CN111646822A - Preparation method of in-situ growth honeycomb-shaped nano structure on surface of zirconia ceramic and prepared modified zirconia ceramic - Google Patents
Preparation method of in-situ growth honeycomb-shaped nano structure on surface of zirconia ceramic and prepared modified zirconia ceramic Download PDFInfo
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Abstract
The invention discloses a preparation method of a honeycomb-shaped nano structure grown on the surface of zirconia ceramic in situ and a prepared modified zirconia ceramic, wherein a series of novel honeycomb-shaped nano structures with controllable pore diameters are successfully prepared on the surface of the zirconia ceramic by a simple high-pressure hydrothermal treatment way for the first time, the obtained nano structure is grown on the surface in situ, the main component is zirconium hydrogen phosphate, the bonding property of material surface decorative porcelain or resin adhesive can be obviously improved, the bonding property is respectively improved by about 10 or 7MPa, the proliferation and osteogenic differentiation properties of surface osteoblasts are effectively promoted, and the modified zirconia ceramic has good clinical application prospect.
Description
Technical Field
The invention belongs to the field of biomedical materials, and relates to a preparation method of a honeycomb-shaped nano structure on the surface of zirconia ceramic and a prepared modified zirconia ceramic.
Background
The zirconia surface has strong chemical stability and difficult modification, so the bonding performance of the zirconia surface with surface decorative porcelain or resin adhesive is poor, and the zirconia surface also lacks the autonomous integration capability with surrounding bone tissues. At present, the modification method for zirconia surface morphology mainly comprises sand blasting, acid etching, sand blasting acid etching, laser, selective permeation acid etching and the like. The methods can change the surface appearance structure of the zirconia, but the preparation methods only adopt surface irregular etching, are difficult to consciously prepare some nanostructures which are beneficial to regulating and controlling functions of osteogenesis related cells, and are difficult to generate chemical groups required for later-stage functionalization. In addition, the construction of the surface functionalized coating is also a common modification strategy of the zirconia material, and the surface coating prepared by utilizing bioactive materials such as calcium phosphate and the like can enhance the bioactivity of the zirconia ceramic. The biggest problem of the coating is that the binding force between the coating and the substrate is not enough, and the coating is easy to peel off from the ceramic surface in long-term application, thereby limiting the clinical application of the coating. Therefore, how to realize the surface functional modification of the zirconia ceramics by a simple way is one of the key bottleneck problems for solving the clinical problems of the zirconia ceramics.
Disclosure of Invention
The patent aims at a preparation method for preparing a series of honeycomb-shaped nano structures on the surface of zirconia ceramic. The preparation method is simple and convenient to operate, good in repeatability and strong in controllability. The zirconia ceramics prepared by the method has good bioactivity, can obviously improve the adhesive property of surface decorative ceramics and resin adhesive, and has good clinical application prospect.
In order to achieve the above object, the present invention provides the following technical route:
the preparation method of the zirconia ceramic surface in-situ growth honeycomb-shaped nano structure mainly comprises the following steps:
placing the polished zirconia material in diluted phosphoric acid solution with the weight percent more than 1 percent and less than 2.5 percent, treating for 12-36 hours at the temperature of 80-160 ℃ in a high-pressure reaction kettle, or placing the polished zirconia material in diluted phosphoric acid solution with the weight percent more than or equal to 0.5-1 percent or less than or equal to 2.5 and less than 5 percent, treating for 12-36 hours at the temperature of 120-160 ℃ in the high-pressure reaction kettle, and then performing secondary calcination treatment to obtain the zirconia ceramic with the in-situ grown honeycomb nano structure.
Preferably, the zirconia ceramic is subjected to surface grinding treatment by using 100-2000-mesh sandpaper.
Preferably, the zirconium oxide material after polishing treatment is placed in 1-2.5 wt% diluted phosphoric acid solution and treated in a high-pressure reaction kettle at the temperature of 120 ℃ and 160 ℃ for 12-36 h.
Preferably, the polished zirconia material is placed in 2.5 wt% diluted phosphoric acid solution and treated in a high-pressure reaction kettle at 160 ℃ for 24 hours.
Preferably, the high-pressure reaction kettle is made of a polytetrafluoroethylene inner container.
