CN113248278B - Modified zirconia ceramic with surface compounded with bioactive substances and preparation method thereof - Google Patents
Modified zirconia ceramic with surface compounded with bioactive substances and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified zirconia ceramic with a surface compounded with a bioactive substance and a preparation method thereof. The method comprises the following steps: preparing calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol; preparing a zirconium oxide suspension; preparing a zirconia ceramic having a porous surface layer; putting the zirconia ceramic with the porous surface layer into calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol by a negative pressure infiltration process, so that the bioactive sol is infiltrated into the porous surface layer, and carrying out heat treatment after drying to obtain the ceramic. According to the invention, calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances are loaded in the pore channels of the porous surface layer of the zirconia to endow the zirconia ceramic with high bioactivity, and the porous surface layer is combined with the zirconia ceramic and synchronously sintered, so that the problem of poor interface bonding strength of a surface active layer and a zirconia matrix material is solved; the bioactive substances only permeate into the porous surface layer, the internal matrix still keeps high density after sintering, and the mechanical property of the material is not obviously influenced.
Description
Technical Field
The invention relates to the field of medical materials for dental restoration, in particular to a modified zirconia ceramic with a surface compounded with bioactive substances and a preparation method thereof.
Background
Titanium and titanium alloy implants in metal implants have found widespread use in the clinical treatment of tooth loss due to dental caries, periodontitis, dental trauma and the like. However, there are problems such as blackening of titanium metal due to gingival atrophy and hypersensitivity due to release of toxic ions. The zirconia ceramic has good biocompatibility and chemical stability, excellent mechanical property and unique aesthetic effect, thereby becoming a dental prosthetic material with good clinical application prospect. The zirconia ceramics as inert materials have no bioactivity, and after being implanted into a body, the surrounding fibrous tissues can block the integration of the implant and the surrounding bone tissues, thereby causing implantation failure, so that the development of the bioactive zirconia dental repair materials has important significance.
In recent years, modified zirconia is generally subjected to surface modification by a coating method, but the coating method generally has the problem of mismatch of thermal expansion coefficients, so that residual stress exists, the bonding degree of a substrate and a coating interface is weak, the substrate and the coating interface can be dissolved and fall off in an oral cavity for a long time and are not suitable for clinical application, the mechanical strength of zirconia ceramics is seriously influenced due to phase change caused by the current surface modification means, the addition amount of bioactive substances and the types of the bioactive substances are limited, and the improvement on the biological performance is limited. CN112028626A discloses a method for preparing zirconia bioactive ceramics, which shows poor bonding degree due to residual stress caused by mismatch of thermal expansion coefficients of the coating and the substrate, and may cause coating peeling in long-term application. CN106904962B discloses a method for preparing bioactive zirconia dental ceramic material, in which the active substance existing in the grain boundary influences the mechanical property of zirconia, and the addition amount of the active substance is limited. CN109867520A discloses a zirconium oxide-based strontium, silicon and fluorine trace doped hydroxyapatite zirconium oxide toughened composite coating, a preparation method and application thereof, and the problem of coating falling caused by insufficient bonding degree exists. CN110917394A discloses the application of ion modified zirconia surface in the preparation of zirconia abutment or implant, and also has the problem of coating peeling caused by insufficient binding degree. The silver ion modified zirconia has improved antibacterial performance, but does not promote the proliferation and differentiation of cells.
The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has a stimulating effect on the gene expression of osteoblasts, and can obviously promote bone regeneration in clinical application. The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has good bioactivity, biocompatibility, biodegradability and mechanical properties, releases active ions such as calcium, magnesium, silicon, phosphorus and the like, can induce the formation of a apatite layer, and is beneficial to the combination of materials and bone tissues. The deposition of wollastonite on the surface of porous alumina ceramic can obviously improve the bioactivity of the porous alumina ceramic and mineralize apatite. Diopside scaffolds induce apatite production, supporting human osteoblast adhesion, growth and alkaline phosphatase (ALP) expression. Therefore, the research of the zirconia dental ceramic which has high bioactivity and high strength and has high bonding strength between the surface modification layer and the matrix is of great significance.
