2a), which mixes zirconium source and yttrium source and other functional elements, is dissolved in water, adjusts pH to 8~10 (8.5,9.0,9.5 Deng)；
Reaction system is heated up and carries out hydrothermal synthesis by (2b)；
(2c) hydrothermal synthesis product is ground after calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder.
Preferably, the zirconium source includes water dissolvable zirconates, preferably zirconium nitrate, zirconium oxychloride, any one in zirconium chloride Kind or at least two combination.
At least two combination examples in the zirconium source may include zirconium nitrate and zirconium oxychloride combination, zirconium nitrate Combination, zirconium nitrate and zirconium oxychloride and the combination of zirconium chloride etc. with zirconium chloride.
Preferably, the yttrium source includes yttrium salt, preferably yttrium nitrate.
Preferably, the adjusting pH value is carried out by the way that ammonium hydroxide is added.
Preferably, the hydrothermal synthesis temperature is 140~200 DEG C (such as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C Deng), the time is 10~72h (such as 15h, 20h, 25h, 30h, 35h, 40h, 45h, 60h, 70h etc.), preferably hydrothermal synthesis temperature It is 140~170 DEG C, the time is 10~50h.
Preferably, the calcining heat treatment temperature be 800~1100 DEG C (such as 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C, etc.), 1~5h of time, preferably 900~1100 DEG C, 2~4h of time.
Preferably, alumina powder is added in step (2c) described process of lapping.
Preferably, step (2c) the hydrothermal synthesis product is washed before calcining heat treatment, is dried.
The three of the object of the invention are to provide a kind of purposes of zirconium oxide muffin as described in the first purpose, the zirconia powder Cake is used as the tooth cake of processing artificial tooth, processes the biscuiting block of backboard or the biscuiting block of processing decoration product.
Zirconium oxide muffin provided by the invention can be used as biscuiting block, and artificial tooth or electronic product are obtained after being sintered Backboard, or as ornament (such as bracelet, necklace).Zirconium oxide muffin provided by the invention has the translucency of gradual change.
The four of the object of the invention are to provide a kind of layering oxidation zirconium base sintered body, and the layering oxidation zirconium base sintered body has The yttrium content of at least two layers of Zirconium oxide sintering layer, different Zirconium oxide sintering layers is different, and the deflection of the zirconia sintered body ≤ 0.3% (such as 0.25%, 0.20%, 0.15%, 0.10% etc.).
The deflection of zirconia sintered body means the layering sample block of long 100mm thickness 10mm, sintering rear end offset Δ d with The ratios delta d/d of thickness d.
In the prior art, the yttrium content of different Zirconium oxide sintering layers is different, and each layer shrinking percentage of sintering process differs greatly, from And cause deflection larger.Deflection≤0.3% of layering oxidation zirconium base sintered body provided by the present application, enables to described point Layer zirconia sintered body has preferable shape and size controllability, is not susceptible to shape distortion, strength reduction, crackle, fracture The problems such as.
Preferably, the different Zirconium oxide sintering layer yttrium content maximum difference > 1mol% (2mol%, 3mol%, 4mol% etc.), preferably 1~5mol%.
Preferably, it is described layering oxidation zirconium base sintered body include at least 3mol% yttrium content Zirconium oxide sintering layer, The Zirconium oxide sintering layer of the Zirconium oxide sintering layer of 4mol% yttrium content, 5mol% yttrium content, and the change of the zirconia sintered body Shape amount≤0.3%.
The five of the object of the invention are to provide a kind of preparation method of layering oxidation zirconium base sintered body as described in the fourth purpose, The preparation method includes being sintered zirconium oxide muffin described in the first purpose, obtains layering oxidation zirconium base sintered body.
Preferably, the sintering temperature is 1400~1550 DEG C, such as 1450 DEG C, 1500 DEG C etc., the time is 1~3h, example Such as 1.5h, 2.0h, 2.5h.
The object of the invention sixth is that provide it is a kind of as described in the fourth purpose layering oxidation zirconium base sintered body purposes, it is described Layering oxidation zirconium base sintered body is for making artificial tooth, backboard or ornament.
The object of the invention seventh is that provide a kind of artificial tooth, the artificial tooth includes that the oxidation zirconium base of layering described in the fourth purpose is burnt Knot body；
Alternatively, the artificial tooth includes the production of the preparation method preparation of layering oxidation zirconium base sintered body described in the fifth purpose Object；
Alternatively, the sintering of artificial tooth zirconium oxide muffin as described in the first purpose obtains；
Alternatively, the zirconium oxide muffin sintering that artificial tooth preparation method as described in the second purpose is prepared obtains.
Zirconium oxide muffin is sintered, Shrinkage behavior, which can be divided into, shrinks initial temperature and shrinking percentage.It will shrink Initial temperature is approximate consistent with shrinking percentage adjustment, both can substantially think that the Shrinkage behavior of the zirconium oxide muffin was unanimous on the whole.
The object of the invention eighth is that providing a kind of adjusting method of zirconia sintered body starting shrinkage temperature, the method packet Include following steps:
(1) according to the yttrium content of scheduled Zirconium powder and scheduled contraction initial temperature, water is obtained according to formula (III) Thermal synthesis temperature:
THydrothermal synthesis=k1XYttrium-TShrink starting+ 859 formulas (III)
Wherein, THydrothermal synthesisFor the hydrothermal synthesis temperature in zirconia powder production procedure, unit is DEG C；XYttriumFor scheduled oxygen Change the yttrium content of zirconium powder body, unit mol%；TShrink startingFor scheduled contraction initial temperature, unit is DEG C；k1For hydrothermal synthesis Coefficient 8.3~8.7；
(2) zirconium source, yttrium source and other function element source are mixed in liquid phase, in THydrothermal synthesisAt a temperature of carry out hydro-thermal conjunction At；The product of hydrothermal synthesis carries out calcining heat treatment, obtains with the predetermined Zirconium powder for shrinking initial temperature.