Preferably, the sample prepared by the high-pressure reaction kettle is ultrasonically cleaned in deionized water, and is dried and then is calcined for the second time.
Preferably: the calcination condition is calcination for 10-30min at 800-1100 ℃.
Preferably: the calcination condition is calcination for 15min at 950 ℃.
The invention also provides the modified zirconia ceramic prepared by the preparation method in any protection.
The invention has the following remarkable advantages: the pressure is controlled by adjusting the temperature in a pressure-maintaining reaction vessel under the condition of high temperature through a simple high-pressure hydrothermal approach, acid etching is carried out by adopting dilute phosphoric acid under the double conditions of high temperature and high pressure, and honeycomb-shaped nano structures with different pore diameters are firstly constructed on the surface of the zirconia ceramic. The novel nano structures can obviously improve the bioactivity and the adhesive property of the decorative porcelain/resin adhesive of the zirconia, solve the problem that the zirconia ceramics are difficult to be biologically functionalized at present, and provide a new idea for the surface modification design of the zirconia ceramics. The preparation method is simple and convenient to operate, good in repeatability and strong in controllability; the zirconia implant prepared by the method has a regular honeycomb-shaped nano structure with controllable pore diameter on the surface, has good bioactivity and good porcelain/resin adhesive bonding performance, and has important research value and clinical significance in the field of dental implantation.
Description of the drawings:
FIG. 1: surface Scanning Electron Microscope (SEM) images (a) and aperture size statistics (B) of different samples.
FIG. 2: three-point bending strength (A) and Rockwell hardness (B) statistics for different samples.
FIG. 3: XPS characteristic peaks and fitting maps of Zr, 0 and P, Y elements on different sample surfaces.
FIG. 4: the bonding strength of the decorative porcelain (A) and the resin adhesive (B) on the surfaces of different samples; the confidence interval was 99.5% (. p < 0.05).
FIG. 5: cell activity (A) and mineralization level (B) of MC3T3-E1 osteoblasts on different sample surfaces; the confidence interval was 99.5% (. p < 0.05).
The specific implementation mode is as follows:
in order to make the technical solution and advantages of the present invention more clear, embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The invention successfully prepares a series of novel honeycomb nano structures with controllable pore diameters on the surface of zirconia ceramics by a simple hydrothermal high-pressure treatment way. In the construction process, a plurality of factors can influence the construction of the honeycomb-shaped nano structure, the volume and concentration of phosphoric acid in the reaction kettle, the temperature and time of hydrothermal treatment, the temperature and time of secondary calcination and the like, and different control conditions can influence the preparation of target materials and the comprehensive biological performance of the target materials. The invention inspects the above influencing factors, and the result shows that: after the zirconia ceramics are polished step by using gradient sand paper of 100 meshes, 400 meshes, 1000 meshes and 2000 meshes, a sample is placed in 25mL of diluted phosphoric acid solution with the concentration of 1.0 or 2.5 wt%, the reaction is carried out for 24 hours at the temperature of 120 or 160 ℃ after the high-pressure reaction kettle is sealed, and the ideal honeycomb-shaped nano structure with different apertures in the range of 30-145nm can be obtained after the calcination is carried out for 15 minutes at the temperature of 950 ℃.
Example 1 preparation of in-situ grown honeycomb nanostructure on zirconia ceramic surface and preparation of physical and chemical characterization of honeycomb nanostructure: firstly, polishing zirconia ceramics step by using sand paper of 100, 400, 1000 and 2000 meshes; after cleaning, placing the sample in a polytetrafluoroethylene inner container of a high-pressure reaction kettle, further pouring 25mL of dilute phosphoric acid solution with the concentration of 0.5, 1.0, 2.5 or 5.0 wt%, sealing the high-pressure reaction kettle, and reacting for 24 hours at the temperature of 80, 120 or 160 ℃; and finally, ultrasonically cleaning the prepared sample in deionized water for 2min, drying and calcining for 15min at 950 ℃ for later use.
