CN109336592A - A kind of zirconia ceramics bone implant prosthese and preparation method thereof - Google Patents

A kind of zirconia ceramics bone implant prosthese and preparation method thereof Download PDF

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CN109336592A
CN109336592A CN201811285524.4A CN201811285524A CN109336592A CN 109336592 A CN109336592 A CN 109336592A CN 201811285524 A CN201811285524 A CN 201811285524A CN 109336592 A CN109336592 A CN 109336592A
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stabilizer
additional amount
zirconia
preparation
zirconia ceramics
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CN109336592B (en
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吴梦飞
李敏杰
曹玉超
张云龙
张纪锋
梁涛
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Beijing Security Technology Co Ltd
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Abstract

The present invention provides a kind of zirconia ceramics bone implant prostheses and preparation method thereof.The preparation method comprises the following steps: zirconia powder, stabilizer A, acidic silicasol and Aluminum sol mixed grinding are obtained slurry；Solvent is added into slurry, mixes, spray drying obtains particle；Particle is placed in mold, cold equal molding, obtains green compact under 150~500MPa；By green compact in 700~1200 DEG C of pre-burnings, biscuit is obtained；Biscuit is obtained into zirconia ceramics in 900~1500 DEG C of 0.2~2h of heat preservation in microwave agglomerating furnace；To get zirconia ceramics bone implant prosthese after zirconia ceramics is processed.The means such as the present invention combined using incorporation Y/Yb, pre-burning with microwave sintering, silica solution and Aluminum sol in-situ preparation mullite, a small amount of mullite grains Dispersed precipitate is made in the bone implant prosthese of zirconia base, improves crystallite dimension, consistency, mechanical performance and the water resistant heat aging performance of zirconia ceramics bone implant prosthese.

Description

A kind of zirconia ceramics bone implant prosthese and preparation method thereof
Technical field
The present invention relates to ceramic material fields, more particularly, to a kind of zirconia ceramics bone implant prosthese and its preparation side Method.
Background technique
Zirconium oxide (ZrO2) chemical property torpescence, there is high-melting-point, high refractive index, low thermal coefficient of expansion and excellent life The characteristics such as object compatibility are widely used in the fields such as refractory material, structural ceramics, bioceramic and electric function ceramic.Oxygen Changing zirconium tool, there are three types of crystal forms: monoclinic phase, density 5.65g/cm3, equilibrium temperature is lower than 1100 DEG C；Tetragonal phase, density are 6.10g/cm3, equilibrium temperature range is 1100~2300 DEG C；Cubic phase, density 6.27g/cm3, equilibrium temperature is higher than 2300 ℃.Therefore under room temperature, zirconium oxide exists in the form of monoclinic phase.
Zirconium oxide is during the sintering process, it may occur that monoclinic phaseTetragonal phase converting generates 3~5% volume change, makes It obtains pure zirconia article fragments and loses value.It is specific frequently with being adulterated in zirconium oxide to avoid zirconium oxide from undergoing phase transition Metal oxide such as yttrium oxide (Y2O3), calcium oxide (CaO), magnesia (MgO) or cerium oxide (CeO2) etc. mode carry out Stable Oxygen Change zirconium.But in the environment existing for vapor, zirconium oxide can spontaneously produce phase transformation at room temperature, be from tetragonal phase converting Monoclinic phase, reduces zirconia ceramics performance, and this process is referred to as " hydrothermal aging ".Hydrothermal aging can reduce zirconia ceramics system The intensity of product increases surface roughness, seriously affects its service life.
Mullite is Al2O3-SiO2Binary compound uniquely stable in system, and be a kind of non-stoichiometric compound, change It learns composition general formula and is represented by A12[Al2+2xSi2-2x]O10-x(O≤x≤1), wherein x indicates Al in unit cell3+Replace Si4+When The Lacking oxygen number of generation, usual 0.17 < x < 0.59.Mullite crystal structure is with alumina octahedral (AlO6) it is parallel to C axis Direction is developed, it is lateral then with [(Si, A1) O4] tetrahedron and (AlO6) octahedra shared rib and the chain structure that links up.Four Some can be replaced coordination silicon ion by aluminium ion, form Lacking oxygen.Therefore mullite grains are to be distributed with Lacking oxygen Unsaturated spacial framework, structural void is big, than more loose, and crystal grain be column, disperse in ceramic structure can To toughening effect.