The other function element has foregoing understanding, such as additive amount >=0,0 of other function element Mean to be added without other function element.Other function element is meant other than zirconium compounds and yttrium compound The selection of other elements compound, the other elements compound is not especially limited, and those skilled in the art can be according to need It asks and is selected.Such as the other function element can be the element with colouring function, such as iron, manganese；Or Erbium, neodymium, praseodymium, cerium, aluminium etc..
The object of the invention ninth is that providing a kind of adjusting method of zirconia sintered body shrinking percentage, the method includes as follows Step:
(1) according to the yttrium content of scheduled Zirconium powder, scheduled shrinking percentage and liquid phase thermal synthesis temperature, according to formula (IV) calcining heat treatment temperature is obtained:
TCalcining heat treatment=(σ -0.0002608Y+0.0001168THydrothermal synthesis- 0.2899)/0.00007426 formula (IV)
Wherein, THydrothermal synthesisFor the hydrothermal synthesis temperature in zirconia powder production procedure, unit is DEG C；XYttriumFor scheduled oxygen Change the yttrium content of zirconium powder body, unit mol%；TCalcining heat treatmentIt is single for the calcining heat treatment temperature in zirconia powder production procedure Position is DEG C；σ is shrinking percentage, %；
(2) zirconium source, yttrium source and other addition element sources are mixed in liquid phase, in THydrothermal synthesisAt a temperature of carry out hydrothermal synthesis； The product of hydrothermal synthesis is in TCalcining heat treatmentAt a temperature of carry out calcining heat treatment, obtain with the predetermined zirconia powder for shrinking initial temperature Body.
The other function element has foregoing understanding, such as additive amount >=0,0 of other function element Mean to be added without other function element.Other function element is meant other than zirconium compounds and yttrium compound The selection of other elements compound, the other elements compound is not especially limited, and those skilled in the art can be according to need It asks and is selected.Such as the other function element can be the element with colouring function, such as iron, manganese；Or Erbium, neodymium, praseodymium, cerium, aluminium etc..
Compared with prior art, the invention has the following beneficial effects:
(1) the present invention provides a kind of zirconium oxide muffin, Preparation method and use, the different oxidations of the zirconium oxide muffin There is different yttrium contents, but still (TMA curve shrinkage initial temperature is poor with Shrinkage behavior unanimous on the whole in zirconium powder layer ≤ 5 DEG C of value；The difference Zirconium powder layer, TMA curve shrinkage rate deviation≤0.3%), to be mentioned for subsequent sintering process For higher deformation stability, effectively avoid because Shrinkage behavior it is inconsistent caused by shape distortion, strength reduction, crackle, open The defects of splitting.
(2) the present invention provides a kind of layering aoxidize zirconium base sintered body, Preparation method and use, the layering zirconium oxide and Sintered body obtains different translucency by the different yttrium contents of the different Zirconium oxide sintering layers of selection, by different saturating to having The selection of the Zirconium oxide sintering layer of photosensitiveness to put in order, obtaining, there is the layering of gradual change translucency to aoxidize zirconium base sintered body.Institute Layering oxidation zirconium base sintered body is stated due to the translucency with gradual change, in use, it can be with the feeling of natural tooth more as artificial tooth It is close.
(3) the present invention also provides a kind of regulation methods of zirconia sintered body Shrinkage behavior, including starting shrinkage temperature With the regulation method of shrinking percentage, difference of the regulation method according to yttrium content, foundation adjusting formula (formula (I) and/or formula (II)) its hydrothermal synthesis temperature and calcining heat treatment temperature, are had adjusted, is realized the purpose of Shrinkage behavior controllable adjustment.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The preparation with the multiple groups zirconia powder (A1, A2, A3) of different yttrium contents is provided, zirconia powder A1 yttrium content is 3mol%, zirconia powder A2 yttrium content are 4mol%, and zirconia powder A3 yttrium content is 5mol%, and preparation method includes following step It is rapid:
(1) zirconia powder A1 is prepared, specifically comprises the following steps: that (1a) 97:6 is mixed in molar ratio with yttrium nitrate by zirconium nitrate Conjunction is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydrothermal synthesis product After washed drying, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder A1 (yttrium content 3mol%)；
(2) zirconia powder A2 is prepared, specifically comprises the following steps: that (2a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × 1=-8.5 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder A2 is 160 DEG C -8.5 DEG C=151.5 DEG C；According to Formula (II) calculates calcining heat treatment temperature: Δ TCalcining heat treatment=16.8 × 1=16.8 DEG C, i.e. the calcining of zirconia powder A2 is heat-treated temperature Degree is 950 DEG C+16.8 DEG C=966.8 DEG C；(2b) 96:8 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, adjust pH to 8~10；Reaction system is warming up to 151.5 DEG C of progress hydrothermal synthesis by (2c)；After the washed drying of (2d) hydrothermal synthesis product, powder Body is ground after 966.8 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder A2 (yttrium content 4mol%)；
(3) zirconia powder A3 is prepared, specifically comprises the following steps: that (3a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × 2=-17 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder A3 is 160 DEG C -17 DEG C=143 DEG C；According to formula (II) calcining heat treatment temperature: Δ T is calculatedCalcining heat treatment=16.8 × 2=33.6 DEG C, i.e. the calcining heat treatment temperature of zirconia powder A3 It is 950 DEG C+33.6 DEG C=983.6 DEG C；(3b) 95:10 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, adjusts pH to 8 ~10；Reaction system is warming up to 143 DEG C of progress hydrothermal synthesis by (3c)；After the washed drying of (3d) hydrothermal synthesis product, powder It after 983.6 DEG C carry out calcining heat treatment, grinds, disperses, be granulated, obtain Zirconium powder A3 (yttrium content 5mol%)；
(4) zirconia powder A1, zirconia powder A2 and zirconia powder A3 body are stacked by sequence from bottom to top, is then carried out Dry-pressing 20MPa obtains zirconium oxide muffin X1.
