CN110092669A - A kind of zirconium oxide bioceramic of surface modification and preparation method thereof - Google Patents

A kind of zirconium oxide bioceramic of surface modification and preparation method thereof Download PDF

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Publication number
CN110092669A
CN110092669A CN201910508546.0A CN201910508546A CN110092669A CN 110092669 A CN110092669 A CN 110092669A CN 201910508546 A CN201910508546 A CN 201910508546A CN 110092669 A CN110092669 A CN 110092669A
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bioceramic
basis material
surface modification
preparation
solution
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孔令兵
张天舒
刘银
董强
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Nanjing Sanotes Material Technology Co Ltd
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Nanjing Sanotes Material Technology Co Ltd
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Priority to CN202010532797.5A priority patent/CN111499416B/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5035—Silica

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to a kind of preparation methods of the zirconium oxide bioceramic of surface modification, the preparation method is the surface modification using the modifier solution of synthesis to the progress of bioceramic basis material at least once, then the bioceramic basis material Jing Guo surface modification is sintered, wherein, the process of the surface modification, which refers to, is placed in the bioceramic basis material in the modifier solution, on the surface of the basis material modifying agent coating is formed after for a period of time to the surface modification of the bioceramic basis material, the sintering processes, which refer to, is formed with the bioceramic basis material of modifying agent coating after the conversion process for completing gel to surface, it is sintered with sintering process, to which modifying agent is incorporated on bioceramic basis material.

Description

A kind of zirconium oxide bioceramic of surface modification and preparation method thereof
Technical field
The present invention relates to a kind of zirconium oxide biology of biomaterial surface technical field of modification more particularly to surface modification potteries Porcelain and preparation method thereof.
Background technique
One kind that zirconium oxide bioceramic is made of high-purity zirconium dioxide is bordering on inert bioceramic, is by that will contain There is the high-purity zirconium dioxide of a small amount of stabilizer to be made by high temperature sintering, high stable agent is, for example, calcium oxide, magnesia or oxygen Change yttrium.Not only there is good wearability, antibiosis reason corrosivity and biocompatibility, but also its fracture toughness and intensity are excellent In aluminium oxide ceramics.It is mainly used for the reparation and replacement of the sclerous tissues such as human synovial, dental implant.
Zirconium oxide has high chemical stability and thermal stability (Tm=2953K), inertia is presented in physiological environment, With good biocompatibility.There are three types of allotropy bodies for pure zirconia tool: monoclinic zirconia (m phase), tetragonal zircite (t Phase) and cubic zirconia (c phase), three kinds of allotropy bodies be present in different temperature ranges, and under certain condition can be with Occur transformation of crystal (phase transformation).Solid solution is formed by being added between additive and zirconium oxide appropriate, zirconium oxide can be made Four directions and cubic still keep stable or metastable state at room temperature.Make zirconia ceramics by stress-induced phase transformation toughening With very high mechanical property.When bearing external force, tetragonal zircite (t phase) is converted to monoclinic zirconia (m phase) Process need to absorb higher energy, make crack tip stress relaxation, increase crackle diffusional resistance and toughening, thus have very high Fracture toughness.For partially stabilized zirconium oxide as aluminium oxide, biocompatibility is good, in In vivo stability height, and compares Aluminium oxide fracture toughness, wearability are higher, advantageous to reduce implantation material size and realize low friction, abrasion, to manufacture root of the tooth, Bone, femoral joint, composite ceramics artificial bone, valve etc..Although zirconia ceramics has outstanding mechanical property, it is as biology Inert material cannot but be formed with bone tissue and is chemically combined, and influence the reliability and long-term efficacy of implant.It is past in the prior art Toward the method modified by addition bioactive ingredients or surface, so that zirconia ceramics has certain bioactivity, it is desirable that It can reach will not generate apparent influence to its mechanical property while assigning zirconia ceramics bioactivity, and biology The bond strength and long-time stability of active surface layer will can satisfy the requirement of clinical application.