Traditional heating is that thermal energy is transferred to heating object by convection current, conduction or radiation mode by heater to make it Reach a certain temperature, heat transmits from outside to inside, and sintering time is long, is difficult to obtain fine grain.Microwave sintering is a kind of using microwave The method being sintered to material is heated, which absorbs the kinetic energy and thermal energy that microwave energy is interior molecules using material, Heat is generated from material internal, so that material is integrally uniformly heated rapidly to certain temperature and realizes densification sintering.Due to micro- Wave has very big penetrability to most of ceramic materials, can be uniformly heated up material, reduces the temperature gradient in sintering process, from And it reduces line of material and changes the deformation unevenly generated；And can be brought rapidly up, making material, residence time substantially contracts at high temperature It is short, inhibit crystal grain to grow up, improves material property.Compared with the workpiece of conventional sintering technique production, workpiece made of microwave sintering With higher density, hardness and obdurability.
Microwave sintering zirconium oxide is existing to be applied to dental polishing more, and sintered body small volume, microwave field distribution is uniform, is easy to Sintering.But for the ceramic material of large scale, complicated shape, the non-uniform probability of microwave field distribution during microwave sintering It greatly increases, adds ceramic reason such as thermal expansion coefficient itself is big and thermal conductivity is low etc., heating non-uniform phenomenon easily occur, sternly It will lead to material cracks when weight.Accordingly, with respect to dental polishing, the pottery of this kind of large scale of ceramic bone implant prosthese, complicated shape Ceramic material, the prior art mostly use the sintering of the ecto-entads such as normal pressure-sintered, hot pressed sintering or HIP sintering transmitting heat Prepared by mode, seldom use microwave sintering.
The prior art mostly uses conventional sintering process to prepare zirconia-mullite complex phase ceramic, and mullite content is generally big In 20% and crystallite dimension it is larger, ceramic dense degree is difficult to be guaranteed.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of zirconia ceramics bone implant prosthese, the preparation method It is combined using incorporation Y/Yb, pre-burning with microwave sintering, the means such as acidic silicasol and Aluminum sol in-situ preparation mullite, is made A small amount of mullite grains Dispersed precipitate improves zirconia ceramics bone implant prosthese in the ceramic bone implant prosthese of zirconia base Crystallite dimension, consistency, bending strength, fracture toughness and water resistant heat aging performance.
The second object of the present invention is to provide the zirconia ceramics bone implant prosthese of above method preparation, bone implant vacation Body is a small amount of mullite grains Dispersed precipitate in the complex phase ceramic of zirconia ceramics, compared to existing product have performance it is stable, Surface without monoclinic phase, even grain size and it is small, that bending strength is high, fracture toughness is high and water resistant heat aging performance is excellent etc. is excellent Point.
In order to solve the above technical problems, the present invention provides following technical schemes:
A kind of preparation method of zirconia ceramics bone implant prosthese, including the following steps:
By zirconia powder, stabilizer A, acidic silicasol and Aluminum sol mixed grinding, slurry is obtained；With the zirconia powder Weight on the basis of, the additional amount of the stabilizer A is 0.5~10%, addition of the acidic silicasol in terms of silica Measure X are as follows: 0 < X≤5%, additional amount Y of the Aluminum sol in terms of aluminium oxide are as follows: 0 < Y≤15%；The stabilizer A is oxidation The mixing of one or both of yttrium and ytterbium oxide；
It is added into the slurry solvent, is mixed, spray drying obtains particle；
The particle is placed in mold, cold equal molding, obtains green compact under 150~500MPa；
The green compact are kept the temperature at 700~1200 DEG C, pre-burning is completed, obtains biscuit；
The biscuit is sintered in microwave agglomerating furnace in 900~1500 DEG C of 0.2~2h of heat preservation, zirconia ceramics is obtained；
After the zirconia ceramics is processed, zirconia ceramics bone implant prosthese is obtained.
Preferably, after the cold grade and before the pre-burning, further includes: dry the green compact.