Disclosure of Invention
In order to overcome the defects that the conventional biological modified zirconia dental ceramic in the prior art cannot simultaneously have excellent biological activity and high mechanical strength, the invention aims to provide a modified zirconia ceramic with a surface compounded with a biological active substance and a preparation method thereof. The zirconia ceramic material has good biological activity, high mechanical property and simple preparation process.
The purpose of the invention is realized by at least one of the following technical solutions.
According to the preparation method provided by the invention, calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol is loaded in the pore channel of the porous surface layer of the zirconia, and the generated calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance is embedded in the pore channel of the surface layer of the zirconia through high-temperature heat treatment, so that the zirconia ceramic is endowed with high bioactivity. The porous surface layer is combined with zirconia ceramics and synchronously sintered, thereby solving the problem of poor interface bonding strength of the surface active layer and the zirconia matrix material; the bioactive substances only permeate into the porous surface layer, the internal matrix still keeps high density after sintering, the mechanical property of the material is not obviously influenced, and the problem that the conventional biological modified zirconia dental ceramic cannot have good bioactivity and high mechanical strength at the same time can be solved.
The preparation method of the modified zirconia ceramic with the surface compounded with the bioactive substances, provided by the invention, comprises the following steps:
(1) preparing calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol: adding a hydrolyzable silicon-containing compound, a water-soluble calcium salt, a water-soluble magnesium salt or a water-soluble phosphorus salt into deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 6.0-8.0, and carrying out hydrolytic polycondensation reaction to obtain calcium-magnesium silica sol or calcium-silicon-phosphorus sol;
(2) pressing and molding zirconia powder to prepare a zirconia ceramic green body, and heating for pre-sintering treatment to obtain a zirconia ceramic pre-sintered body;
(3) preparation of zirconia suspension: adding a pore-forming agent, a stabilizing agent, a dispersing agent and zirconia powder into a solvent, and uniformly mixing to obtain a suspension; dipping (dip-coating process) or spraying the suspension (high-stability and high-dispersity zirconia suspension) on the surface of the zirconia ceramic pre-sintered body (the suspension is permeated and adsorbed on the surface of the pre-sintered body) in the step (2), drying to form a pore-forming surface layer, and heating to perform sintering treatment to obtain the zirconia ceramic with the porous surface layer;
(4) soaking the zirconia ceramic with the porous surface layer in the step (3) in the calcium-magnesium-silica sol or calcium-silicon-phosphorus sol prepared in the step (1) in a container, performing negative pressure infiltration treatment (the calcium-magnesium-silica or calcium-silicon-phosphorus bioactive sol is infiltrated into the porous surface layer of the zirconia ceramic through the negative pressure infiltration treatment), taking out, standing, aging and drying to obtain the zirconia ceramic with the composite surface layer; and heating the zirconia ceramic with the compounded surface layer for heat treatment to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the compounded surface bioactive substances.
Further, the silicon-containing compound in the step (1) is at least one of ethyl orthosilicate, silicon acetate and methyl silicate;
further, the calcium salt in the step (1) is at least one of calcium nitrate, calcium chloride, calcium acetate and calcium citrate;
further, the magnesium salt in the step (1) is at least one of magnesium nitrate, magnesium chloride, magnesium acetate and magnesium citrate;
further, the phosphorus salt in step (1) is at least one of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Further, the mixed solution in the step (1) comprises the following components in parts by weight:
further, the time of the hydrolytic polycondensation reaction in the step (1) is 24-48 h.
Further, the pressure of the compression molding in the step (2) is 100-220MPa, and the time of the compression molding is 2-30 min;
preferably, the press-forming of step (2) comprises: filling zirconia powder into a plastic mould, sealing and molding by using an isostatic press.