Comparative example 1
The preparation with the multiple groups zirconia powder (' 2 A1, A, A ' 3) of different yttrium contents is provided, zirconia powder A1 yttrium content is 2 yttrium content of 3mol%, zirconia powder A ' is 4mol%, and 3 yttrium content of zirconia powder A ' is 5mol%, and preparation method includes following step It is rapid:
(1) zirconia powder A1 is prepared, specifically comprises the following steps: that (1a) 97:6 is mixed in molar ratio with yttrium nitrate by zirconium nitrate Conjunction is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydrothermal synthesis product After washed drying, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder A1 (yttrium content 3mol%)；
(2) zirconia powder A ' 2 is prepared, specifically comprises the following steps: (2a) by zirconium nitrate and yttrium nitrate 96:8 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (2b)；(2c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained 2 (yttrium of Zirconium powder A ' Content 4mol%)；
(3) zirconia powder A ' 3 is prepared, specifically comprises the following steps: (3a) by zirconium nitrate and yttrium nitrate 95:10 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (3b)；(3c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained 3 (yttrium of Zirconium powder A ' Content 5mol%)；
(4) zirconia powder A ' 1, zirconia powder A ' 2 and 3 body of zirconia powder A ' are stacked by sequence from bottom to top, then Dry-pressing 20MPa is carried out, zirconium oxide muffin X ' 1 is obtained.
Performance test:
(1) by Zirconium powder A1, Zirconium powder A2, Zirconium powder A3, Zirconium powder A ' 2, Zirconium powder A ' 3 is dry-pressing formed at 20MPa, then through the static pressure 30s such as 200MPa, obtains green compact sample block, by green compact sample block through 900 DEG C of biscuitings, Test specimens block is obtained, test specimens block is tested using TMA, is warming up in air atmosphere by the heating rate of 1 DEG C/min 1600 DEG C, obtain starting shrinkage temperature and shrinking percentage；
Three-point bending resistance strength test method: the above biscuiting sample block after cutting, polishing, 1500 DEG C of sintering 1h, obtain 4.0 × 1.0 × 20mm batten, after spline surfaces polishing, test three-point bending resistance intensity, span 16mm, test speed 0.5mm/min, each 10 battens of sample test, and be averaged.
Permeability test method: the above biscuiting sample block obtains 1.0mm thickness print after cutting, polishing, 1500 DEG C of sintering 1h, After twin polishing, transmittance data at spectrophotometer test 500nm wavelength is used.
Test result such as table 1:
Table 1
Serial number A1 A2 A3 A’2 A’3
Contraction initial temperature/DEG C 1043 1047 1045 1057 1064
Shrinking percentage/% 20.14 20.13 20.13 20.18 20.23
Intensity/MPa 1205 868 563 886 547
Permeability/% 43.53 46.18 49.53 46.26 49.41
(2) the sintering 1h time that zirconium oxide muffin X1 and X ' 1 is carried out to 1500 DEG C, its 1. deformation quantity, test method are monitored For sample block is put on horizontal table, one end is pushed it is with workbench seamless, with the clearance gauge measurement other end and workbench Gap size Δ d is calculated using calliper to measure batten thickness d and is obtained deformation data Δ d/d；, test result such as table 2；
Table 2
As can be seen from Table 1 and Table 2, after by the adjusting of hydrothermal synthesis temperature and calcination temperature, the contraction of different powders Rate (between 20.13~20.14%) and contraction initial temperature (between 1043~1047 DEG C) reach unanimity, intensity, Permeability has no significant effect, and the sintering warpage amount of muffin is obviously reduced.
Embodiment 2
The preparation with the multiple groups zirconia powder (B1, B2, B3) of different yttrium contents is provided, zirconia powder B1 yttrium content is 5mol%, zirconia powder B2 yttrium content are 4mol%, and zirconia powder B3 yttrium content is 3mol%, and preparation method includes following step It is rapid:
(1) zirconia powder B1 is prepared, specifically comprises the following steps: (1a) by zirconium nitrate and yttrium nitrate 95:10 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, obtaining Zirconium powder B1, (yttrium contains Measure 5mol%)；
(2) zirconia powder B2 is prepared, specifically comprises the following steps: that (2a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × (- 1)=8.5 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder B2 are 160 DEG C+8.5 DEG C=168.5 DEG C；Root Calcining heat treatment temperature: Δ T is calculated according to formula (II)Calcining heat treatment=16.8 × (- 1)=- 16.8 DEG C, i.e. the calcining heat of zirconia powder B2 Treatment temperature is 950 DEG C -16.8 DEG C=933.2 DEG C；(2b) 96:8 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, is adjusted Save pH to 8~10；Reaction system is warming up to 168.5 DEG C of progress hydrothermal synthesis by (2c)；(2d) hydrothermal synthesis product is washed dry After dry, powder is ground after 933.2 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder B2 (yttrium content 4mol%)；
(3) zirconia powder B3 is prepared, specifically comprises the following steps: that (3a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × (- 2)=17 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder B3 are 160 DEG C+17 DEG C=177 DEG C；According to formula (II) calcining heat treatment temperature: Δ T is calculatedCalcining heat treatment=16.8 × (- 2)=- 33.6 DEG C, i.e. the calcining heat treatment of zirconia powder B3 Temperature is 950 DEG C -33.6 DEG C=916.4 DEG C；(3b) 97:6 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, adjusts pH To 8~10；Reaction system is warming up to 177 DEG C of progress hydrothermal synthesis by (3c)；After the washed drying of (3d) hydrothermal synthesis product, powder Body is ground after 914.6 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder B3 (yttrium content 3mol%)；
(4) zirconia powder B3, zirconia powder B2 and zirconia powder B1 body are stacked by sequence from bottom to top, is then carried out Dry-pressing 20MPa obtains zirconium oxide muffin X2.