Compared with prior art, above method of the invention has reached following technical effect:
(1) present invention uses Y2O3(yttrium oxide) or Yb2O3(ytterbium oxide) or both mixing and doping ZrO2Ceramics, ceramics strength Height, and zirconia ceramics prosthese is prepared using microwave sintering, it is substantially shorter the ceramic post sintering time, crystal grain is inhibited to grow up, is improved Ceramic dense degree.During microwave sintering, high-frequency electric field can promote the migration in Grain Surface electrification vacancy, cause regional area Ionization promotes Particle diffusion and solid solution to generate.Y2O3(yttrium oxide) or Yb2O3(ytterbium oxide) or both mixing and doping ZrO2In, Lacking oxygen can be formed in ceramic matrix, at this time under high-frequency electric field effect, Grain Surface Lacking oxygen migration rate increases, and can mention Absorption rate of the high ceramic matrix to microwave, acceleration of sintering.
(2) silica solution added by the present invention is acidic silicasol, is that a kind of nanosized silica particles are evenly dispersed Dispersion liquid formed in water, contains great amount of hydroxy group.After the hydrone in silica solution evaporates, silicon oxygen is formed between colloidal particle In conjunction with can firmly be attached to other particle surfaces, improve product strength, be provided for microwave sintering and be preferably sintered matrix.This Aluminum sol added by inventing is the colloidal solution that the positively charged featheriness aluminium oxide micelle of one kind is dispersed in water, energy It is mixed with water and acidic silicasol with arbitrary proportion.Therefore acidic silicasol and Aluminum sol can be sufficiently mixed uniformly.In addition, silica solution In silica and Aluminum sol in alumina particle it is small, large specific surface area, activity is high, is easy to be sintered.In zirconia ceramics In sintering process, silica and aluminium oxide can reaction in-situ generate rod-like mullite, the rod-like mullite crystal grain is tiny and equal Even to be distributed in zirconia ceramics, main function is as follows: a, zirconia grains being inhibited to grow up；B, inhibit tetragonal zircite phase transformation； C, inhibit crack propagation, extend crack propagation approach, increase the consumption function in zirconia ceramics fracture process, toughened zirconium oxide pottery Porcelain；D, mullite grains Lacking oxygen is more, short texture, can absorb certain failure energy, further toughened zirconium oxide ceramic, and Mullite content of the Dispersed precipitate in zirconia ceramics is no more than 10%, and crystal grain is tiny, therefore can play good toughening effect Without reducing zirconia ceramics consistency to influence performance.
(3) present invention carries out pre-burning to zirconia ceramics green compact using 700~1200 DEG C of heat preservations, and biscuit is made.The process There is following positive effect: a, moisture, volatile impurity and stomata sufficiently in discharge green compact；B, tiny tetragonal zircite is formed Crystal grain and mullite grains, and both crystal grain all contain Lacking oxygen, and it is empty that a certain amount of electrification can be provided for microwave sintering initial stage Position and promote microwave sintering to carry out；C, since zirconium oxide thermal coefficient is low, thermal expansion coefficient is larger, fissipation factor 250~ 400 DEG C start to increase rapidly, and therefore, will lead to product cracking when microwave field uniformity is bad.The burn-in process can be microwave Sintering provides even compact and is sintered matrix, keeps microwave sintering more uniform, local burning caused by preventing due to uneven heating Phenomenon and product cracking.
To sum up, not only process is simple for preparation method of the invention, high production efficiency, and using incorporation Y/Yb, pre-burning with Multimedia synergistic effects such as microwave sintering combines, acidic silicasol and Aluminum sol in-situ preparation mullite significantly improve A small amount of mullite grains Dispersed precipitate is made in the complex phase ceramic of zirconia ceramics, the ceramics in the comprehensive performance of zirconia ceramics The property such as stability, surface monoclinic phase content, even grain size, bending strength, fracture toughness and water resistant heat aging performance Can it improve than existing product.
Through detecting, zirconia ceramics bone implant prosthese mullite content≤10wt% prepared by the present invention, bulk density ≥5.90g/cm3, ZrO2+HfO2>=90wt%, surface is without monoclinic phase, crystallite dimension≤0.35 μm, and four point bending strength >= 800MPa, fracture toughness >=9MPam0.5；After 134 DEG C of hydro-thermal process 5h, surface monoclinic phase content≤1%, four point bending strength >=750MPa and conservation rate >=85%.
Solvent used in the present invention can be the common solvents such as water, methanol or ethyl alcohol.
In addition, the raw material of raw material and process conditions can be also further improved in above-mentioned preparation method, it is specific as follows.
On the basis of the weight of the zirconia powder, the additional amount of the stabilizer A can appoint in 0.5~10% range Meaning selection, such as 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% etc..Wherein preferably Range has 1~10%, preferably 3~10%, preferably 5~10%, preferably 5~8%, to obtain better mechanical performance and water resistant heat Ageing properties.
