Preparation method and device of zirconium oxide implant surface osteogenesis promoting and antibacterial zinc phosphate coating

Abstract

The invention belongs to the field of dental implants, and particularly relates to a preparation method and device of a zirconium oxide implant surface osteogenesis-promoting and antibacterial zinc phosphate coating, and the preparation method of the zinc phosphate coating comprises the following steps: S4, mixing zinc oxide, phosphoric acid, nitric acid and deionized water, and adding an additive to prepare a phosphating solution; s5, putting the phosphating solution and the zirconium oxide implant into a reaction kettle, heating the reaction kettle in a baking oven at 150-230 DEG C for 3-12 hours, and taking out the zirconium oxide implant after natural cooling; and S6, carrying out ultrasonic cleaning for 1-5 minutes by adopting deionized water, and drying in a drying oven at 40-60 DEG C to finally obtain the zirconium oxide implant coated with the zinc phosphate coating. The zinc phosphate coating is prepared on the surface of the zirconium oxide dental implant by applying a hydrothermal method, and the zirconium oxide dental implant has good mechanical properties, cytocompatibility, osteogenesis performance and antibacterial performance by changing the formula of a phosphating solution and adjusting the temperature and time of a hydrothermal reaction, and has important significance for expanding clinical application of a zirconium oxide ceramic implant material in the field of oral cavities.

Description

Technical Field

[0001] The invention belongs to the field of dental implants, and in particular relates to a method and a device for preparing an osteopromoting and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant. Background Art

[0002] For decades, titanium implants have been widely used in the field of oral restoration implants, but they have some obvious disadvantages: titanium implants have a high elastic modulus, which can lead to a stress shielding effect, thereby inhibiting bone regeneration and even leading to bone resorption; titanium will be corroded and release toxic aluminum and vanadium metal ions when exposed to the human oral electrolyte environment for a long time, causing allergic and inflammatory reactions to the tissues around the implant, and even causing local tissue pain and swelling; the color of titanium is very different from that of natural teeth, which is not conducive to aesthetics, limiting its application in the anterior teeth area and some patients with insufficient mucosal thickness around implants, and gradually restricting the clinical use of titanium implants.

[0003] Zirconia ceramics have unique advantages in the field of dental ceramic restorative materials due to their high mechanical properties, good biocompatibility, excellent chemical stability and unique aesthetic properties, and are expected to replace titanium implants.

[0004] Dental ceramic restorations prepared by SLA have the characteristics of good surface quality, high density, high precision and excellent mechanical properties; however, due to its lack of biological activity, this has greatly limited the application and expansion of ceramic implants; the methods for introducing bioactive ingredients mostly use a composite method, that is, directly mechanically mixing zirconium oxide powder and bioactive substances and then sintering them at high temperature into ceramics to improve the bioactivity of zirconium oxide, but the disadvantage of the direct composite method is that the strength of these active substances is generally low. Summary of the invention

[0005] The purpose of the present invention is to address the above-mentioned technical problems and provide a method and device for preparing an osteopromoting and antibacterial zinc phosphate coating on the surface of a zirconia implant, so as to promote the adhesion, proliferation and differentiation of osteoblasts and fibroblasts on its surface by changing the physical and chemical properties of the ceramic surface, thereby effectively improving its biological activity and bone integration.

[0006] In view of this, the present invention provides a method for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant, comprising the following steps: S1: The zirconia implant model was designed by software, and the slurry was formed by mixing nano-zirconia powder containing 3% mol of yttrium with resin. Then, the implant embryo was prepared by a stereolithography printer with a laser power of 0.3-2W. S2: The green embryo is ultrasonically cleaned with 75% ethanol for 1 to 5 minutes, and then placed in an oven at a temperature of 100 to 250°C for curing for 2 to 5 hours to preliminarily remove part of the resin used as an adhesive; S3: transferring the green embryo to a muffle furnace at a temperature of 300-600°C for degreasing for 1-4 hours, and then transferring the green embryo to a muffle furnace at a temperature of 1300-1600°C for sintering for 3-5 hours, and finally cooling to room temperature with the furnace to obtain a zirconia implant; S4: mixing zinc oxide, phosphoric acid, nitric acid and deionized water, and adding additives to prepare a phosphating solution; S5: placing the phosphating solution and the zirconium oxide implant in a reaction kettle, heating the reaction kettle in an oven at 150-230° C. for 3-12 hours, and taking it out after natural cooling; S6: Use deionized water for ultrasonic cleaning for 1 to 5 minutes, and place in an oven for drying at 40 to 60°C to finally obtain a zirconia implant covered with a zinc phosphate coating.