Further, the temperature of the pre-sintering treatment in the step (2) is 500-; the rate of temperature rise is 2-10 ℃/min.
Further, the pore-forming agent in the step (3) is at least one of a polyethylacrylate microsphere, a polylactic acid-glycolic acid copolymer microsphere, a polyacrylic acid microsphere and a polystyrene microsphere, a polymethyl methacrylate microsphere and a graphite microsphere, and the particle size of the pore-forming agent is 1-20 μm;
further, the stabilizer in the step (3) is at least one of polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral and glycerol;
further, the dispersant in the step (3) is at least one of polyethylene glycol, polyacrylic acid and polymethacrylate ammonia;
further, the solvent in the step (3) is at least one of water and absolute ethyl alcohol.
Further, the suspension in the step (3) comprises the following components in parts by weight:
further, the drying temperature in the step (3) is 60-100 ℃, and the drying time is 6-12 h;
further, the thickness of the pore-forming surface layer in the step (3) is 10-80 μm;
preferably, the thickness of the pore-forming surface layer in the step (3) is 20-80 μm.
Preferably, the average pore diameter in the pore-forming surface layer in the step (3) is 0.1-50 μm, and the porosity is 20% -70%.
Further, the temperature of the sintering treatment in the step (3) is 1300-.
Preferably, the impregnating of step (3) comprises: and (3) soaking the zirconia ceramic pre-sintered body in zirconia suspension for 10s-2min, and quickly pulling out the zirconia ceramic pre-sintered body from the suspension 1 after soaking.
Preferably, the spraying of step (3) comprises: and spraying the suspension 1 on the zirconia ceramic pre-sintered body, wherein the spraying pressure is 0.2MPa, and the spraying time is 0.5-4 min.
Preferably, the zirconia powder in step (2) and step (3) is partially stabilized tetragonal zirconia powder with any one or more of Y2O3, MgO, CaO and La2O3 as a stabilizer.
Further preferably, the zirconia powder in step (2) and step (3) is yttria-stabilized zirconia powder.
Further, the infiltration pressure of the negative pressure infiltration treatment in the step (4) is 0-0.2 MPa, and the time of the negative pressure infiltration treatment is 10s-80 min;
further, the standing and aging time in the step (4) is 6-48 h; the drying temperature in the step (4) is 60-180 ℃, and the drying time is 12-72 h;
preferably, the temperature of the drying in step (4) is 60-100 ℃.
Further, the temperature of the heat treatment in the step (4) is 600-.
The invention provides a modified zirconia ceramic with a surface compounded with bioactive substances, which is prepared by the preparation method.
The invention permeates the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol into a zirconia pore canal with a porous surface layer structure, the sol is converted into gel after being dried at low temperature, then the sol is subjected to high-temperature heat treatment to generate calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances, and partial liquid phase or solid phase diffusion is generated in the high-temperature sintering process, so that certain bonding strength is ensured between the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances and zirconia, and the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances are embedded into the non-through pore canal, thereby ensuring that the bioactive substances cannot fall off from the pore canal and endowing the zirconia with high bioactivity.