Comparative example 2
The preparation with the multiple groups zirconia powder (' 2 B1, B, B ' 3) of different yttrium contents is provided, zirconia powder B1 yttrium content is 2 yttrium content of 5mol%, zirconia powder B ' is 4mol%, and 3 yttrium content of zirconia powder B ' is 3mol%, and preparation method includes following step It is rapid:
(1) zirconia powder B1 is prepared, specifically comprises the following steps: (1a) by zirconium nitrate and yttrium nitrate 95:10 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, obtaining Zirconium powder B1, (yttrium contains Measure 5mol%)；
(2) zirconia powder B ' 2 is prepared, specifically comprises the following steps: (2a) by zirconium nitrate and yttrium nitrate 96:8 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (2b)；(2c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained 2 (yttrium of Zirconium powder B ' Content 4mol%)；
(3) zirconia powder B ' 3 is prepared, specifically comprises the following steps: (3a) by zirconium nitrate and yttrium nitrate 97:6 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (3b)；(3c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained 3 (yttrium of Zirconium powder B ' Content 3mol%)；
(4) zirconia powder B3, zirconia powder B ' 2 and 1 body of zirconia powder B ' are stacked by sequence from bottom to top, then into Row dry-pressing 20MPa obtains zirconium oxide muffin X ' 2.
Performance test:
(1) by Zirconium powder B1, Zirconium powder B2, Zirconium powder B3, Zirconium powder B ' 2, Zirconium powder B ' 3 is dry-pressing formed at 20MPa, then through the static pressure 30s such as 200MPa, obtains green compact sample block, by green compact sample block through 900 DEG C of biscuitings, Test specimens block is obtained, test specimens block is tested using TMA, is warming up in air atmosphere by the heating rate of 1 DEG C/min 1600 DEG C, obtain starting shrinkage temperature and shrinking percentage；
Three-point bending resistance strength test method: the above biscuiting sample block after cutting, polishing, 1500 DEG C of sintering 1h, obtain 4.0 × 1.0 × 20mm batten, after spline surfaces polishing, test three-point bending resistance intensity, span 16mm, test speed 0.5mm/min, each 10 battens of sample test, and be averaged.
Permeability test method: the above biscuiting sample block obtains 1.0mm thickness print after cutting, polishing, 1500 DEG C of sintering 1h, After twin polishing, transmittance data at spectrophotometer test 500nm wavelength is used.
Test result such as table 3:
Table 3
Serial number B1 B2 B3 B’2 B’3
Contraction initial temperature/DEG C 1062 1060 1061 1053 1043
Shrinking percentage/% 20.20 20.20 20.21 20.16 20.10
Intensity/MPa 547 893 1235 886 1205
Permeability/% 547 46.38 43.36 46.26 43.53
(2) the sintering 1h that zirconium oxide muffin X2 and X ' 2 is carried out to 1500 DEG C, monitors its deformation quantity, and test method is by sample Block is put on horizontal table, and one end pushing is seamless with workbench, and the gap for measuring the other end and workbench with clearance gauge is big Small Δ d is calculated using calliper to measure batten thickness d and is obtained deformation data Δ d/d, test result such as table 4:
Table 4
Serial number Zirconium oxide muffin X2 Zirconium oxide muffin X ' 2
Deformation quantity/% 0.19 1.43
As can be seen from tables 3 and 4 that after adjusting by hydrothermal synthesis temperature and calcination temperature, with the contraction temperature of powder Degree (at 1060~1062 DEG C) reaches unanimity with shrinking percentage (20.20~20.21%), and intensity, permeability have no significant effect, muffin Sintering warpage amount be obviously reduced.