[0007] In the above technical solution, further: The additive in S4 is one or more of MXene, HA and graphene.

[0008] In the above technical solution, further: The MXene phase is M2XT x and M3XT x phase, and is in a powdery form with a graphene-like structure; Wherein M is one or more of the transition metal elements Ti, Nb, Zr, Cu, Zn, Au, Ag, Mn and Mo with good biological activity; X is one or two of C and N; T x -OH, -O, -F and -Cl One or more of the surface groups.

[0009] In the above technical solution, further: The particle size of the HA phase is nanometer or submicron level.

[0010] In the above technical solution, further: The graphene is a single-layer or multi-layer structure.

[0011] In the above technical solution, further: The zinc oxide in the S4 is 0.3-0.9 mol / L, the phosphoric acid is 0.2-0.6 mol / L, the nitric acid is 0.6-1.8 mol / L, the additive is 0.5-2 g / L, and the molar ratio of zinc oxide to phosphoric acid is 3:2.

[0012] The present invention provides a device for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant, comprising: The oven comprises a box body and a heating mechanism installed on the inner wall of the box body; The kettle body is installed in the box body, and the interior is divided into a plurality of active stirring chambers and passive stirring chambers which are arranged alternately, and a feed pipe is installed on the side and a discharge pipe is installed on the bottom; The stirring mechanism is installed in the kettle body and includes a rotating shaft penetrating through a plurality of active stirring chambers and passive stirring chambers and a stirring rod installed on the rotating shaft, and the stirring rod is located in the active stirring chamber; A driving mechanism is installed on the oven and is used to drive the rotating shaft to rotate; Wherein, a partition net is provided between the active stirring chamber and the passive stirring chamber.

[0013] In the above technical solution, further, it also includes: The feeding mechanism is plugged into the side of the kettle body and comprises a first supporting net for supporting the zirconium oxide implant and a cover plate for detachably connecting with the kettle body, and is arranged corresponding to the passive stirring chamber; A sealing strip is installed between the cover plate and the kettle body and is used for sealing connection between the cover plate and the kettle body; A locking member is installed between the cover plate and the kettle body and is used for detachable connection between the cover plate and the kettle body; Wherein, the first supporting net is provided with a slot for avoiding the rotating shaft when inserted into the kettle body, and the second supporting net is hingedly connected to the inner wall of the slot.

[0014] In the above technical solution, further: The cover plate is provided with a plurality of strip-shaped holes on its circumference, wherein the locking member comprises: The clamping strip is rotatably connected to the side of the kettle body through a cylindrical body and is adapted to the strip-shaped hole; The arc-shaped convex strip is installed on the surface of the cover plate and is used to generate static friction with the surface of the card strip under the action of the sealing strip when the card strip is perpendicular to the strip hole; There are two arc-shaped convex strips, which are symmetrically arranged with each other, and one end of the symmetrical ends is chamfered.

[0015] In the above technical solution, further, the locking member also includes: The limiting structure is installed on the arc-shaped convex strip and is used for limiting the position of the card strip and the strip hole after they are in a vertical state; Among them, the limiting structure includes an embedding groove opened at one end of an arc-shaped convex strip away from its chamfered end and a protrusion arranged at another arc-shaped convex strip away from its chamfered end, and a toggle plate is installed in the embedding groove, and the toggle plate is hingedly connected to the arc-shaped convex strip and is used to press one end to drive the toggle plate to leave the embedding groove.

[0016] The beneficial effects of the present invention are: 1. Zirconia dental implants were prepared by stereolithography (SLA) technology, and zinc phosphate coatings were prepared on their surfaces by hydrothermal method. By changing the formula of phosphating solution and adjusting the temperature and time of hydrothermal reaction, the implants had good mechanical properties, cell compatibility, osteogenic properties and antibacterial properties, which is of great significance for expanding the clinical application of zirconia ceramic implant materials in the oral field.