In the preparation method provided by the invention, the sol is dried at low temperature and subjected to high-temperature heat treatment to generate the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances, and through controlling the composition and the heat treatment system of the sol, one or more of calcium-magnesium-silicon bioactive crystalline substances such as wollastonite, akermanite, diopside, whitlaite, and amesite or calcium-silicon-phosphorus bioactive glass substances can be generated, and the existence of the bioactive substances endows the zirconium oxide with high bioactivity. The porous surface layer structure and the zirconia ceramic are synchronously sintered, the materials are consistent, the problem of poor interface bonding strength of the surface active layer and the zirconia matrix material is solved, and the porosity, the pore size and the thickness of the porous surface layer structure can be regulated and controlled. The porous surface layer structure can permeate various active substances, is not limited by the types of the active substances, improves the dental ceramic repairing effect, promotes wider clinical application of the dental ceramic, and has certain social and economic values.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method provided by the invention, the porous zirconia layer is constructed on the surface of the zirconia ceramic with the compact structure for the first time, the thickness, the pore diameter and the porosity of the porous zirconia layer can be adjusted at will, the zirconia ceramic with the compact structure in the interior ensures that the dental ceramic has excellent mechanical strength, and the calcium, magnesium, silicon or calcium, silicon and phosphorus bioactive substances are loaded on the pore channel of the porous zirconia surface layer. The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has a stimulating effect on the gene expression of osteoblasts, can obviously promote bone regeneration in clinical application, has a stimulating effect on the gene expression of osteoblasts, and can obviously promote bone regeneration in clinical application. The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has good bioactivity, biocompatibility, biodegradability and mechanical properties, releases active ions such as calcium, magnesium, silicon, phosphorus and the like, can induce the formation of a apatite layer, and is beneficial to the combination of materials and bone tissues.
(2) After the modified zirconia dental ceramic with the surface compounded with the bioactive substances prepared by the invention is soaked in simulated body fluid for a period of time, weakly crystallized hydroxyapatite which is an inorganic substance in bone tissues can be mineralized on the surface, so that the bioactivity is obviously improved;
(3) the porous zirconia surface layer prepared by the invention can permeate various active sols without being limited by components and is not limited to one or more bioactive sols. The infiltration capacity of the bioactive sol can be adjusted by regulating the thickness, the pore diameter and the porosity of the porous surface layer of the zirconia, so that the bioactivity of the dental ceramic can be obviously improved;
(4) in the preparation method provided by the invention, the related zirconia ceramic surface modification treatment method is implemented on a presintered body formed and processed by zirconia ceramic, so that the problem of high processing difficulty of the sintered zirconia ceramic due to high hardness and high density is avoided, special equipment is not needed, the preparation method is simple, the yield is high, and the cost is low;
(5) compared with the problems that the bioactive coating prepared on the surface of a zirconia ceramic compact sintered body in the prior art is easy to peel off and dissolve in a complex oral environment due to poor interface bonding, the porous surface layer and the internal matrix of the zirconia ceramic with the porous surface layer are made of the same material, so that the prepared bioactive surface layer and the zirconia ceramic are an integrated material, the problem of residual stress caused by mismatch of thermal expansion coefficients is solved, the bioactive coating is more stably and firmly bonded with alveolar bone tissues, long-term stable bioactivity can be maintained, and the long-term clinical treatment effect is better.
Drawings
FIG. 1 is a cross-sectional microstructure result diagram of a modified zirconia ceramic with a surface compounded with a bioactive substance prepared in examples 1 to 4.
Fig. 2 is a surface microstructure result diagram of the modified zirconia ceramic surface-compounded with the bioactive substance according to example 1.
Fig. 3 is a graph showing the result of the microstructure of the modified zirconia ceramic with the surface compounded with bioactive substances of example 1 after 7 days of simulated body fluid mineralization by SBF.
Fig. 4 is a graph showing the result of the microstructure of the modified zirconia ceramic with the surface compounded with bioactive substances of example 2 after 7 days of simulated body fluid mineralization by SBF.
Fig. 5 is a graph showing the result of the microstructure of the modified zirconia ceramic with the surface compounded with bioactive substances of example 3 after 7 days of simulated body fluid mineralization by SBF.
FIG. 6 is a graph showing the results of co-culturing the modified zirconia ceramics with bioactive substances compounded on the surfaces thereof in examples 1 to 3, zirconia ceramics without any modification treatment, and mouse bone marrow mesenchymal stem cells for 1 day and 3 days.