Influencing material bioactive factor mainly has surface roughness, configuration of surface, surface energy and surface chemical composition Deng, and surface chemical composition play the role of it is key.The biological activity combination of bone tissue takes place mostly in bioactive materials Combination between surface and bone tissue.Two types can be divided into: a kind of such as dense hydroxy apatite ceramic, surface are hydroxy-apatite Stone, directly in conjunction with bone tissue；Another kind of such as bio-vitric and biological active glass ceramic, can be in physiological environment in surface shape At hydroxyapatite layer.The bioceramics such as zirconium oxide are widely used at present with its good biocompatibility and aesthetic effect In mouth mending material hat and fixed bridge, also have broad application prospects as planting body material.But since inorganic oxide zirconium etc. is raw The intensity of object ceramics is high, and electric conductivity is poor, causes to be surface-treated difficulty to it.
Carrying out surface modification treatment to zirconium oxide becomes the focus studied at present to improve its adhesive property, mainly includes object Reason method and chemical method, blasting treatment: usually improving roughness with sandblasting improves its bonding, and sandblasting equally damages zirconium oxide Surface, this may influence whether that the mechanical performance of zirconium oxide ontology, the variation size of mechanical performance may cause to aoxidize with damage The content of zirconium phase transformation and the scratch depth on surface are related.Existing producer is it is not recommended that with the surface of blasted rough zirconium oxide.Acid etching Processing: acid etching silicates ceramics can dissolve porcelain surface portion glass matrix, be allowed to form coarse surface texture, Increase bond area.And for zirconia ceramics, the effect of this processing of acid etching, which needs follow-up study further, to be confirmed, to obtain More accurate conclusion.Laser-induced thermal etching: can increase surface roughness, but after laser treatment, the mechanical performance of zirconium oxide, especially It, which is anti-aging property, and whether fatigue performance is affected etc. needs further to detect.Selectively penetrating acid etching: logical The bond area for crossing increase zirconium surface increases micromechanics packing interaction to reach.Surface silicon coating: including chemical rubbing manipulation, Sol-gel method, plasma spraying, pyrolysismethod etc..But due to matching of thermal expansion coefficient etc., the combination of coating and substrate Problem into one up for inquiring into.Cold plasma processing: being a kind of effective measures of reinforcing material surface hydrophilicity, if material Expect that the hydrophily on surface is stronger, is more conducive to the adherency of early stage cell and the differentiation of cell, there is also the matchings of coating and substrate Problem.The carbonato hydroxyapatite coating layer in surface: the planting body of the coating containing HA shows good early stage bon e formation Osteoconductive, but equally exist the combination problem of coating and substrate.
Chinese patent (Publication No. CN106669440A) provides the modification method and modified pottery of a kind of ceramic membrane Porcelain film.The modification method of the ceramic membrane are as follows: ceramic membrane is surface-treated, fresh ceramic membrane is obtained；By silanes Compound is coated to the surface of ceramic membrane by infusion process or sedimentation；Ceramic membrane after coating is carried out to heat under protective atmosphere It handles, obtains modified modified ceramic film after Temperature fall.The modification method for the ceramic membrane that the patent provides, which has, to be repaired Decorations process is simple, low raw-material cost, and modification not will cause the secondary pollution of environment；Pass through the modified ceramic of modification preparation Film has the features such as long-time stability are high, anti acid alkali performance is strong, ultra-hydrophobicity relative to common are machine maintenance exterior material；It can be extensive Applied to fields such as sea water desalination, water-oil separating, wastewater treatments.
Chinese patent (Publication No. CN103409715B) discloses a kind of porous TiO2/SiO2The preparation side of composite coating Method belongs to medical bio field of ceramic coatings.The patent uses the preparation spraying of planetary ball mill mixing method to use TiO first2/SiO2It is multiple Close powder；Secondly TiO is prepared using air plasma spraying method2/SiO2Composite coating；Then hydro-thermal etching processing pair is utilized TiO2/SiO2Composite coating surface carries out porous and bioactivation processing, is immersed in induction osteoid apatite shape in simulated body fluid At.After impregnating 28 days, porous TiO2/SiO2Composite coating Surface Creation osteoid apatite, and TiO as a comparison2/SiO2 Composite coating surface is then generated without osteoid apatite.The standby porous TiO of the patent system2/SiO2Composite coating, which is conducive to improve, plants Enter the bioactivity of body ceramic coating and improve the combination of bone tissue and coating, can be used for novel bioactive bone replacement material Material.