Embodiment 3
The preparation with the multiple groups zirconia powder (C1, C2, C3) of different yttrium contents is provided, zirconia powder C1 yttrium content is 4mol%, zirconia powder C2 yttrium content are 6mol%, and zirconia powder C3 yttrium content is 2mol%, and preparation method includes following step It is rapid:
(1) zirconia powder C1 is prepared, specifically comprises the following steps: that (1a) 96:8 is mixed in molar ratio with yttrium nitrate by zirconium nitrate Conjunction is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydrothermal synthesis product After washed drying, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder C1；
(2) zirconia powder C2 is prepared, specifically comprises the following steps: that (2a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × 2=-17 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder C2 is 160 DEG C -17 DEG C=143 DEG C；According to formula (II) calcining heat treatment temperature: Δ T is calculatedCalcining heat treatment=16.8 × 2=33.6 DEG C, i.e. the calcining heat treatment temperature of zirconia powder C2 It is 950 DEG C+33.6 DEG C=983.6 DEG C；(2b) 94:12 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, adjusts pH to 8 ~10；Reaction system is warming up to 143 DEG C of progress hydrothermal synthesis by (2c)；After the washed drying of (2d) hydrothermal synthesis product, powder It after 983.6 DEG C carry out calcining heat treatment, grinds, disperses, be granulated, obtain Zirconium powder C2；
(3) zirconia powder C3 is prepared, specifically comprises the following steps: that (3a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × (- 2)=17 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder C3 are 160 DEG C+17 DEG C=177 DEG C；According to formula (II) calcining heat treatment temperature: Δ T is calculatedCalcining heat treatment=16.8 × (- 2)=- 33.6 DEG C, i.e. the calcining heat treatment of zirconia powder C3 Temperature is 950 DEG C -33.6 DEG C=916.4 DEG C；(3b) 98:4 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, adjusts pH To 8~10；Reaction system is warming up to 177 DEG C of progress hydrothermal synthesis by (3c)；After the washed drying of (3d) hydrothermal synthesis product, powder Body is ground after 914.6 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder C3；
(4) zirconia powder C3, zirconia powder C1 and zirconia powder C2 body are stacked by sequence from bottom to top, is then carried out Dry-pressing 20MPa obtains zirconium oxide muffin X3.
Comparative example 3
The preparation with the multiple groups zirconia powder (' 2 C1, C, C ' 3) of different yttrium contents is provided, zirconia powder C1 yttrium content is 2 yttrium content of 4mol%, zirconia powder C ' is 6mol%, and 3 yttrium content of zirconia powder C ' is 2mol%, and preparation method includes following step It is rapid:
(1) zirconia powder C1 is prepared, specifically comprises the following steps: that (1a) 96:8 is mixed in molar ratio with yttrium nitrate by zirconium nitrate Conjunction is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydrothermal synthesis product After washed drying, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder C1；
(2) zirconia powder C ' 2 is prepared, specifically comprises the following steps: (2a) by zirconium nitrate and yttrium nitrate 94:12 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (2b)；(2c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder C ' 2；
(3) zirconia powder C ' 3 is prepared, specifically comprises the following steps: (3a) by zirconium nitrate and yttrium nitrate 98:4 in molar ratio Mixing is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (3b)；(3c) hydrothermal synthesis produces After the washed drying of object, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder C ' 3；
(4) zirconia powder C ' 3, zirconia powder C1 and 2 body of zirconia powder C ' are stacked by sequence from bottom to top, then into Row dry-pressing 20MPa obtains zirconium oxide muffin X ' 3.
Performance test:
(1) by Zirconium powder C1, Zirconium powder C2, Zirconium powder C3, Zirconium powder C ' 2, Zirconium powder C ' 3 is dry-pressing formed at 20MPa, then through the static pressure 30s such as 200MPa, obtains green compact sample block, by green compact sample block through 900 DEG C of biscuitings, Test specimens block is obtained, test specimens block is tested using TMA, is warming up in air atmosphere by the heating rate of 1 DEG C/min 1600 DEG C, obtain starting shrinkage temperature and shrinking percentage；
Three-point bending resistance strength test method: the above biscuiting sample block after cutting, polishing, 1500 DEG C of sintering 1h, obtain 4.0 × 1.0 × 20mm batten, after spline surfaces polishing, test three-point bending resistance intensity, span 16mm, test speed 0.5mm/min, each 10 battens of sample test, and be averaged.
Permeability test method: the above biscuiting sample block obtains 1.0mm thickness print after cutting, polishing, 1500 DEG C of sintering 1h, After twin polishing, transmittance data at spectrophotometer test 500nm wavelength is used.
Test result such as table 5:
Table 5
Serial number C1 C2 C3 C’2 C’3
Contraction initial temperature/DEG C 1053 1053 1054 1036 1070
Shrinking percentage/% 20.17 20.17 20.19 20.12 20.22
Intensity/MPa 886 487 1308 492 1294
Permeability/% 46.26 49.09 32.56 49.05 32.60
(2) the sintering 1h that zirconium oxide muffin X3 and X ' 3 is carried out to 1500 DEG C, monitors its deformation quantity, and test method is by sample Block is put on horizontal table, and one end pushing is seamless with workbench, and the gap for measuring the other end and workbench with clearance gauge is big Small Δ d is calculated using calliper to measure batten thickness d and is obtained deformation data Δ d/d, test result such as table 6:
Table 6
Serial number Zirconium oxide muffin X3 Zirconium oxide muffin X ' 3
Deformation quantity/% 0.28 1.62
From table 5 and table 6 as can be seen that after adjusting by hydrothermal synthesis temperature and calcination temperature, with the shrinking percentage of powder (20.17~20.19%) and shrinkage temperature (1053~1054 DEG C) reach unanimity, and intensity, permeability have no significant effect, muffin Sintering warpage amount be obviously reduced.