FIG. 7 is a graph showing ALP quantification results of co-culture of the modified zirconia ceramics with bioactive substances compounded on the surfaces, which are obtained in examples 1 to 3, and zirconia ceramics without any modification treatment with mouse bone marrow mesenchymal stem cells for 7 days and 14 days.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
(1) Preparing the calcium-magnesium-silicon bioactive sol: adding 10g of ethyl orthosilicate, 20g of calcium nitrate and 30g of magnesium nitrate into 50g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and performing hydrolytic polycondensation reaction (the reaction time is 12 hours) to form calcium-magnesium-silica sol;
(2) pressing and molding yttria-stabilized zirconia powder at 220MPa for 2min to prepare a zirconia ceramic green body, and heating to 500 ℃ for presintering treatment at the speed of 10 ℃/min for 2h to obtain a zirconia ceramic presintering body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:10:2:53:25, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process, wherein the dipping time is 10s, the porous surface layer is dried for 12h at the temperature of 60 ℃ after the zirconia suspension is permeated and adsorbed, a pore-forming surface layer (the thickness is 10um) is formed, and then the sintering is carried out for 2h at the temperature of 1350 ℃ and the heating rate is 5 ℃/min, so as to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-magnesium-silicon bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-magnesium-silicon bioactive sol suspension is permeated into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive sol;
(6) and (4) heating the zirconia ceramic of the porous surface layer composite calcium-magnesium-silicon bioactive sol prepared in the step (5) to 1300 ℃ for heat treatment for 0.5h at the heating rate of 10 ℃/min to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) of the surface composite bioactive substance.
Part a of fig. 1 is a cross-sectional microstructure result diagram of the modified zirconia ceramic surface-composited with bioactive substances prepared in example 1; as can be seen from fig. 1, the porous surface layer is tightly bonded to the zirconia matrix, and the thickness of the porous surface layer is about 10 μm.
Fig. 2 is a surface microstructure result diagram of the modified zirconia ceramic surface-compounded with the bioactive substance according to example 1. As can be seen from fig. 2, the pore size distribution of the porous surface layer is relatively uniform and the porosity is relatively high.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in the embodiment has high bioactivity, as shown in fig. 3, after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of a sample with the surface layer permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is remarkably improved.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1100MPa, and the thickness of the surface porous layer is 10 mu m by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Example 2
(1) Preparing the calcium-magnesium-silicon bioactive sol: adding 10g of ethyl orthosilicate, 20g of calcium nitrate and 30g of magnesium citrate into 50g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and carrying out hydrolytic polycondensation reaction (the reaction time is 24 hours) to form calcium-magnesium-silica sol;
(2) pressing and molding yttria-stabilized zirconia powder under the pressure of 100MPa for 30min to prepare a zirconia ceramic green body, and heating to 500 ℃ for pre-sintering treatment at the temperature of 2h and the heating rate of 2 ℃/min to obtain a zirconia ceramic pre-sintered body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:10:2:53:25, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process for 20s, drying the suspension at 60 ℃ for 12h after the porous surface layer permeates and adsorbs the zirconia suspension to form a pore-forming surface layer (the thickness is 10 mu m), and then sintering the surface layer at 1350 ℃ for 2h, wherein the temperature rising rate is 5 ℃/min to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-magnesium-silicon bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-magnesium-silicon bioactive sol permeates into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive substance;
(7) and (4) heating the zirconia ceramic of the porous surface layer composite calcium-magnesium-silicon bioactive sol prepared in the step (6) to 1300 ℃ for heat treatment for 0.5h at the heating rate of 10 ℃/min to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) of the surface composite calcium-magnesium-silicon bioactive substance.