However, chemical stability high for intensity be high and matrix in not for the biology pottery basis material of silicon oxide-containing, pass The mode of surface modification provided by the silane coupled and above-mentioned patent of the silicate ceramics of system is applied to such biology Tao Ji There is biggish difficulty on body material such as zirconia ceramics.
In addition, on the one hand since the understanding to those skilled in the art has differences；On the other hand since inventor makes Lot of documents and patent are had studied when of the invention, but length limits and do not enumerate all details and content in detail, however this is absolutely Non-present invention does not have the feature of these prior arts, and present invention has been provided with all features of the prior art, Er Qieshen Ask someone to retain the right for increasing related art in the background technology.
Summary of the invention
For the deficiencies of the prior art, the present invention provides a kind of preparation sides of the zirconium oxide bioceramic of surface modification Method, the preparation method are the surface modifications using the modifier solution of synthesis to the progress of bioceramic basis material at least once, Then the bioceramic basis material Jing Guo surface modification is sintered, wherein the process of the surface modification refers to The bioceramic basis material is placed in the modifier solution, to one section of surface modification of the bioceramic basis material Modifying agent coating is formed on the surface of the basis material after time, the sintering processes, which refer to, is formed with modifying agent coating to surface Bioceramic basis material after the conversion process for completing gel, be sintered with sintering process so that modifying agent to be incorporated in On bioceramic basis material.
According to a kind of preferred embodiment, the bioceramic basis material can be ZrO2、Al2O3, in carbon fiber one A or several combination or the bioceramic basis material can be the high-temperature superconductor of the suitable transition metal oxide of mixing The monocrystal chip ZrO of film2With the monocrystal chip ZrO for the high-temperature superconducting thin film for mixing suitable rare earth oxide2。
According to a kind of preferred embodiment, the preparation method is at least further comprising the steps of: to by surface modification Bioceramic basis material be sintered after, with process for treating surface to this by this by surface modification biology make pottery Porcelain basal body material is surface-treated, the Surface Characterization of the bioceramic basis material to proceed through surface modification.
According to a kind of preferred embodiment, the modifying agent includes at least unmodified silica solution and/or modified silicasol.
According to a kind of preferred embodiment, the step of synthesizing the unmodified silica solution, is included at least CH3CH2OH, go from Sub- water, Si (OC2H5)4And HCl is sequentially added in mixed liquid equipment with certain volume ratio, at normal temperature carry out ultrasonic vibration and/ Or be performed under heating conditions and be stirred, the pH value and insulation reaction at least 1H of acquired solution are adjusted, it is molten to obtain unmodified silicon Glue.
According to a kind of preferred embodiment, the step of synthesizing the modified silicasol, is including at least the CH in offer3Si (CH3O)3Middle addition deionized water simultaneously carries out ultrasonic vibration mixing, obtains uniformly mixed CH3Si(CH3O)3Solution passes through addition HCl adjusts CH3Si(CH3O)3The pH value of solution makes its pH value no more than 7 reaction is hydrolyzed.
According to a kind of preferred embodiment, the step of synthesizing the modified silicasol, is included at least in a heated condition to water The CH obtained after solution3Si(CH3O)3Solution, unmodified silica solution and ammonium hydroxide are stirred mixing with certain molal volume ratio, To obtain the modified silicasol that pH value is not less than 7.
According to a kind of preferred embodiment, by being split, being sintered to bioceramic idiosome, sanding and polishing, at sandblasting It manages to obtain multiple bioceramic basis materials of identical size, the bioceramic matrix that will be obtained after processing Material is put into deionized water or CH3CH2It is cleaned by ultrasonic in OH and is dried, obtains at least one of pending surface modification Bioceramic basis material.