[0017] 2. Zinc phosphate can exert biological functionality by releasing zinc ions and phosphate ions after degradation. Among them, zinc plays a vital role in various biological functions; it is a component or activator of various enzymes, and participates in the regulation or catalysis of various biochemical reactions; in addition, zinc also plays an important role in bone metabolism and human growth; zinc supplementation can promote bone formation, and at the same time enhance bone strength by stimulating osteoblasts and inhibiting the differentiation of osteoclasts; while phosphate ions can provide a phosphorus source for bone proliferation, thereby promoting bone repair and regeneration.

[0018] 3. During the preparation of the zinc phosphate coating, the phosphating solution is properly stirred to improve the uniformity of the mixing of the various substances in the phosphating solution, reduce the concentration gradient in the kettle body, ensure the uniformity of the coating, and divide the kettle body into an active stirring chamber and a passive stirring chamber to avoid collision between the stirring rod and the zirconia implant when the stirring rod is stirring the phosphating solution, avoid damage to the coating on the surface of the zirconia implant, and ensure the quality of the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is an XRD diagram of the zirconium oxide implant with and without a zinc phosphate coating according to the present invention; Figure 2 is a SEM image of the zirconia implant with and without a zinc phosphate coating of the present invention; Figure 3 This is a surface scanning EDS chemical composition diagram of the zirconium oxide implant with and without zinc phosphate coating of the present invention; Figure 4 This is a comparison diagram of the bending strength of the zirconia implant with and without the zinc phosphate coating before and after aging; Figure 5 The nano scratch images of the zirconia implant with and without zinc phosphate coating of the present invention; Figure 6 The results of cell activity after co-culturing MC3T3-E1 cells with or without the zinc phosphate coating on the zirconium oxide implants of the present invention for 1, 3, and 5 days; Figure 7 The results of the in vitro osteogenic differentiation and mineralization of MC3T3-E1 cells by the zirconia implant and the titanium implant with or without the zinc phosphate coating of the present invention; Figure 8 The CFU morphology of the zirconia implant with or without the zinc phosphate coating and the titanium implant after co-culture with Staphylococcus aureus and Escherichia coli (A), and the CFU analysis results of Staphylococcus aureus (B) and Escherichia coli (C); Fig. 9 It is a schematic structural diagram of the preparation device of the present invention; Fig.10 It is a schematic diagram of the internal structure of the preparation device of the present invention; Fig.11 It is a structural schematic diagram of the oven of the present invention; Fig.12 The present invention Fig.11 The enlarged view of point A in the middle; Fig.13 It is a structural schematic diagram of the feeding mechanism of the present invention; The markings in the figure are as follows: 1. oven; 10. box body; 11. heating mechanism; 2. kettle body; 20. active stirring chamber; 21. passive stirring chamber; 22. feed pipe; 23. discharge pipe; 24. partition; 3. stirring mechanism; 30. rotating shaft; 31. stirring rod; 4. driving mechanism; 5. feeding mechanism; 50. first supporting net; 51. cover plate; 52. notch; 53. second supporting net; 54. strip hole; 6. sealing strip; 7. locking piece; 70. clamping strip; 71. cylinder; 72. arc-shaped convex strip; 73. limiting structure; 730. embedded groove; 731. protrusion; 732. toggle plate. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present application to clearly describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments in the present application belong to the scope of protection of this application.