On the basis of the weight of the zirconia powder, additional amount X of the acidic silicasol in terms of silica are as follows: 0 < X ≤ 5%, it can arbitrarily select in the range, such as 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 5% etc..Wherein Preferred range has: 0.2≤X≤5%, preferably 0.5≤X≤5%, preferably 2≤X≤5%.
On the basis of the weight of the zirconia powder, additional amount Y of the Aluminum sol in terms of aluminium oxide are as follows: 0.5≤Y≤ 15%, can arbitrarily select in the range, such as 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15% etc..Wherein preferred range has: 1.5≤Y≤15%, preferably 3≤Y≤10%, preferably 5≤Y≤10%.
Preferably, the mass fraction of silica is 10~25% in the acidic silicasol.
Preferably, the mass fraction of aluminium oxide is 10~30% in the Aluminum sol.
Preferably, stabilizer B is additionally added when preparing the slurry；The stabilizer B is cerium oxide, calcium oxide and oxidation The combination of one or more of magnesium.
Cerium oxide, calcium oxide and magnesia can act synergistically with yttrium oxide/ytterbium oxide, further increase zirconia ceramics Water resistant heat aging performance.
Cerium oxide, calcium oxide and magnesia can be added simultaneously, can select one of or certain several addition, such as aoxidize The mixing of the mixing of cerium, calcium oxide or magnesia or cerium oxide and magnesia, calcium oxide and magnesia, cerium oxide and calcium oxide Mixing or cerium oxide, magnesia and the combination of calcium oxide three etc..
On the basis of the weight of the zirconia powder, the additional amount of the stabilizer B is 0.5~20%, wherein preferably Range is 10~20%, preferably 10~15%.
Preferably, the stabilizer B partial size is at 44 μm hereinafter, purity is preferably in 99.9wt% or more.
Preferably, the purity of the zirconia powder are as follows: ZrO2+HfO2>=99.9wt%, preferably 74 μm or less of partial size.
Preferably, the grinding are as follows: 10~50h of wet grinding, preferably 10~40h, preferably 10~30h.
Preferably, the cold equal pressure is 200~500MPa, preferably 200~400MPa, preferably 200~300MPa.
Preferably, the temperature of the pre-burning is 700~1000 DEG C, preferably 800~1000 DEG C.
Preferably, the temperature of the sintering is 900~1400 DEG C, preferably 1000~1300 DEG C.
Preferably, after the cold grade and before the pre-burning, further includes: dry the green compact.
Preferably, it also needs to process zirconia ceramics after being sintered.
In addition, needing to control adding for stabilizer A and stabilizer B to further improve the water resistant heat aging performance of ceramics Enter amount.When usual stabilizer A additional amount is below 5%, stabilizer B need to be added；The amount of stabilizer A is fewer, then the amount of stabilizer B is got over Greatly, preferred following scheme:
Preferably, on the basis of the weight of the zirconia powder, when the additional amount of the stabilizer A is 0.5~5%, institute The additional amount for stating stabilizer B is 0.5~20%；
Preferably, on the basis of the weight of the zirconia powder, when the additional amount of the stabilizer A is 5%~10%, institute The additional amount for stating stabilizer B is 0；
Preferably, on the basis of the weight of the zirconia powder, when the additional amount of the stabilizer A is 5%~10%, institute The additional amount for stating stabilizer B is 0.5~20%.
Preferably, the additional amount of acidic silicasol is related to concentration, controls the total additional amount of silica below 5%.
Preferably, the additional amount of Aluminum sol is related to concentration, controls total alumina addition below 15%.