Part b of fig. 1 is a cross-sectional microstructure result diagram of the modified zirconia ceramic with a surface-compounded bioactive substance prepared in example 2; as can be seen from fig. 1, the porous surface layer is tightly bonded to the zirconia matrix, and the thickness of the porous surface layer is about 15 μm.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in the embodiment has high bioactivity, as shown in fig. 4, after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of a sample with the surface layer permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is remarkably improved.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1050MPa, and the thickness of the surface porous layer is 15 mu m by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Example 3
(1) Preparing the calcium-silicon-phosphorus bioactive sol: adding 31g of ethyl orthosilicate, 29g of calcium nitrate and 20g of sodium phosphate into 20g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and performing a hydrolysis polycondensation reaction (the reaction time is 24 hours) to form calcium-silicon-phosphorus sol;
(2) pressing and molding yttria-stabilized zirconia powder at the pressure of 180MPa for 10min to prepare a zirconia ceramic green body, and heating to 500 ℃ for presintering treatment at the temperature of 2h and the heating rate of 5 ℃/min to obtain a zirconia ceramic presintering body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:10:2:53:25, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process for 20s, drying the porous surface layer at 60 ℃ for 12h after the porous surface layer permeates and adsorbs the zirconia suspension to form a pore-forming surface layer (the thickness is 10um), and sintering the pore-forming surface layer at 1350 ℃ for 2h, wherein the temperature rising rate is 5 ℃/min to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-silicon-phosphorus bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-magnesium-silicon bioactive sol permeates into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive substances;
(6) and (3) heating the zirconia ceramic with the porous surface layer compounded with the calcium-phosphorus-silicon bioactive sol prepared in the step (5) to 800 ℃ for heat treatment for 0.5h, wherein the heating rate is 10 ℃/min, so as to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the surface compounded with the calcium-phosphorus-silicon bioactive substances.
Part c of fig. 1 is a cross-sectional microstructure result of the modified zirconia ceramic surface-compounded with bioactive substances prepared in example 3; as can be seen from fig. 1, the porous surface layer is tightly bonded to the zirconia matrix, and the thickness of the porous surface layer is about 25 μm.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in this example has high bioactivity, as shown in fig. 5, after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of the sample after the surface layer is permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is significantly improved.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1120MPa, and the thickness of the surface porous layer is 25 mu m by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Example 4
(1) Preparing the calcium-silicon-phosphorus bioactive sol: adding 31g of ethyl orthosilicate, 34g of calcium nitrate and 15g of sodium phosphate into 20g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and performing a hydrolysis polycondensation reaction (the reaction time is 24 hours) to form calcium-silicon-phosphorus sol;
(2) pressing and molding yttria-stabilized zirconia powder at the pressure of 200MPa for 10min to prepare a zirconia ceramic green body, and heating to 500 ℃ for presintering treatment at the temperature of 2h and the heating rate of 5 ℃/min to obtain a zirconia ceramic presintering body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:5:2:53:30, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process for 20s, drying the porous surface layer at 60 ℃ for 12h after the porous surface layer permeates and adsorbs the zirconia suspension to form a pore-forming surface layer (the thickness is 10um), and sintering the pore-forming surface layer at 1350 ℃ for 2h, wherein the temperature rising rate is 5 ℃/min to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-phosphorus-silicon bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-phosphorus-silicon bioactive sol permeates into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive substance;
(6) and (3) heating the zirconia ceramic with the porous surface layer compounded with the calcium-phosphorus-silicon bioactive sol prepared in the step (5) to 900 ℃ for heat treatment for 0.5h, wherein the heating rate is 10 ℃/min, so as to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the surface compounded with the calcium-phosphorus-silicon bioactive substances.