[0021] Embodiment 1: This embodiment provides a method for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant, comprising the following steps: S1: The zirconia implant model was designed by software, and the slurry was formed by mixing nano-zirconia powder containing 3% mol of yttrium with resin. Then, the implant embryo was prepared by a stereolithography printer with a laser power of 1.5W. S2: The embryo was ultrasonically cleaned with 75% ethanol for 5 minutes, and then placed in an oven at 120°C for curing for 2 hours to preliminarily remove part of the resin used as an adhesive; S3: transferring the green embryo to a muffle furnace at a temperature of 600°C for degreasing for 4 hours, and then transferring the green embryo to a muffle furnace at a temperature of 1550°C for sintering for 3 hours, and finally cooling it to room temperature in the furnace to obtain a zirconia implant; S4: mixing zinc oxide, phosphoric acid, nitric acid and deionized water, and adding additives to prepare a phosphating solution; S5: placing the phosphating solution and the zirconium oxide implant in a reaction kettle, heating the reaction kettle in an oven at 200° C. for 6 h, and taking it out after natural cooling; S6: ultrasonically clean the implant with deionized water for 1 min and dry it in an oven at 60°C to obtain a zirconia implant covered with a zinc phosphate coating; Zirconia implants coated with zinc phosphate were prepared by the above method and compared with zirconia implants without zinc phosphate coating and titanium implants. Figure 1 It can be seen that after the hydrothermal reaction, a large amount of ZnP phase is formed on the surface of the implant, and the surface hydrothermal method can form a ZnP coating on the surface of the zirconia implant; Figure 2 It can be seen that after hydrothermal treatment, needle-like and granular crystals can be seen on the surface of the specimen, and the surface is completely covered by crystals, without the base zirconia. It can be considered that after hydrothermal treatment, a zinc phosphate coating is formed on the surface of the zirconia implant, and the coating completely covers the zirconia base. Figure 3 It can be seen that Zn, P, C, O, Zr, C, and Ti elements exist on the surface of the zirconia implant after hydrothermal treatment, which indicates that there is a zinc phosphate coating on the implant surface after hydrothermal treatment; at the same time, the content of O, Zr, and Y elements decreases after hydrothermal treatment, indicating that the zinc phosphate coating on the implant surface has a large coverage area; Figure 4 It can be seen that although the strength of the zirconia implants decreased after hydrothermal treatment, it was still 934±46MPa, which can meet clinical needs; and the aging test of the zirconia implants before and after treatment showed that the strength of pure zirconia implants decreased significantly, by 35%, while the strength of the zirconia implants covered with zinc phosphate coating decreased by only 7.6%, and the difference was not statistically significant, indicating that the zinc phosphate coating can effectively prevent the aging of zirconia implants; Figure 5 It can be seen that the coating thickness is 2.2μm and the coating adhesion is 71.5MPa; Figure 6It can be seen that the data measured by CCK-8 method after 1 d, 3 d, and 5 d of co-culture of MC3T3-E1 cells with zirconia implants before and after hydrothermal treatment showed that the survival rate of cells on zirconia implants after hydrothermal treatment exceeded 100%. From the third day, the cell survival rate on zirconia implants loaded with ZnP was significantly higher than that on zirconia implants without coating, indicating that zinc phosphate coating can effectively promote the proliferation of MC3T3-E1 cells. Figure 7 As can be seen from the figure, the ALP staining results after 7 days of osteogenic differentiation ( Figure 7 ) showed that the staining depth of the zirconia implants coated with the coating was deeper than that of the pure titanium group and the pure zirconia group, indicating that the zirconia implants coated with zinc phosphate coating can significantly promote the expression of alkaline phosphatase in MC3T3-E1 cells; the staining results of ARS after 21 days of osteogenic differentiation ( Figure 7 ) showed that the surfaces of titanium implants and zirconia implants without coatings were mainly unmineralized blank areas, with only discrete spot-like nodules visible, and the color was lighter. The number and area of ​​mineralized nodules on the surface of zirconia implants with coatings increased significantly, and the color was significantly deepened. The above results showed that zirconia implants coated with zinc phosphate coatings can significantly promote the mineralization of the extracellular matrix, and its mineralization level is higher than that of zirconia implants without coatings and titanium implants; the above results showed that zinc phosphate coatings exhibited good osteogenic properties; Figure 8 As can be seen from the figure, the CFU count results of titanium implants, zirconia implants without coatings, and zirconia implants with coatings are as follows ( Figure 8 As shown in the figure (A), there was no statistical difference in the CFU results of Staphylococcus aureus and Escherichia coli between titanium implants and zirconia implants without coating, while the CFU results of zirconia implants with coating were significantly different from those of titanium implants and zirconia implants without coating, and the colony count was significantly reduced; the above results showed that zirconia implants coated with zinc phosphate showed good anti-Staphylococcus aureus and Escherichia coli performance; Among them, the software design can adopt existing design software such as 3Dmax, AbyssFish, etc., and the stereolithography technology printer is an existing mature technology and will not be described in detail here.