Prepared by the stepsA Scanning Electron Microscope (SEM) picture of the sample is shown in fig. 1: pure zirconium oxide (ZrO)2) Slight scratches appear on the surface; when the sample is treated by 0.5 wt% phosphoric acid, a small amount of sheet structures appear on the surface of the sample at 80 ℃, but no obvious pore-shaped structures are formed, while obvious honeycomb-shaped structures can be observed at 120 ℃ and 160 ℃, and the pore diameters are respectively about 27.6 +/-9.8 nm and 47.2 +/-10.7 nm; distinct honeycomb-like nanostructures were observed for all three temperature groups at 1.0 wt% phosphoric acid treatment, with pore sizes of about 26.2 + -8.0 nm (80 deg.C), 33.8 + -10.5 nm (120 deg.C), and 85.7 + -20.7 nm (160 deg.C), respectively; 2.5 wt% phosphoric acid treatment, no nanostructure appeared in the 80 ℃ group, while the pore sizes in the 120 ℃ and 160 ℃ groups were about 65.2 + -19.3 nm and 145.3 + -34.2 nm, respectively; in addition, no honeycomb structure was formed in all groups (only 160 ℃ group showed sheet structure) at 5.0 wt% phosphoric acid treatment. The above results demonstrate that: in a certain acid concentration range (0.5-2.5 wt%), the pore diameter of the target sample surface nano structure is gradually increased along with the increase of the hydrothermal temperature; however, when the acid concentration is too high (5.0 wt%), the honeycomb-like nanostructure cannot be formed. This may be closely related to the degree of ionization and concentration of hydrogen phosphate in solution: it is well known that temperature increases accelerate phosphate ionization and hydrogen phosphate formation, which in turn promotes the formation of honeycomb zirconium hydrogen phosphate nanostructures; and high-concentration phosphoric acid can inhibit self ionization, so that hydrogen phosphate radicals in the solution are less and less along with the increase of the initial concentration of phosphoric acid in the reaction kettle, and the formation of zirconium hydrogen phosphate sediments is further influenced. In addition, if the sample is not subjected to polishing and polishing pretreatment, the formed zirconium hydrogen phosphate precipitate is deposited around the micron-sized zirconium oxide particles on the surface, and an ideal honeycomb-shaped nano structure cannot be obtained.
Experimental example 2 detection of bending strength and hardness of different samples
And taking the square zirconia ceramic with the thickness of 0.3cm and the side length of 2cm, preparing a sample according to the experimental steps, and then detecting the strength and the hardness. Firstly, a three-point bending strength test is carried out by using a universal mechanical testing machine: the diameter of a pressure head of the experimental machine is 0.2cm, the span is 2cm, the loading speed is 0.5mm/min, and the three-point bending strength is calculated according to the formula of R ═ 3F × L)/(2b × h:): f is the load (N) at the time of fracture of the specimen, L is the span (mm), b is the specimen width (mm), and h is the specimen thickness (mm). Next, the hardness of each sample was measured using a rockwell hardness tester: the experiment was carried out using a conical diamond bit, with a load of 60kg and a load time of 10 s.
FIG. 2 shows that: the flexural strength (fig. 2A) and hardness (fig. 2B) of all samples were similar with no significant difference; the hardness and strength were about 1200MPa and 88HRA, respectively. The above results indicate that the high pressure hydrothermal treatment in a dilute phosphoric acid environment does not cause damage to the strength and hardness of the zirconia ceramics.
Experimental example 3 compositional testing of surface deposits of various samples
Because the surface nanostructures of the samples of 80 deg.C (1.0 wt%), 120 deg.C (2.5 wt%), 160 deg.C (1.0 wt%), 160 deg.C (2.5 wt%) were highly reproducible and had a broad pore size distribution (30-140nm, covering the pore size of each set of nanostructures in this patent), we chose them and ZrO2The unmodified control samples were subjected to a surface composition detection experiment. X-ray photoelectron spectroscopy (XPS) was used to detect the surface composition of each sample at a detection power of 150W, and the target binding energy was calibrated at C1s 284.8.8.