Part d of FIG. 1 is a cross-sectional microstructure result diagram of the surface-composite bioactive substance-modified zirconia ceramic prepared in example 4; as can be seen from FIG. 1, the surface porous layer was tightly bonded to the zirconia matrix, and the thickness of the porous layer was about 35 μm.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in this embodiment has high bioactivity, and after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of a sample with the surface layer permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is significantly improved, as shown in fig. 3-5.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1150MPa, and the thickness of the surface porous layer is 35um by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Cell experiments
Measuring proliferation of cells: under aseptic conditions, the modified zirconia ceramics with the surface compounded with the calcium, phosphorus and silicon bioactive substances prepared in the examples 1-3 and the zirconia ceramics without any modification treatment are sterilized at high temperature and high pressure and then dried to obtain zirconia ceramic samples (respectively marked as the example 1 sample, the example 2 sample, the example 3 sample and a blank group sample). Then putting each zirconia ceramic sample into a 48-pore plate respectively, soaking for 6h by using a complete culture medium, sucking away the complete culture medium, adding the mouse bone marrow mesenchymal stem cell suspension with the generation of 9 into the pore plate, wherein the number of cells in each pore is 10000, and the culture process is changed into the complete culture medium every other day. When the cells were cultured for 1d and 3d, the cells were assayed for expression of osteogenic differentiation alkaline phosphatase activity.
Determination of alkaline phosphatase expression: under aseptic conditions, the modified zirconia ceramics with the surface compounded with the calcium, phosphorus and silicon bioactive substances prepared in the examples 1-3 and the zirconia ceramics without any modification treatment are sterilized at high temperature and high pressure and then dried to obtain zirconia ceramic samples (respectively marked as the example 1 sample, the example 2 sample, the example 3 sample and a blank group sample). Then respectively putting each zirconia ceramic sample into a 48-pore plate, soaking for 6h by using a complete culture medium, sucking away the complete culture medium, adding mouse bone marrow mesenchymal stem cell suspension with the generation of 9 into the pore plate, wherein the number of cells in each pore is 20000, and replacing osteogenic induction liquid every other day in the culture process. When the cells were cultured for 7d and 14d, the cells were assayed for expression of osteogenic differentiation alkaline phosphatase activity.
The preparation of the zirconia ceramic without any modification treatment comprises the following steps: pre-sintering body of zirconia ceramic and calcining treatment. The zirconia ceramic pre-sintered body can be obtained by referring to step (2) of example 1, and then the zirconia ceramic pre-sintered body is subjected to a firing treatment, the firing treatment being: heating to 1300 deg.C for 0.5h at a heating rate of 10 deg.C/min.
FIG. 6 is a graph showing the results of co-culturing the modified zirconia ceramics with bioactive substances compounded on the surfaces thereof in examples 1 to 3, zirconia ceramics without any modification treatment, and mouse bone marrow mesenchymal stem cells for 1 day and 3 days.
As can be seen from fig. 6, the modified zirconia ceramic with a surface compounded with a bioactive substance prepared in the example and the mouse bone marrow mesenchymal stem cells were cultured together for 1 day and 3 days, and the cell proliferation effect was better than that of the zirconia ceramic without any modification treatment, and the cell proliferation condition was significantly improved.
At the time of 7 days and 14 days of co-culture, mouse bone marrow mesenchymal stem cells in each sample group were taken and detected using an ALP quantification kit. FIG. 7 is a graph showing ALP quantification results of co-culture of the modified zirconia ceramics with bioactive substances compounded on the surfaces, which are obtained in examples 1 to 3, and zirconia ceramics without any modification treatment with mouse bone marrow mesenchymal stem cells for 7 days and 14 days.