To sum up, compared with prior art, invention achieves following technical effects:
(1) performance that ceramics are produced using conventional sintering mode is not only optimized, but also process flow is simple, production effect Rate is high；
(2) with a variety of hands such as Y/Yb doping, pre-burning and microwave sintering, acidic silicasol and Aluminum sol in-situ preparation mullite Section combines, and collaboration improves the mechanical performance and water resistant heat aging performance of zirconia ceramics, and the present invention generates mullite Mode is unlike the prior art: acidic silicasol and Aluminum sol is separately added into a manner of colloidal sol, the two is former during the sintering process Position reaction generates mullite, and this generated in-situ mullite grains Dispersed precipitate can be significantly improved in zirconia ceramics matrix The mechanical performance and water resistant heat aging performance of zirconia ceramics；
(3) factors such as dosage, the process conditions of raw material have been screened, zirconia ceramics bone implant prosthese is further improved Performance, including crystallite dimension, consistency, bending strength, fracture toughness and water resistant heat aging performance etc.；
(4) zirconia ceramics bone implant prosthese mullite content≤10wt% prepared by the present invention, bulk density >= 5.90g/cm3, ZrO2+HfO2>=90wt%, surface is without monoclinic phase, crystallite dimension≤0.35 μm, and four point bending strength >= 800MPa, fracture toughness >=9MPam0.5；After 134 DEG C of hydro-thermal process 5h, surface monoclinic phase content≤1%, four point bending strength >=750MPa and conservation rate >=85%.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments, It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
The first step, by zirconia powder, stabilizer A, acidic silicasol (concentration 10wt%) and Aluminum sol, (concentration is It 10wt%) mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, acidic silicasol (with Silica meter), the additional amount of Aluminum sol (in terms of aluminium oxide) be respectively 5%, 3%, 7.5%；Stabilizer A is yttrium oxide, grain Diameter≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 2
The difference from embodiment 1 is that the additional amount of stabilizer A is different, it is specific as follows.
The first step, by zirconia powder, stabilizer A, acidic silicasol (concentration 10wt%) and Aluminum sol, (concentration is It 10wt%) mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, acidic silicasol (with Silica meter), the additional amount of Aluminum sol (in terms of aluminium oxide) be respectively 8%, 3%, 7.5%；Stabilizer A is yttrium oxide, grain Diameter≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 3
The difference from embodiment 1 is that the additional amount of stabilizer A is different, it is specific as follows.
The first step, by zirconia powder, stabilizer A, acidic silicasol (in terms of silica), Aluminum sol (in terms of aluminium oxide) Mixing, wet grinding 30h obtain slurry；On the basis of the weight of zirconia powder, stabilizer A and acidic silicasol are (with titanium dioxide Silicon meter) additional amount be respectively 10%, 3%, 7.5%；Stabilizer A is yttrium oxide, partial size≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 4
The difference from embodiment 1 is that the additional amount of acidic silicasol, Aluminum sol is different, it is specific as follows.
The first step, by zirconia powder, stabilizer A, acidic silicasol (concentration 10wt%) and Aluminum sol, (concentration is It 10wt%) mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, acidic silicasol (with Silica meter), the additional amount of Aluminum sol (in terms of aluminium oxide) be respectively 5%, 5%, 15%；Stabilizer A is yttrium oxide, partial size ≤5μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 5
The difference from embodiment 1 is that the additional amount of acidic silicasol, Aluminum sol is different, it is specific as follows.
The first step mixes zirconia powder, stabilizer A and acidic silicasol, and wet grinding 30h obtains slurry；With oxidation On the basis of the weight of zirconium powder, the additional amount of stabilizer A and acidic silicasol (in terms of silica) is respectively 5%, 0.2%, 0.5%；Stabilizer A is yttrium oxide, partial size≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μ m；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 6
The difference from embodiment 1 is that another stabilizer is added in raw material, it is specific as follows.
It is the first step, zirconia powder, stabilizer A, stabilizer B, acidic silicasol (concentration 10wt%) and Aluminum sol is (dense Degree is 10wt%) it mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, stabilizer B and Acidic silicasol (in terms of silica), Aluminum sol (in terms of aluminium oxide) additional amount be respectively 5%, 10%, 3%, 7.5%； Stabilizer A is yttrium oxide, partial size≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；Stablize Agent B is cerium oxide, and partial size is at 44 μm hereinafter, purity is preferably in 99.9wt% or more；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 7
It is that the type of stabilizer B is different from the difference of embodiment 6, it is specific as follows.
It is the first step, zirconia powder, stabilizer A, stabilizer B, acidic silicasol (concentration 10wt%) and Aluminum sol is (dense Degree is 10wt%) it mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, stabilizer B, Acidic silicasol (in terms of silica), Aluminum sol (in terms of calcium oxide) additional amount be respectively 5%, 10%, 3%, 7.5%； Stabilizer A is yttrium oxide, partial size≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；Stablize Agent B is magnesia, and partial size is at 44 μm hereinafter, purity is preferably in 99.9wt% or more；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 8
It is that the additional amount of stabilizer B is different from the difference of embodiment 6, other conditions are the same as embodiment 6.