[0022] Embodiment 2: This embodiment provides a method for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant, comprising the following steps: S1: The zirconia implant model was designed by software, and a slurry with a solid content of 47% was prepared using nano-zirconia powder containing 3% mol of yttrium and resin as raw materials. Then, the implant embryo was prepared by a stereolithography printer with a thickness of 50 um and a laser power of 1.5 W. S2: The embryo was ultrasonically cleaned with 75% ethanol for 5 minutes, and then placed in an oven at 120°C for curing for 2 hours to preliminarily remove part of the resin used as an adhesive; S3: transferring the green embryo to a muffle furnace at a temperature of 500°C for degreasing for 3 hours, and then transferring the green embryo to a muffle furnace at a temperature of 1550°C for sintering for 4 hours, and finally cooling to room temperature with the furnace to obtain a zirconia implant; S4: zinc oxide, phosphoric acid, nitric acid and deionized water are mixed to prepare a phosphating solution, wherein the zinc oxide is 0.3 mol / L, the graphene (single-layer structure) is 2 g / L, the phosphoric acid is 0.5 mol / L, and the nitric acid is 0.8 mol / L; S5: Pour the phosphating solution into the reaction kettle, put the zirconia implant in it, heat the reaction kettle in an oven at 200°C for 3h, and take it out after natural cooling; S6: ultrasonically clean the implant with deionized water for 1 min and dry it in an oven at 60°C to obtain a zirconia implant covered with a zinc phosphate coating; Comparison example: S1: The zirconia implant model was designed by software, and a slurry with a solid content of 45% was prepared using nano-zirconia powder containing 3% mol of yttrium and resin as raw materials. Then, the implant embryo was prepared by a stereolithography printer with a thickness of 50 um and a laser power of 0.5 W. S2: The embryo was ultrasonically cleaned with 75% ethanol for 5 minutes, and then placed in an oven at 120°C for curing for 2 hours to preliminarily remove part of the resin used as an adhesive; S3: transferring the green embryo to a muffle furnace at a temperature of 600°C for degreasing for 4 hours, and then transferring the green embryo to a muffle furnace at a temperature of 1550°C for sintering for 3 hours, and finally cooling it to room temperature in the furnace to obtain a zirconia implant; S4: zinc oxide, phosphoric acid, nitric acid and deionized water are mixed to prepare a phosphating solution, wherein the zinc oxide is 0.5 mol / L, the MXene with the composition of Mo2TiC is 2 g / L, the phosphoric acid is 0.5 mol / L, and the nitric acid is 0.7 mol / L; S5: Pour the phosphating solution into the reaction kettle, put the zirconium oxide implant in it, heat the reaction kettle in an oven at 250°C for 12 hours, and take it out after natural cooling; The results of this example are as follows: the flexural strength of the zirconia implant covered with zinc phosphate coating is 933 MPa; the cell survival rates of MC3T3-E1 cells and the zirconia implant covered with zinc phosphate coating after co-culture for 3 days are 97.6%, 140.3% and 168.5%, respectively, showing good cell compatibility; the antibacterial rates of the zirconia implant covered with zinc phosphate coating, Staphylococcus aureus and Escherichia coli after co-culture for 1 day are 83.3% and 85.9%, showing excellent antibacterial properties; Results of the control example: When the reactor was opened, it was found that the zirconia implant was broken. This was mainly due to the low laser power, high hydrothermal temperature and long time, which resulted in defects in the printed green body and poor thermal stability.

[0023] Embodiment 3: This embodiment provides a device for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant, comprising: The oven 1 comprises a box body 10 and a heating mechanism 11 installed on the inner wall of the box body 10; The kettle body 2 is installed in the box body 10, and the interior is divided into a plurality of active stirring chambers 20 and passive stirring chambers 21 which are arranged alternately, and a feed pipe 22 is installed on the side surface, and a discharge pipe 23 is installed on the bottom surface; The stirring mechanism 3 is installed in the kettle body 2 and includes a rotating shaft 30 that passes through the multiple active stirring chambers 20 and the passive stirring chambers 21 and a stirring rod 31 installed on the rotating shaft 30, and the stirring rod 31 is located in the active stirring chamber 20; The driving mechanism 4 is installed on the oven 1 and is used to drive the rotating shaft 30 to rotate; Wherein, a partition net 24 is provided between the active stirring chamber 20 and the passive stirring chamber 21; Meanwhile, the driving mechanism 4 may adopt a motor, and gear transmission may be adopted between the driving mechanism 4 and the rotating shaft 30, while the heating mechanism 11 may adopt resistance wire heating. The specific structure thereof is an existing mature technology and will not be described in detail here.