Embodiment 4
The preparation with the multiple groups zirconia powder (D1, D2, D3) of different yttrium contents is provided, zirconia powder D1 yttrium content is 2.6mol%, zirconia powder D2 yttrium content are 4.4mol%, and zirconia powder D3 yttrium content is 4.6mol%, and preparation method includes such as Lower step:
(1) zirconia powder D1 is prepared, specifically comprises the following steps: (1a) by zirconium nitrate and yttrium nitrate in molar ratio 97.4: 5.2 mixing are dissolved in water, adjust pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydro-thermal is closed After the washed drying of product, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder D1；
(2) zirconia powder D2 is prepared, specifically comprises the following steps: that (2a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × 1.8=-15.3 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder D2 is 160 DEG C -15.3 DEG C=144.7 DEG C； Calcining heat treatment temperature: Δ T is calculated according to formula (II)Calcining heat treatment=16.8 × 1.8=30.24 DEG C, the i.e. calcining of zirconia powder D2 Heat treatment temperature is 950 DEG C+30.24 DEG C=980.24 DEG C；(2b) 95.6:8.8 is mixed in molar ratio with yttrium nitrate by zirconium nitrate It is dissolved in water, adjusts pH to 8~10；Reaction system is warming up to 144.7 DEG C of progress hydrothermal synthesis by (2c)；(2d) hydrothermal synthesis product After washed drying, powder is ground after 980.24 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder D2；
(3) zirconia powder D3 is prepared, specifically comprises the following steps: that (3a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × 2=-17 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder B3 is 160 DEG C -17 DEG C=143 DEG C；According to formula (II) calcining heat treatment temperature: Δ T is calculatedCalcining heat treatment=16.8 × 2=33.6 DEG C, i.e. the calcining heat treatment temperature of zirconia powder B3 It is 950 DEG C+33.6 DEG C=983.6 DEG C；(3b) 95.4:9.2 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, adjusts pH To 8~10；Reaction system is warming up to 143 DEG C of progress hydrothermal synthesis by (3c)；After the washed drying of (3d) hydrothermal synthesis product, powder Body is ground after 983.6 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder D3；
(4) zirconia powder D1, zirconia powder D2 and zirconia powder D3 body are stacked by sequence from bottom to top, is then carried out Dry-pressing 20MPa obtains zirconium oxide muffin X4；
(5) the sintering 1h that zirconium oxide muffin X4 is carried out to 1400 DEG C, monitors its deformation quantity, and test method is to be put in sample block It is on horizontal table, one end pushing is seamless with workbench, the gap size Δ d of the other end and workbench is measured with clearance gauge, Using calliper to measure batten thickness d, calculating and obtaining deformation data Δ d/d is 0.25.
Performance test:
(1) Zirconium powder D1, Zirconium powder D2, Zirconium powder D3 is dry-pressing formed at 20MPa, then pass through The static pressure 30s such as 200MPa obtains green compact sample block, by green compact sample block through 900 DEG C of biscuitings, obtains test specimens block, test specimens block is made Tested with TMA, be warming up to 1600 DEG C by the heating rate of 1 DEG C/min in air atmosphere, obtain starting shrinkage temperature and Shrinking percentage；
Three-point bending resistance strength test method: the above biscuiting sample block after cutting, polishing, 1500 DEG C of sintering 1h, obtain 4.0 × 1.0 × 20mm batten, after spline surfaces polishing, test three-point bending resistance intensity, span 16mm, test speed 0.5mm/min, each 10 battens of sample test, and be averaged.
Permeability test method: the above biscuiting sample block obtains 1.0mm thickness print after cutting, polishing, 1500 DEG C of sintering 1h, After twin polishing, transmittance data at spectrophotometer test 500nm wavelength is used.
Test result such as table 7:
Table 7
Serial number D1 D2 D3
Contraction initial temperature/DEG C 1041 1041 1040
Shrinking percentage/% 20.13 20.14 20.14
Intensity/MPa 1315 887 853
Permeability/% 37.85 46.26 47.31
(2) after the adjusting that the performance test results can be seen that through hydrothermal synthesis temperature and calcination temperature, with powder Shrinking percentage (in 20.13-20.14%) and starting shrinkage temperature (1040-1041 DEG C) reach unanimity, the sintering warpage amount of muffin It is obviously reduced.
Embodiment 5
The preparation with the multiple groups zirconia powder (E1, E2, E3) of different yttrium contents is provided, zirconia powder E1 yttrium content is 3.4mol%, zirconia powder E2 yttrium content are 3.6mol%, and zirconia powder E3 yttrium content is 5.4mol%, and preparation method includes such as Lower step:
(1) zirconia powder E1 is prepared, specifically comprises the following steps: (1a) by zirconium nitrate and yttrium nitrate in molar ratio 96.6: 6.8 mixing are dissolved in water, adjust pH to 8~10；Reaction system is warming up to 160 DEG C of progress hydrothermal synthesis by (1b)；(1c) hydro-thermal is closed After the washed drying of product, powder is ground after 950 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder E1；
(2) zirconia powder E2 is prepared, specifically comprises the following steps: that (2a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × 0.2=-1.7 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder E2 is 160 DEG C -1.7 DEG C=158.3 DEG C；Root Calcining heat treatment temperature: Δ T is calculated according to formula (II)Calcining heat treatment=16.8 × 0.2=3.36 DEG C, i.e., at the calcining heat of zirconia powder E2 Managing temperature is 950 DEG C+3.36 DEG C=953.6 DEG C；(2b) 96.4:7.2 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, Adjust pH to 8~10；Reaction system is warming up to 158.3 DEG C of progress hydrothermal synthesis by (2c)；(2d) hydrothermal synthesis product is washed After drying, powder is ground after 953.6 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder E2；
(3) zirconia powder E3 is prepared, specifically comprises the following steps: that (3a) calculates hydrothermal synthesis temperature: Δ according to formula (I) THydrothermal synthesis=-8.5 × 2=-17 DEG C, i.e. the hydrothermal synthesis temperature of zirconia powder E3 is 160 DEG C -17 DEG C=143 DEG C；According to formula (II) calcining heat treatment temperature: Δ T is calculatedCalcining heat treatment=16.8 × 2=33.6 DEG C, i.e. the calcining heat treatment temperature of zirconia powder E3 It is 950 DEG C+33.6 DEG C=983.6 DEG C；(3b) 94.6:10.8 is mixed and is dissolved in water in molar ratio by zirconium nitrate and yttrium nitrate, is adjusted PH to 8~10；Reaction system is warming up to 143 DEG C of progress hydrothermal synthesis by (3c)；After the washed drying of (3d) hydrothermal synthesis product, Powder is ground after 983.6 DEG C carry out calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder E3；
(4) zirconia powder E3, zirconia powder E2 and zirconia powder E1 body are stacked by sequence from bottom to top, is then carried out Dry-pressing 20MPa obtains zirconium oxide muffin X5；
(5) the sintering 1h that zirconium oxide muffin X5 is carried out to 1550 DEG C, monitors its deformation quantity, and test method is to be put in sample block It is on horizontal table, one end pushing is seamless with workbench, the gap size Δ d of the other end and workbench is measured with clearance gauge, Using calliper to measure batten thickness d, calculating and obtaining deformation data Δ d/d is 0.21.