FIG. 3 shows: and ZrO2In contrast, a distinct P characteristic peak appears on the sample surface; as the treatment temperature and the phosphoric acid concentration increased, characteristic peaks of Zr in the crystal phase [ Zr3d5/2(O-Zr-O) and Zr3d3/2(O-Zr-O) ]]Gradually decreases and the characteristic peaks of Zr binding with phosphate radical [ Zr3d5/2(P-O-Zr) and Zr3d3/2(P-O-Zr)]Gradually enhancing; the oxygen (P-O, H) gradually flows from the lattice oxygen (Zr-O, Y-O) to the surface oxygen (P-O, H)2O) and the characteristic peak of Y gradually disappears. The XPS results above demonstrate that the material surface nanostructure component is zirconium hydrogen phosphate [ Zr (HPO)4)2·H2O]. The above results further confirm that the material of interest was successfully prepared and that the composition was predominantly zirconium hydrogen phosphate.
Experimental example 4 detection of bonding Strength of porcelain or resin paste on surfaces of different samples
Selected ZrO2Samples of the unmodified group, 80 ℃ (1.0 wt%), 120 ℃ (2.5 wt%), 160 ℃ (1.0 wt%) and 160 ℃ (2.5 wt%) were tested for the bonding strength of the surface decorated porcelain or resin glue. In order to detect the bonding strength of the decorative porcelain, firstly, the special decorative porcelain powder for zirconia is coated on the surfaces of different zirconia ceramic chips by a powder slurry plastic coating methodPreparing a cylinder with the diameter of 4mm and the height of 5mm, and sintering to obtain a decorative porcelain; then the probe is placed at the joint of the porcelain and the zirconia substrate, the plane of the lower end of the probe is parallel to the center line of the porcelain cylinder, and the probe is loaded at a constant speed of 5 mm/min. In order to detect the bonding strength of the resin adhesive, a mold with the bottom surface diameter of 4mm and the height of 5mm is placed on the surfaces of different zirconia ceramic materials, an adhesive is uniformly coated on the bonding surface by a small brush and then is kept stand for 10s, and the adhesive is cured by a light curing lamp for 10 s; after the resin cement is blended and stirred strictly according to the requirements of product specifications, the mixture is uniformly filled into a mold, after a light curing lamp is used for short-time illumination, overflowing cement is removed, and the edges of the bonding surface are respectively cured by illumination for 20 s; the test piece is fixed on a universal tester base by a clamp, and a single-blade loading head is loaded at the speed of 0.5mm/min in the direction parallel to the bonding surface until the test piece is separated from the resin. The shear strength formula is that P is F/S: p is the shear strength (MPa), F is the shear force value (N) when the test piece is damaged, and S is the bonding area (mm)2)。
Fig. 4A shows: with untreated ZrO2Compared with the prior art, the binding strength of the porcelain of the sample after phosphorylation is obviously improved, and the sample with large aperture (120 ℃ (2.5 wt%), 160 ℃ (1.0 wt%), 160 ℃ (2.5 wt%)]The effect is better and obvious. The measurement results of the resin paste (fig. 4B) also showed a similar trend. The results show that the honeycomb-shaped nano structure can obviously improve the bonding strength of the surface decorative porcelain and the resin adhesive.
Experimental example 5 detection of osteoblast Activity and mineralization levels on the surface of different samples
ZrO likewise being selected2Surface osteoblast activity and mineralization level were measured on samples of five groups, namely, unmodified group, 80 deg.C (1.0 wt%), 120 deg.C (2.5 wt%), 160 deg.C (1.0 wt%) and 160 deg.C (2.5 wt%), at an initial concentration of 2 × 104Individual/well MC3T3-E1 osteoblasts were seeded onto the material surface and after 3 or 7 days of culture, thiazole blue (MTT) and mineralization experiments were used to investigate the cell activity and mineralization levels in each group. To characterize the activity of bone cells of different compositions, old culture medium was removed after 3 days of culture, serum-free cell culture medium containing MTT (0.5. mu.g/mL) was added to each well one by one, and formazan insolubles formed in the cells were solubilized using dimethyl sulfoxide after 4h of cell incubationFinally, measuring the absorbance value of the solution at 490 nm; in order to detect the mineralization level of cells, osteoblasts are fixed by 4% paraformaldehyde after 7 days of culture, and then are stained and quantitatively analyzed by using a commercial alizarin red staining solution, and the specific process can refer to detailed kit instructions.