[0024] It can be seen from the present embodiment that by configuring the interior of the kettle body 2 into a plurality of alternating active stirring chambers 20 and passive stirring chambers 21, and connecting the two via a partition 24, and placing the stirring rod 31 of the stirring mechanism 3 in the active stirring chamber 20, and placing the zirconia implant in the passive stirring chamber 21, it is possible to effectively avoid that when the stirring rod 31 stirs the phosphating solution, most of the zirconia implants can be driven to follow the phosphating solution to a certain extent and be in a suspended state. On the one hand, the stirring rod 31 is avoided from contacting the surface of the zirconia implant, thereby avoiding affecting the coating on the surface of the zirconia implant. On the other hand, the stirring of the phosphating solution can effectively improve the mixing uniformity of the components of the phosphating solution, avoid the occurrence of concentration steps that affect the uniformity of the coating on the surface of the zirconia implant, and at the same time, improve the uniformity of heating.

[0025] Embodiment 4: This embodiment provides a device for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant. In addition to the technical solutions of the above embodiments, it also has the following technical features, including: The feeding mechanism 5 is plugged into the side of the kettle body 2 and includes a first supporting net 50 for supporting the zirconia implant and a cover plate 51 for detachably connecting with the kettle body 2, and is arranged corresponding to the passive stirring chamber 21; The sealing strip 6 is installed between the cover plate 51 and the kettle body 2 and is used for sealing connection between the cover plate 51 and the kettle body 2; The locking member 7 is installed between the cover plate 51 and the kettle body 2 and is used for detachable connection between the cover plate 51 and the kettle body 2; The first support net 50 is provided with a slot 52 for avoiding the rotating shaft 30 when inserted into the kettle body 2, and a second support net 53 is hingedly connected to the inner wall of the slot 52; Meanwhile, the sealing strip 6 is made of rubber, and in order to ensure resistance to corrosion by the phosphating solution, fluororubber may be used. The specific component materials are existing mature technologies, and can give the sealing strip 6 better sealing performance, which will not be described in detail here.

[0026] It can be seen from this embodiment that the feeding mechanism 5 adopts the first support net 50 and the cover plate 51, that is, the zirconia implant is first placed on the first support net 50, and then inserted into the passive stirring chamber 21, and then the cover plate 51 and the kettle body 2 are fixed by the locking member 7, and the sealing strip 6 can ensure the sealing connection between the cover plate 51 and the kettle body 2, and then the phosphating solution is introduced into the kettle body 2 to ensure the formation of the surface coating of the zirconia implant, thereby improving convenience; The notch 52 on the first supporting net 50 facilitates the insertion of the first supporting net 50 into the kettle body 2 without being affected by the rotating shaft 30, and the second supporting net 53 hinged on the inner wall of the notch 52 can ensure the convenience of taking out the zirconia implant that has fallen into the notch 52 due to the stirring of the phosphating liquid after the surface coating of the zirconia implant is completed, that is, by moving the second supporting net 53, the zirconia implant on the second supporting net 53 falls onto the first supporting net 50, and then the second supporting net 53 is turned over and the loading mechanism 5 is taken out, thereby ensuring the unloading of the zirconia implant that has been coated.

[0027] Embodiment 5: This embodiment provides a device for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant. In addition to the technical solutions of the above embodiments, it also has the following technical features: The cover plate 51 is provided with a plurality of strip-shaped holes 54 on its circumference, wherein the locking member 7 comprises: The clamping strip 70 is rotatably connected to the side of the kettle body 2 by means of a cylinder 71 and is adapted to the strip-shaped hole 54; The arc-shaped convex strip 72 is installed on the surface of the cover plate 51 and is used to generate static friction with the surface of the clamping strip 70 under the action of the sealing strip 6 when the clamping strip 70 is perpendicular to the strip-shaped hole 54; There are two arc-shaped convex strips 72, which are symmetrically arranged with each other, and one end of the symmetrical ends is chamfered.