According to a kind of preferred embodiment, the modified silicasol of synthesis is coated in pending surface modification at least one On bioceramic basis material, or at least one bioceramic basis material of pending surface modification is placed in changing for synthesis Property silica solution in, by the surface of the bioceramic basis material modifier solution complete wetting, and be transferred to certain wet It is dried under the atmospheric condition of degree, is converted into gel to complete the colloidal sol of surface modification of the bioceramic basis material Process.
According to a kind of preferred embodiment, when being sintered the bioceramic basis material Jing Guo surface modification, control sintering The technological parameter of technique, to obtain the bioceramic basis material by surface modification for reaching target particles diameter, the technique Parameter includes at least sintering time, heating rate, cooling rate.
Zirconium oxide bioceramic of a kind of surface modification provided by the invention and preparation method thereof at least has following beneficial Technical effect:
The preparation method of the zirconium oxide bioceramic of surface modification provided by the present invention, can effectively improve such as oxygen Change the adhesive strength between the such bioceramic basis material and resin of zirconium bioceramic, and with it is conventional in the prior art The technology that chemical rubbing manipulation and sedimentation etc. carry out surface covering is compared, process equipment required for preparation method of the invention Simply, equipment cost is low low with temperature needed for preparation process.It uses in preparation method provided by the present invention and first adjusts simultaneously Acidic environment is hydrolyzed, then adjusts the method that alkaline environment carries out heat preservation catalysis and prepare the modifying agent, shortens carry out water Time needed for solution reaction and polymerization reaction, greatly increase the preparation efficiency of preparation method, and the preparation method gram The mode for having taken the surface modifications such as silane coupled of traditional silicate ceramics is applied to have biggish difficulty on zirconia ceramics The problem of spending, the zirconium oxide after obtaining the surface modification that mechanical performance, biocompatibility and surface adhesive property have both Bioceramic.
Specific embodiment
A kind of preparation method of the zirconium oxide bioceramic of surface modification, the preparation method are molten using the modifying agent of synthesis Liquid carries out surface modification at least once to bioceramic basis material, then to the bioceramic matrix material Jing Guo surface modification Material is sintered.Traditional surface modification or surface are modified just like surface covering method, nitriding, anodic oxidation, chemical gas Mutually deposition, physical vapour deposition (PVD), ion beam sputter depositing etc., in the prior art novel surface modification or process for modifying surface Just like metal vapor vacuum arc ion source ion implanting, ion beam enhanced/assistant depositing, plasma source ion implantation, laser table Surface alloying, laser chemical vapor deposition, plasma auxiliary chemical vapor deposition, Double Glow Plasma surface alloying Deng passing through that surface is modified to assign traditional ceramics product certain functionality.The process of the surface modification refers to the biology Ceramic matrix material is placed in the modifier solution, to the surface modification of the bioceramic basis material for a period of time after at this The surface of basis material forms silicon coating.The sintering processes refer to the bioceramic matrix that modifying agent coating is formed with to surface Material is sintered modifying agent being incorporated in bioceramic matrix material with sintering process after the conversion process for completing gel On material.
According to a kind of preferred embodiment, the bioceramic basis material can be zirconium dioxide, aluminum oxide, carbon One or several combinations in fiber.Wherein, carbon fiber refers to high strength and modulus fiber of the carbon content 90% or more.Carbon Fiber is to be carbonized by doing raw material with acrylic fibers and viscose rayon through high-temperature oxydation.The bioceramic basis material can be with For the monocrystal chip ZrO of the high-temperature superconducting thin film of the suitable transition metal oxide of mixing2With the suitable rare earth oxide of mixing High-temperature superconducting thin film monocrystal chip ZrO2.Wherein, the monocrystal chip ZrO of high-temperature superconducting thin film2, i.e. zirconium oxide (ZrO2) by In ZrO2Monocrystalline need to mix yttrium to stablize its structure, and what is generally actually used is the oxidation that yttrium stabilizer is added in YSZ single-crystal-- Zirconium monocrystalline.Wherein, 15 kinds of lanthanide series that rare earth oxide refers to that period of element atom ordinal number is 57 to 71 aoxidize Object, and the oxide of scandium similar with lanthanide series chemical property and yttrium totally 17 kinds of elements.