The results of MTT (fig. 5A) show that: after 3d incubation, with ZrO2Group comparison, four other groups of samples [120 deg.C (1.0 wt%), 120 deg.C (2.5 wt%), 160 deg.C (1.0 wt%), 160 deg.C (2.5 wt%)]The surface MC3T3-E1 cells were significantly enhanced in activity (p < 0.05), but there was no significant difference in cell activity between the four groups. The mineralization results (fig. 5B) show: after the phosphoric acid treatment, the mineralization level of osteoblasts on the surface of each group of samples is also obviously enhanced (p < 0.05), and the samples show obvious pore diameter dependence (ZrO)2< 120 ℃ (1.0 wt%) < 120 ℃ (2.5 wt%)/160 ℃ (1.0 wt%) < 160 ℃ (2.5 wt%)). The results show that the honeycomb-shaped nano structure can obviously promote osteoblast proliferation and osteogenic differentiation performance.
Therefore, the research prepares the zirconium hydrogen phosphate honeycomb-shaped nano structure on the surface of the zirconia ceramic in situ through a simple hydrothermal high-pressure way, endows the material with excellent bioactivity and decorative porcelain/resin adhesive bonding performance, and further solves the problem that the zirconia ceramic is difficult to surface modify and biologically functionalize at present.
Finally, the above embodiments are only used to illustrate the technical solutions of the present invention, and do not limit the content of the present invention. Although the present invention has been illustrated in greater detail by the foregoing examples, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the zirconia ceramic surface in-situ growth honeycomb-shaped nano structure mainly comprises the following steps:
the zirconium oxide material after polishing treatment is placed in 1-2.5 wt% diluted phosphoric acid solution, treated for 12-36h at 80-160 ℃ in a high-pressure reaction kettle, or the zirconium oxide material after polishing treatment is placed in 0.5-1 wt% or more than or equal to 2.5 and less than 5 wt% diluted phosphoric acid solution, treated for 12-36h at 120-160 ℃ in the high-pressure reaction kettle, and then subjected to secondary calcination treatment, so as to obtain the zirconium oxide ceramic with the in-situ grown honeycomb nano structure.
2. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: the zirconia ceramics are subjected to surface grinding treatment by using 100-2000-mesh sandpaper.
3. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 2, which is characterized in that: the zirconium oxide material after polishing treatment is placed in 0.5-2.5 wt% diluted phosphoric acid solution and treated for 24 hours in a high-pressure reaction kettle at the temperature of 120-.
4. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 2, wherein the zirconia material after polishing treatment is placed in 2.5 wt% diluted phosphoric acid solution and treated for 24h at 160 ℃ in a high-pressure reaction kettle.
5. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: the high-pressure reaction kettle is made of a polytetrafluoroethylene inner container.
6. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: and ultrasonically cleaning a sample prepared by the reaction of the high-pressure reaction kettle in deionized water, and drying and then carrying out secondary calcination.
7. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: the calcination condition is calcination for 10-30min at 800-1100 ℃.
8. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 7, which is characterized in that: the calcination condition is calcination for 15min at 950 ℃.
9. A modified zirconia ceramic produced by the production method according to any one of claims 1 to 8.
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| US20160106524A1 (en) * | 2001-11-30 | 2016-04-21 | Straumann Holding Ag | Ceramic dental implant |
| CN105854080A (en) * | 2016-04-29 | 2016-08-17 | 成都贝施美生物科技有限公司 | Zirconia dental implant surface treatment method |
| CN110085337A (en) * | 2019-05-20 | 2019-08-02 | 中国核动力研究设计院 | A kind of UO2-ZrO2The preparation method of ceramic fuel microscopic examination sample |
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2020
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|---|---|---|---|---|
| US4135012A (en) * | 1977-04-25 | 1979-01-16 | Corning Glass Works | Surface treatment of zirconia ceramic |
| US4318770A (en) * | 1980-08-13 | 1982-03-09 | General Motors Corporation | Surface etching before electroding zirconia exhaust gas oxygen sensors |
| CN1369465A (en) * | 2001-01-31 | 2002-09-18 | 东芝陶磁股份有限公司 | Ceramic parts formed micro crowning on its surface and its mfg. method |
| US20160106524A1 (en) * | 2001-11-30 | 2016-04-21 | Straumann Holding Ag | Ceramic dental implant |
| US20150056574A1 (en) * | 2007-04-19 | 2015-02-26 | Straumann Holding Ag | Process for providing a topography to the surface of a dental implant |
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