[0028] It can be seen from this embodiment that by using the clamping strip 70 as the locking member 7 and rotating it to connect it to the side of the kettle body 2, after the bar-shaped hole 54 on the cover plate 51 corresponds to it, the clamping strip 70 can be rotated to fix the cover plate 51, which is convenient. In addition, the provision of the arc-shaped ridge 72 can increase the force of the clamping strip 70 on the cover plate 51, prompting the cover plate 51 to squeeze the sealing strip 6, thereby ensuring the sealing effect. At the same time, two arc-shaped ridges 72 are provided, which can effectively ensure the stability of the clamping strip 70 locking the cover plate 51, and the chamfering of one end of the arc-shaped ridge 72 can avoid restricting the rotation of the clamping strip 70, and at the same time can better guide the clamping strip 70 to move to the surface of the arc-shaped ridge 72, thereby applying force to the arc-shaped ridge 72 to squeeze the cover plate 51, thereby ensuring the sealing performance.

[0029] Embodiment 6: This embodiment provides a device for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant. In addition to the technical solutions of the above embodiments, it also has the following technical features. The locking member 7 also includes: The limiting structure 73 is installed on the arc-shaped convex strip 72 and is used for limiting the position of the clamping strip 70 and the strip-shaped hole 54 after they are in a vertical state; The limiting structure 73 includes an embedding groove 730 provided at one end of an arc-shaped convex strip 72 away from the chamfer thereof and a protrusion 731 provided at another end of the arc-shaped convex strip 72 away from the chamfer thereof, and a toggle plate 732 is installed in the embedding groove 730, and the toggle plate 732 is hingedly connected to the arc-shaped convex strip 72 and is used to press one end to drive the toggle plate 732 to leave the embedding groove 730; Specifically, the setting of the embedding groove 730 will form an abutment portion at the end of the arc-shaped ridge 72 away from the chamfer to limit the movement of the clamping strip 70 after entering the embedding groove 730, and the abutment portion is located on the same side as the protrusion 731 on the other arc-shaped ridge 72, thereby limiting the clamping strip 70 in both directions.

[0030] It can be seen from this embodiment that, by setting the limiting structure 73, after the clamping strip 70 passes through the strip hole 54 and the cover plate 51 is locked, the clamping strip 70 can be limited to prevent the clamping strip 70 from loosening, causing the locking member 7 to fail and affecting the sealing performance; The limiting structure 73 adopts a protrusion 731 set on one arc-shaped convex strip 72, an embedding groove 730 and a toggle plate 732 on the other arc-shaped convex strip 72. On the one hand, the protrusion 731 can cause the card strip 70 and the strip block to finally be in a vertical state. On the other hand, the embedding groove 730 can move the other end of the card strip 70 into place, thereby limiting the final state of the card strip 70 well. The toggle plate 732 can then press one end away from the card strip 70, thereby causing the card strip 70 to move out of the embedding groove 730, thereby facilitating the rotation of the card strip 70 and realizing the release of the locking member 7, which is highly convenient.

[0031] The embodiments of the present application are described above in conjunction with the accompanying drawings. In the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present application is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of the present application, ordinary technicians in this field can also make many forms without departing from the purpose of the present application and the scope of protection of the claims, all of which are within the protection of the present application.

Claims

1. A method for preparing an osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant, characterized in that: The following steps are involved: S1: The zirconia implant model was designed by software, and the slurry was formed by mixing nano-zirconia powder containing 3% mol of yttrium with resin. Then, the implant embryo was prepared by a stereolithography printer with a laser power of 0.3-2W. S2: The green embryo is ultrasonically cleaned with 75% ethanol for 1 to 5 minutes, and then placed in an oven at a temperature of 100 to 250°C for curing for 2 to 5 hours to preliminarily remove part of the resin used as an adhesive; S3: transferring the green embryo to a muffle furnace at a temperature of 300-600°C for degreasing for 1-4 hours, and then transferring the green embryo to a muffle furnace at a temperature of 1300-1600°C for sintering for 3-5 hours, and finally cooling to room temperature with the furnace to obtain a zirconia implant; S4: mixing zinc oxide, phosphoric acid, nitric acid and deionized water, and adding additives to prepare a phosphating solution; S5: placing the phosphating solution and the zirconium oxide implant in a reaction kettle, placing the reaction kettle in an oven (1) at 150 to 230° C. for heating for 3 to 12 hours, and taking it out after natural cooling; S6: Use deionized water for ultrasonic cleaning for 1 to 5 minutes, and place in an oven for drying at 40 to 60°C to finally obtain a zirconia implant covered with a zinc phosphate coating.