It is the first step, zirconia powder, stabilizer A, stabilizer B, acidic silicasol (concentration 10wt%) and Aluminum sol is (dense Degree is 10wt%) it mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, stabilizer B and Acidic silicasol (in terms of silica), Aluminum sol (in terms of aluminium oxide) additional amount be respectively 5%, 0.5%, 3%, 7.5%； Stabilizer A is yttrium oxide, partial size≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；Stablize Agent B is cerium oxide, and partial size is at 44 μm hereinafter, purity is preferably in 99.9wt% or more；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 9
The difference from embodiment 1 is that the addition type of stabilizer A is different, yttrium oxide is replaced with into ytterbium oxide, other Part is the same as embodiment 1.
The first step, by zirconia powder, stabilizer A, acidic silicasol (concentration 10wt%) and Aluminum sol, (concentration is It 10wt%) mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, acidic silicasol (with Silica meter), the additional amount of Aluminum sol (in terms of aluminium oxide) be respectively 5%, 3%, 7.5%；Stabilizer A is ytterbium oxide, grain Diameter≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 10
The difference from embodiment 1 is that the addition type of stabilizer A is different, partial oxidation yttrium is replaced with into ytterbium oxide, two The weight such as person, total additional amount is still the 5% of powdered zirconium oxide, and other conditions are the same as embodiment 1.
The first step, by zirconia powder, stabilizer A, acidic silicasol (concentration 10wt%) and Aluminum sol, (concentration is It 10wt%) mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, acidic silicasol (with Silica meter), the additional amount of Aluminum sol (in terms of aluminium oxide) be respectively 5%, 3%, 7.5%；Stabilizer A is yttrium oxide and oxygen Change ytterbium etc. to mix again, partial size≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 250MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1000 DEG C of heat preservation 5h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1200 DEG C of heat preservation 1h by the 5th step, zirconia ceramics is obtained, finally by oxygen Change zircon ceramic to be processed to get zirconia ceramics bone implant prosthese.
Embodiment 11
The difference from embodiment 1 is that process conditions have difference, it is specific as follows.
The first step, by zirconia powder, stabilizer A, acidic silicasol (concentration 10wt%) and Aluminum sol, (concentration is It 10wt%) mixes, wet grinding 30h obtains slurry；On the basis of the weight of zirconia powder, stabilizer A, acidic silicasol (with Silica meter), the additional amount of Aluminum sol (in terms of aluminium oxide) be respectively 5%, 3%, 7.5%；Stabilizer A is yttrium oxide, grain Diameter≤5 μm；Powdered zirconium oxide purity are as follows: ZrO2+HfO2>=99.9wt%, partial size≤74 μm；
Water is added into slurry for second step, mixes, and spray drying obtains particle；
Third step, the molding such as cold under 150MPa by particle in a mold, obtain green compact；
4th step after drying green compact, in 1100 DEG C of heat preservation 3h, completes pre-burning, obtains biscuit；
Biscuit is sintered in microwave agglomerating furnace in 1400 DEG C of heat preservation 0.5h by the 5th step, is obtained zirconia ceramics, finally will Zirconia ceramics is processed to get zirconia ceramics bone implant prosthese.
Comparative example 1
Difference with embodiment 11 is to mix 10% stabilizer B in raw material, and the dosage and technique of other raw materials are homogeneous Together.
The performance for the zirconia ceramics prosthese that above embodiments obtain is as shown in table 1.
The performance of 1 zirconia ceramics prosthese of table
It can determine by table 1, zirconia ceramics bone implant prosthese bulk density >=5.90g/cm prepared by the present invention3, ZrO2 +HfO2>=90wt%, surface monoclinic phase≤0.5%, crystallite dimension≤0.35 μm, four point bending strength >=800MPa are broken tough Property >=9MPam0.5；After 134 DEG C of hydro-thermal process 5h, surface monoclinic phase content≤1%, four point bending strength >=750MPa and guarantor Holdup >=85%.The purity that the present invention is also tested for zirconium oxide in final products is ZrO2+HfO2>=90wt%, surface is without monocline Phase.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of preparation method of zirconia ceramics bone implant prosthese, characterized in that it comprises the following steps:
By zirconia powder, stabilizer A, acidic silicasol and Aluminum sol mixed grinding, slurry is obtained；With the weight of the zirconia powder On the basis of amount, the additional amount of the stabilizer A is 0.5~10%, additional amount X of the acidic silicasol in terms of silica Are as follows: 0 < X≤5%, additional amount Y of the Aluminum sol in terms of aluminium oxide are as follows: 0 < Y≤15%；The stabilizer A be yttrium oxide and The mixing of one or both of ytterbium oxide；
It is added into the slurry solvent, is mixed, spray drying obtains particle；
The particle is placed in mold, cold equal molding, obtains green compact under 150~500MPa；
The green compact are kept the temperature at 700~1200 DEG C, pre-burning is completed, obtains biscuit；
The biscuit is sintered in microwave agglomerating furnace in 900~1500 DEG C of 0.2~2h of heat preservation, zirconia ceramics is obtained；
The zirconia ceramics is processed to get zirconia ceramics bone implant prosthese；
Preferably, after the cold grade and before the pre-burning, further includes: dry the green compact.