Performance test:
(1) Zirconium powder E1, Zirconium powder E2, Zirconium powder E3 is dry-pressing formed at 20MPa, then pass through The static pressure 30s such as 200MPa obtains green compact sample block, by green compact sample block through 900 DEG C of biscuitings, obtains test specimens block, test specimens block is made Tested with TMA, be warming up to 1600 DEG C by the heating rate of 1 DEG C/min in air atmosphere, obtain starting shrinkage temperature and Shrinking percentage；
Three-point bending resistance strength test method: the above biscuiting sample block after cutting, polishing, 1500 DEG C of sintering 1h, obtain 4.0 × 1.0 × 20mm batten, after spline surfaces polishing, test three-point bending resistance intensity, span 16mm, test speed 0.5mm/min, each 10 battens of sample test, and be averaged.
Permeability test method: the above biscuiting sample block obtains 1.0mm thickness print after cutting, polishing, 1500 DEG C of sintering 1h, After twin polishing, transmittance data at spectrophotometer test 500nm wavelength is used.
Test result such as table 7:
Table 7
Serial number E1 E2 E3
Contraction initial temperature/DEG C 1048 1047 1048
Shrinking percentage/% 20.16 20.15 20.16
Intensity/MPa 1132 1028 532
From the performance test results as can be seen that after the adjusting for passing through hydrothermal synthesis temperature and calcination temperature, with the receipts of powder Shrinkage (in 20.15-20.16%) and shrinkage temperature (1047-1048 DEG C) reach unanimity, and intensity, permeability have no significant effect, powder The sintering warpage amount of cake is obviously reduced.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention, But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention Within protection scope and the open scope.

Claims (13)

1. a kind of zirconium oxide muffin, which is characterized in that the zirconium oxide muffin includes at least two layers of Zirconium powder layer, different oxygen The yttrium content for changing zirconium powder layer is different, and the different Zirconium powder layers, TMA curve shrinkage initial temperature difference≤5 DEG C；Institute State different Zirconium powder layers, TMA curve shrinkage rate deviation≤0.3%.
2. zirconium oxide muffin as described in claim 1, which is characterized in that in the zirconium oxide muffin, different Zirconium powders Yttrium content maximum difference the > 1mol%, preferably 1~5mol% of layer.
3. zirconium oxide muffin as described in claim 1, which is characterized in that the Zirconium powder layer from the bottom to top yttrium content according to Secondary increase；
Preferably, the Zirconium powder include 3 layers of Zirconium powder layer, wherein yttrium content be followed successively by 2.6~3.4mol%, 3.6~4.4mol% and 4.6~5.4mol%；The yttrium content of further preferred 3 layers of Zirconium powder layer is followed successively by 3mol%, 4mol% and 5mol%.
4. a kind of preparation method of zirconium oxide muffin, which is characterized in that the preparation method includes the following steps:
(1) zirconium source, yttrium source and other function element source are mixed in liquid phase, carry out hydrothermal synthesis；The production of liquid phase thermal synthesis Object carries out calcining heat treatment, obtains the Zirconium powder with different yttrium contents；
According to the yttrium content in Zirconium powder raw material, closed according to the hydro-thermal in following formula selective oxidation zirconium powder production procedure At temperature and calcining heat treatment temperature:
ΔTHydrothermal synthesis=-k1ΔXYttriumFormula (I)
ΔTCalcining heat treatment=k2ΔXYttriumFormula (II)
Wherein, Δ THydrothermal synthesisFor the difference of hydrothermal synthesis temperature in any two groups of Zirconium powder stock preparation process, unit is ℃；ΔTCalcining heat treatmentFor the difference for calcining heat treatment temperature in any two groups of Zirconium powder stock preparation process, unit is DEG C；Δ XYttriumFor the difference of yttrium molar content in any two groups of Zirconium powder raw materials, unit mol%；k1For the coefficient of hydrothermal synthesis 8.3~8.7；k2For the coefficient 16.6~17.0 of calcining heat treatment；
(3) Zirconium powder with yttrium content is stacked in a predetermined order, then carries out dry-pressing, obtain zirconium oxide muffin；
Preferably, the pressure of the dry-pressing is 5~100MPa, and the time is 5~30s；
Preferably, the other function element include iron, manganese, erbium, neodymium, praseodymium, cerium, in aluminium any one or at least two Combination；
Preferably, the zirconium oxide muffin includes zirconium oxide muffin described in one of claims 1 to 3.