As can be seen from FIG. 7, the osteogenic differentiation effect of the cells of the modified zirconia ceramic with the surface compounded with the bioactive substances and the mouse bone marrow mesenchymal stem cells cultured together for 7 days and 14 days is better than that of the zirconia ceramic without any modification treatment, and the osteogenic differentiation condition of the cells is remarkably improved. Blank groups in fig. 6 and 7 show zirconia ceramics without any modification treatment, and 1, 2, and 3 show the example 1 sample, the example 2 sample, and the example 3 sample, respectively.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (9)
1. A preparation method of modified zirconia ceramics with a surface compounded with bioactive substances is characterized by comprising the following steps:
(1) adding a silicon-containing compound, a calcium salt, a magnesium salt or a phosphorus salt into water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 6.0-8.0, and performing hydrolytic polycondensation reaction to obtain calcium-magnesium silica sol or calcium-silicon-phosphorus sol;
(2) pressing and molding zirconia powder, heating to perform presintering treatment to obtain a zirconia ceramic presintering body;
(3) adding a pore-forming agent, a stabilizing agent, a dispersing agent and zirconia powder into a solvent, and uniformly mixing to obtain a suspension; dipping or spraying the suspension on the surface of the zirconia ceramic pre-sintered body in the step (2), drying to form a pore-forming surface layer, and heating for sintering treatment to obtain the zirconia ceramic with a porous surface layer;
(4) soaking the zirconia ceramic with the porous surface layer in the step (3) in the calcium-magnesium-silica sol or calcium-silicon-phosphorus sol prepared in the step (1), performing negative pressure infiltration treatment, taking out, standing for aging, and drying to obtain the zirconia ceramic with the composite surface layer; and heating the zirconia ceramic with the surface layer compounded for heat treatment to obtain the modified zirconia ceramic with the surface compounded with the bioactive substances.
2. The method for preparing the surface-composite bioactive substance-modified zirconia ceramic according to claim 1, wherein the silicon-containing compound in the step (1) is at least one of tetraethoxysilane, silicon acetate and methyl silicate; the calcium salt in the step (1) is at least one of calcium nitrate, calcium chloride, calcium acetate and calcium citrate; the magnesium salt in the step (1) is at least one of magnesium nitrate, magnesium chloride, magnesium acetate and magnesium citrate; the phosphorus salt in the step (1) is at least one of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
3. The method for preparing the surface-modified zirconia ceramic with a bioactive substance compounded thereon according to claim 1, wherein the time of the hydrolytic polycondensation reaction in the step (1) is 24 to 48 hours.
4. The method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances as claimed in claim 1, wherein the pressure for the compression molding in the step (2) is 100-220MPa, and the time for the compression molding is 2-30 min; the temperature of the pre-sintering treatment is 500-1000 ℃, and the time of the pre-sintering treatment is 0.5-3 h; the rate of temperature rise is 2-10 ℃/min.
5. The method of claim 1, wherein the pore-forming agent in step (3) is at least one of polyethylacrylate microspheres, polylactic acid-glycolic acid copolymer microspheres, polyacrylic acid microspheres and polystyrene microspheres, polymethyl methacrylate microspheres, and graphite microspheres, and the particle size of the pore-forming agent is 1-20 μm; the stabilizer in the step (3) is at least one of polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral and glycerol; the dispersant in the step (3) is at least one of polyethylene glycol and polyacrylic acid; and (4) the solvent in the step (3) is at least one of water and absolute ethyl alcohol.
6. The method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances according to claim 1, wherein the suspension in the step (3) comprises the following components in parts by mass:
0.5-10 parts of pore-forming agent;
5-40 parts of a stabilizer;
0.1-2 parts of a dispersant;
15-40 parts of zirconia powder;
20-50 parts of a solvent.
7. The method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances according to claim 1, wherein the drying temperature in the step (3) is 60-100 ℃, and the drying time is 6-12 h; the thickness of the pore-forming surface layer in the step (3) is 20-80 μm; the sintering treatment temperature in the step (3) is 1300-1600 ℃, the sintering treatment time is 2-4h, and the heating rate is 2-10 ℃/min.
8. The method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances according to the claim 1, characterized in that the infiltration pressure of the negative pressure infiltration treatment in the step (4) is 0-0.2 MPa, and the time of the negative pressure infiltration treatment is 10s-80 min; the standing and aging time of the step (4) is 6-48 h; the drying temperature in the step (4) is 60-180 ℃, and the drying time is 12-72 h; the temperature of the heat treatment in the step (4) is 600-1300 ℃, the time of the heat treatment is 0.5-4h, and the heating rate is 2-10 ℃/min.
9. A modified zirconia ceramic with a surface compounded with a bioactive substance, which is prepared by the preparation method according to any one of claims 1 to 8.
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