According to a kind of preferred embodiment, the preparation method is at least further comprising the steps of: to by surface modification Bioceramic basis material be sintered after, with process for treating surface to this by this by surface modification biology make pottery Porcelain basal body material is surface-treated, the Surface Characterization of the bioceramic basis material to proceed through surface modification.The table Fourier infrared spectrograph characterization that face characterization includes at least field emission microscopy observation, X-ray energy spectrum analysis meter is sought peace.
According to a kind of preferred embodiment, the modifying agent includes at least unmodified silica solution and/or modified silicasol.Silicon Colloidal sol is the grade amorphous SiO of nanometer2Particle, by charge or other supplementary forms, the colloid of stably dispersing in water is molten in water Liquid is a kind of environmentally friendly, inexpensive inorganic nano material.Silica solution can be divided into water silica sol according to the difference of solvent property and have Solvent silica solution, organic solvent silicasol are primarily used to form the hard of the molding synthetic resins body surface such as lens, bottle, film, piece face Film.
According to a kind of preferred embodiment, the step of synthesizing the unmodified silica solution, is included at least ethyl alcohol, deionization Water, TEOS and concentrated hydrochloric acid are sequentially added in mixed liquid equipment with certain volume ratio, at normal temperature carry out ultrasonic vibration and/or It is stirred mixing under heating condition, adjusts the pH value and insulation reaction at least 1H of acquired solution, obtains unmodified silica solution.It is super The high frequency sound wave generation oscillation referred to using ultrasonic wave is swung in acoustic shock, and the high frequency sound wave of ultrasonic wave generates oscillation, mainly makes liquid Strong cavitation and emulsion occurs, the effect as experimental analysis is mainly reflected in elution and dissolution, for extracting, stirring It mixes, cleaning vessel etc..Ultrasonic wave refers to that frequency is 20 kilo hertzs~50 megahertzs or so of electromagnetic wave.
According to a kind of preferred embodiment, the step of synthesizing the modified silicasol, is including at least the CH in offer3Si (CH3O)3Middle addition deionized water simultaneously carries out ultrasonic vibration mixing, obtains uniformly mixed CH3Si(CH3O)3Solution passes through addition HCl adjusts CH3Si(CH3O)3The pH value of solution makes its pH value no more than 7 reaction is hydrolyzed.Wherein, hydrolysis is salt electricity Hydrogen ion and hydroxide ion that the ions binding separated out water power separates out generate the reaction of weak electrolyte molecule.Hydrolysis is What substance and water occurred cause, and substance decomposes reacts and (be not necessarily metathesis reaction) and could also say that in substance and water Hydrogen ion either hydroxide ion react.
According to a kind of preferred embodiment, the step of synthesizing the modified silicasol, is included at least in a heated condition to water The CH obtained after solution3Si(CH3O)3Solution, unmodified silica solution and ammonium hydroxide are stirred mixing with certain molal volume ratio, To obtain the modified silicasol that pH value is not less than 7.
According to a kind of preferred embodiment, by being split, being sintered to bioceramic idiosome, sanding and polishing, at sandblasting It manages to obtain multiple bioceramic basis materials of identical size, the bioceramic matrix that will be obtained after processing Material is put into deionized water or CH3CH2It is cleaned by ultrasonic in OH and is dried, obtains at least one of pending surface modification Bioceramic basis material.Blasting treatment, which refers to, uses compressed air for power, to form high velocity spray beam for material spray (copper mine Sand, quartz sand, diamond dust, iron sand, sea sand) it is ejected into need to handle workpiece surface at a high speed, make the appearance or shape hair of workpiece surface Changing.Impact and shear action due to abrasive material to workpiece surface make the surface of workpiece obtain certain cleannes and difference Roughness, improve the mechanical performance of workpiece surface, therefore improve the fatigue resistance of workpiece.Polishing, which refers to, utilizes machine The effect of tool, chemistry or electrochemistry, reduces workpiece surface roughness, the processing method to obtain bright, flat surface.