2. preparation method according to claim 1, which is characterized in that described on the basis of the weight of the zirconia powder The additional amount of stabilizer A is 1~10%, preferably 3~10%, preferably 5~10%, preferably 5~8%.
3. preparation method according to claim 1, which is characterized in that described on the basis of the weight of the zirconia powder Additional amount X of the additional amount of acidic silicasol in terms of silica are as follows: 0.2≤X≤5%, preferably 0.5≤X≤5%, preferably 2≤ X≤5%；Additional amount Y of the Aluminum sol in terms of aluminium oxide are as follows: 0.5≤Y≤15%, preferably 1.5≤Y≤15%, preferably 3≤Y ≤ 10%, preferably 5≤Y≤10%；
Preferably, the mass fraction of silica is 10~25% in the acidic silicasol；Aluminium oxide in the Aluminum sol Mass fraction is 10~30%.
4. described in any item preparation methods according to claim 1, which is characterized in that be additionally added stabilization when preparing the slurry Agent B；The stabilizer B is the combination of one or more of cerium oxide, calcium oxide and magnesia.
5. the preparation method according to claim 4, which is characterized in that described on the basis of the weight of the zirconia powder The additional amount of stabilizer B is 0.5~20%, preferably 10~20%, preferably 10~15%；
Preferably, described steady when the additional amount of the stabilizer A is 0.5~5% on the basis of the weight of the zirconia powder The additional amount for determining agent B is 0.5~20%；
Preferably, described steady when the additional amount of the stabilizer A is 5%~10% on the basis of the weight of the zirconia powder The additional amount for determining agent B is 0；
Preferably, described steady when the additional amount of the stabilizer A is 5%~10% on the basis of the weight of the zirconia powder The additional amount for determining agent B is 0.5~20%.
6. the preparation method according to claim 4, which is characterized in that the stabilizer B partial size is at 44 μm hereinafter, purity is excellent Select mass fraction 99.9% or more.
7. preparation method according to claim 1, which is characterized in that the purity of the zirconia powder are as follows: ZrO2+HfO2≥ 99.9wt%, preferably 74 μm or less of partial size.
8. preparation method according to claim 1, which is characterized in that the grinding are as follows: 10~50h of wet grinding, preferably 10~40h, preferably 10~30h.
9. preparation method according to claim 1, which is characterized in that the cold equal pressure is 200~500MPa, preferably 200~400MPa, preferably 200~300MPa；
Preferably, the temperature of the pre-burning is 700~1000 DEG C, preferably 800~1000 DEG C；
Preferably, the temperature of the sintering is 900~1400 DEG C, preferably 1000~1300 DEG C.
10. a kind of zirconia ceramics bone implant prosthese, which is characterized in that use the described in any item preparation sides claim 1-9 Method is made.
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CN109773183A (en) * 2019-04-08 2019-05-21 长沙集智创新工业设计有限公司 A kind of medical metal ceramic material and preparation method thereof
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CN112030028B (en) * 2020-09-03 2022-03-01 北京安颂科技有限公司 Aluminum oxide-based metal composite ceramic, preparation method thereof, aluminum oxide-based metal composite ceramic bone implantation prosthesis and application
CN115304370A (en) * 2021-05-07 2022-11-08 苏州宸泰医疗器械有限公司 Zirconia-yttrium aluminum garnet composite ceramic and bone implant prosthesis prepared from same
CN115233336A (en) * 2022-06-27 2022-10-25 东华大学 Preparation method of uniform and compact high-temperature continuous zirconia filament

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