5. preparation method as claimed in claim 4, which is characterized in that the hydrothermal synthesis specifically comprises the following steps:
(2a), which mixes zirconium source and yttrium source and other functional elements, is dissolved in water, adjusts pH to 8~10；
Reaction system is heated up and carries out hydrothermal synthesis by (2b)；
(2c) hydrothermal synthesis product is ground after calcining heat treatment, is dispersed, and is granulated, is obtained Zirconium powder；
Preferably, the zirconium source includes water dissolvable zirconates, preferably zirconium nitrate, zirconium oxychloride, in zirconium chloride any one or At least two combination；
Preferably, the yttrium source includes yttrium salt, preferably yttrium nitrate；
Preferably, the adjusting pH value is carried out by the way that ammonium hydroxide is added；
Preferably, the hydrothermal synthesis temperature be 140~200 DEG C, the time be 10~72h, preferably hydrothermal synthesis temperature be 140~ 170 DEG C, the time is 10~50h；
Preferably, the calcining heat treatment temperature be 800~1100 DEG C, 1~5h of time, preferably 900~1100 DEG C, the time 2~ 4h；
Preferably, step (2c) the hydrothermal synthesis product is washed before calcining heat treatment, is dried.
6. a kind of purposes of the zirconium oxide muffin as described in one of claims 1 to 3, which is characterized in that the zirconium oxide muffin Tooth cake, the biscuiting block of processing backboard or the biscuiting block of processing decoration product as processing artificial tooth.
7. a kind of layering aoxidizes zirconium base sintered body, which is characterized in that the layering oxidation zirconium base sintered body has at least two layers of oxygen Change zirconium sinter layer, the yttrium content of different Zirconium oxide sintering layers is different, and deflection≤0.3% of the zirconia sintered body.
8. layering oxidation zirconium base sintered body as claimed in claim 7, which is characterized in that the yttrium of the difference Zirconium oxide sintering layer Content maximum difference > 1mol%, preferably 1~5mol%；
Preferably, the layering oxidation zirconium base sintered body includes at least Zirconium oxide sintering layer, the 4mol% yttrium of 3mol% yttrium content The Zirconium oxide sintering layer of the Zirconium oxide sintering layer of content, 5mol% yttrium content, and the deflection of the zirconia sintered body≤ 0.3%.
9. a kind of preparation method of the oxidation zirconium base sintered body of layering as claimed in claim 7 or 8, which is characterized in that the system Preparation Method includes being sintered zirconium oxide muffin described in one of claims 1 to 3, obtains layering oxidation zirconium base sintered body；
Preferably, the sintering temperature is 1400~1550 DEG C, and the time is 1~3h.
10. a kind of purposes of the oxidation zirconium base sintered body of layering as claimed in claim 7 or 8, which is characterized in that the layering oxygen Change zirconium base sintered body for making artificial tooth, backboard or ornament.
11. a kind of artificial tooth, which is characterized in that the artificial tooth includes the oxidation zirconium base sintered body of layering described in claim 7 or 8；
Alternatively, the artificial tooth includes the product of the preparation method preparation of layering oxidation zirconium base sintered body as claimed in claim 9；
Alternatively, the sintering of artificial tooth zirconium oxide muffin as described in one of claims 1 to 3 obtains；
Alternatively, the zirconium oxide muffin sintering that the artificial tooth is prepared by preparation method described in claim 4 or 5 obtains.
12. a kind of adjusting method of zirconia sintered body starting shrinkage temperature, which is characterized in that the method includes walking as follows It is rapid:
(1) according to the yttrium content of scheduled Zirconium powder and scheduled contraction initial temperature, hydro-thermal is obtained according to formula (III) and is closed At temperature:
THydrothermal synthesis=k1XYttrium-TShrink starting+ 859 formulas (III)
Wherein, THydrothermal synthesisFor the hydrothermal synthesis temperature in zirconia powder production procedure, unit is DEG C；XYttriumFor scheduled zirconium oxide The yttrium content of powder, unit mol%；TShrink startingFor scheduled contraction initial temperature, unit is DEG C；k1What it is for hydrothermal synthesis is Number 8.3~8.7；
(2) zirconium source, yttrium source and other function element source are mixed in liquid phase, in THydrothermal synthesisAt a temperature of carry out hydrothermal synthesis；Water The product of thermal synthesis carries out calcining heat treatment, obtains with the predetermined Zirconium powder for shrinking initial temperature.
13. a kind of adjusting method of zirconia sintered body shrinking percentage, which is characterized in that described method includes following steps:
(1) it according to the yttrium content of scheduled Zirconium powder, scheduled shrinking percentage and liquid phase thermal synthesis temperature, is obtained according to formula (IV) Heat treatment temperature must be calcined:
TCalcining heat treatment=(σ -0.0002608Y+0.0001168THydrothermal synthesis-0.2899)/0.00007426
Formula (IV)
Wherein, THydrothermal synthesisFor the hydrothermal synthesis temperature in zirconia powder production procedure, unit is DEG C；XYttriumFor scheduled zirconium oxide The yttrium content of powder, unit mol%；TCalcining heat treatmentFor the calcining heat treatment temperature in zirconia powder production procedure, unit is ℃；σ is shrinking percentage, %；
(2) zirconium source, yttrium source and other addition element sources are mixed in liquid phase, in THydrothermal synthesisAt a temperature of carry out hydrothermal synthesis；Hydro-thermal The product of synthesis is in TCalcining heat treatmentAt a temperature of carry out calcining heat treatment, obtain with the predetermined Zirconium powder for shrinking initial temperature.
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