According to a kind of preferred embodiment, the modified silicasol of synthesis is coated in pending surface modification at least one On bioceramic basis material, or at least one bioceramic basis material of pending surface modification is placed in changing for synthesis Property silica solution in, by the surface of the bioceramic basis material modifier solution complete wetting, and be transferred to certain wet It is dried under the atmospheric condition of degree, is converted into gel to complete the colloidal sol of surface modification of the bioceramic basis material Process.There are two types of state, colloidal sol and gels for colloid.Colloidal sol is liquefied half flowing shape, the property of approximate fluid.Colloidal sol can turn Become a kind of gel of semi-solid state for having certain elasticity, this process is known as gelatification, gel and colloidal sol in certain item It can be mutually converted under part, gel conversion claims colloidal sol to act at the process of colloidal sol.Colloidal sol and gel is caused to mutually convert main Factor is temperature.When the temperature decreases, the kinetic energy of micelle reduces, and micelle both ends are interconnected so that form reticular structure, Hydrone is all in the hole of eyed structure, and at this moment colloid is in gel state.When the temperature increases, the kinetic energy of micelle increases, The movement velocity of molecule is speeded, and the connection of micelle disappears, and reticular structure no longer exists, and micelle is in free movement state, here it is Colloidal sol.The difference of colloidal sol and gel is colloidal sol and flow behavior is pseudoplastic behavior, and gel flow behavior is Bingham fluid.
According to a kind of preferred embodiment, when being sintered the bioceramic basis material Jing Guo surface modification, control sintering The technological parameter of technique, to obtain the bioceramic basis material by surface modification for reaching target particles diameter, the technique Parameter includes at least sintering time, heating rate, cooling rate.Wherein, sintering process, which refers to, is changed into densification granular material Body is a traditional technical process, can use this technique to produce ceramics, powder metallurgy, refractory material, superhigh temperature material Material etc..In general, powder is after overmolding, is a kind of polycrystalline material by being sintered obtained dense body, microstructure by Crystal, vitreum and stomata composition.Sintering process directly affects crystallite dimension, pore size and grain-boundary shape in microstructure And distribution, and then influence the performance of material.
The preparation method of the zirconium oxide bioceramic of surface modification provided by the present invention, can effectively improve such as oxygen Change the adhesive strength between the such bioceramic basis material and resin of zirconium bioceramic, and with it is conventional in the prior art The technology that chemical rubbing manipulation and sedimentation etc. carry out surface covering is compared, process equipment required for preparation method of the invention Simply, equipment cost is low low with temperature needed for preparation process.It uses in preparation method provided by the present invention and first adjusts simultaneously Acidic environment is hydrolyzed, then adjusts the method that alkaline environment carries out heat preservation catalysis and prepare the modifying agent, shortens carry out water Time needed for solution reaction and polymerization reaction, greatly increase the preparation efficiency of preparation method, and the preparation method gram The mode for having taken the surface modifications such as silane coupled of traditional silicate ceramics is applied to have biggish difficulty on zirconia ceramics The problem of spending, the zirconium oxide after obtaining the surface modification that mechanical performance, biocompatibility and surface adhesive property have both Bioceramic.
It should be noted that above-mentioned specific embodiment is exemplary, those skilled in the art can disclose in the present invention Various solutions are found out under the inspiration of content, and these solutions also belong to disclosure of the invention range and fall into this hair Within bright protection scope.It will be understood by those skilled in the art that description of the invention be it is illustrative and not constitute to power The limitation that benefit requires.Protection scope of the present invention is defined by the claims and their equivalents.

Claims (10)

1. a kind of preparation method of the zirconium oxide bioceramic of surface modification, which is characterized in that the preparation method is to utilize synthesis Modifier solution surface modification at least once is carried out to bioceramic basis material, then to the biology Jing Guo surface modification Ceramic matrix material is sintered, wherein
The process of the surface modification, which refers to, is placed in the bioceramic basis material in the modifier solution, to the biology The surface modification of ceramic matrix material for a period of time after the basis material surface formed modifying agent coating, the sintering processes Refer to and the bioceramic basis material of modifying agent coating is formed with after the conversion process for completing gel to surface, with sintering process It is sintered, so that modifying agent is incorporated on bioceramic basis material.
2. preparation method according to claim 1, which is characterized in that the bioceramic basis material can be ZrO2、 Al2O3, one or several combination in carbon fiber or the bioceramic basis material can be to be mixed with suitable transition The monocrystal chip ZrO of the high-temperature superconducting thin film of metal oxide2With the high-temperature superconducting thin film for being mixed with suitable rare earth oxide Monocrystal chip ZrO2。
3. the preparation method according to one of preceding claims, which is characterized in that the preparation method at least further include with Lower step: after being sintered to the bioceramic basis material by surface modification, with process for treating surface to the warp It crosses the bioceramic basis material Jing Guo surface modification to be surface-treated, to proceed through the bioceramic of surface modification The Surface Characterization of basis material.
4. the preparation method according to one of preceding claims, which is characterized in that the modifying agent includes at least unmodified Silica solution and/or modified silicasol.
5. the preparation method according to one of preceding claims, which is characterized in that the step of the synthesis unmodified silica solution It is rapid to include at least CH3CH2OH, deionized water, Si (OC2H5)4And HCl sequentially adds mixed liquid equipment with certain volume ratio In, ultrasonic vibration is carried out at normal temperature and/or is performed under heating conditions to be stirred, and adjusts the pH value of acquired solution and heat preservation At least 1H is reacted, unmodified silica solution is obtained.
6. the preparation method according to one of preceding claims, which is characterized in that the step of synthesizing the modified silicasol Including at least the CH in offer3Si(CH3O)3Middle addition deionized water simultaneously carries out ultrasonic vibration mixing, obtains uniformly mixed CH3Si(CH3O)3Solution adjusts CH by addition HCl3Si(CH3O)3The pH value of solution makes its pH value no more than 7 to be hydrolyzed Reaction.
7. the preparation method according to one of preceding claims, which is characterized in that the step of synthesizing the modified silicasol Including at least in a heated condition to the CH obtained after hydrolysis3Si(CH3O)3Solution, unmodified silica solution and ammonium hydroxide are with certain Molal volume ratio be stirred mixing, with obtain pH value be not less than 7 modified silicasol.
8. the preparation method according to one of preceding claims, which is characterized in that by dividing bioceramic idiosome Cut, be sintered, sanding and polishing, blasting treatment to obtain multiple bioceramic basis materials of identical size, will handle The bioceramic basis material obtained afterwards is put into deionized water or CH3CH2It is cleaned by ultrasonic in OH and is dried, is obtained At least one bioceramic basis material of pending surface modification.
9. the preparation method according to one of preceding claims, which is characterized in that the modified silicasol of synthesis to be coated in On at least one bioceramic basis material of pending surface modification, or by pending surface modification at least one biology Ceramic matrix material is placed in the modified silicasol of synthesis, by the surface of the bioceramic basis material modifier solution Complete wetting, and be transferred under the atmospheric condition of certain humidity and be dried, to complete the table of the bioceramic basis material The colloidal sol of face modification is converted into the process of gel.
10. the preparation method according to one of preceding claims, which is characterized in that be sintered the biology Jing Guo surface modification When ceramic matrix material, control the technological parameter of sintering process, with obtain reach target particles diameter by surface modification Bioceramic basis material, the technological parameter include at least sintering time, heating rate, cooling rate.
CN201910508546.0A 2019-06-12 2019-06-12 A kind of zirconium oxide bioceramic of surface modification and preparation method thereof Pending CN110092669A (en)

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CN201910508546.0A CN110092669A (en) 2019-06-12 2019-06-12 A kind of zirconium oxide bioceramic of surface modification and preparation method thereof
CN202010532797.5A CN111499416B (en) 2019-06-12 2020-06-11 Surface-modified zirconia biological ceramic and preparation method thereof

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CN116751078B (en) * 2023-06-28 2024-05-14 浙江大学 Preparation method, product and application of zirconia surface micro-nano structure based on precipitation-heat treatment

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