2. The method for preparing the osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 1, characterized in that: The additive in S4 is one or more of MXene, HA and graphene.

3. The method for preparing the osteopromoting and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 2, characterized in that: The MXene phase is M2XT x and M3XT x phase, and is in a powdery form with a graphene-like structure; Wherein M is one or more of the transition metal elements Ti, Nb, Zr, Cu, Zn, Au, Ag, Mn and Mo with good biological activity; X is one or two of C and N; T x -OH, -O, -F and -Cl One or more of the surface groups.

4. The method for preparing the osteopromoting and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 2, characterized in that: The particle size of the HA phase is nanometer or submicron level.

5. The method for preparing the osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 2, characterized in that: The graphene is a single-layer or multi-layer structure.

6. The method for preparing the osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 1, characterized in that: The zinc oxide in the S4 is 0.3-0.9 mol / L, the phosphoric acid is 0.2-0.6 mol / L, the nitric acid is 0.6-1.8 mol / L, the additive is 0.5-2 g / L, and the molar ratio of zinc oxide to phosphoric acid is 3:

2.

7. A device for preparing the osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant as claimed in any one of claims 1 to 6, characterized in that: include: An oven (1) comprises a box body (10) and a heating mechanism (11) mounted on the inner wall of the box body (10); The kettle body (2) is installed in the box body (10), and the interior is divided into a plurality of active stirring chambers (20) and passive stirring chambers (21) arranged alternately, and a feed pipe (22) is installed on the side surface, and a discharge pipe (23) is installed on the bottom surface; A stirring mechanism (3) is installed in the kettle body (2) and comprises a rotating shaft (30) that passes through the plurality of active stirring chambers (20) and the passive stirring chambers (21) and a stirring rod (31) installed on the rotating shaft (30), wherein the stirring rod (31) is located in the active stirring chamber (20); A driving mechanism (4) is mounted on the oven (1) and is used to drive the rotating shaft (30) to rotate; Wherein, a partition net (24) is provided between the active stirring chamber (20) and the passive stirring chamber (21).

8. The device for preparing the osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 7, characterized in that: Also includes: A feeding mechanism (5) is plugged into the side of the kettle body (2), and comprises a first support net (50) for supporting the zirconium oxide implant and a cover plate (51) for being detachably connected to the kettle body (2), and is arranged corresponding to the passive stirring chamber (21); A sealing strip (6) is installed between the cover plate (51) and the kettle body (2) and is used for sealing the connection between the cover plate (51) and the kettle body (2); A locking member (7) is installed between the cover plate (51) and the kettle body (2) and is used for detachably connecting the cover plate (51) and the kettle body (2); The first support net (50) is provided with a notch (52) for avoiding the rotating shaft (30) when inserted into the kettle body (2), and a second support net (53) is hingedly connected to the inner wall of the notch (52).

9. The device for preparing the osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 8, characterized in that: The cover plate (51) is provided with a plurality of strip-shaped holes (54) on its circumference, wherein the locking member (7) comprises: The clamping strip (70) is rotatably connected to the side of the kettle body (2) by means of a cylinder (71) and is adapted to fit the strip-shaped hole (54); The arc-shaped convex strip (72) is installed on the surface of the cover plate (51) and is used to generate static friction force with the surface of the card strip (70) under the action of the sealing strip (6) when the card strip (70) is perpendicular to the strip hole (54); There are two arc-shaped convex strips (72), which are symmetrically arranged with each other, and one end of the symmetrical ends is chamfered.

10. The device for preparing the osteogenic and antibacterial zinc phosphate coating on the surface of a zirconium oxide implant according to claim 9, characterized in that: The locking member (7) further comprises: A limiting structure (73) is mounted on the arc-shaped convex strip (72) and is used for limiting the position of the clamping strip (70) and the strip-shaped hole (54) after they are in a vertical state; The limiting structure (73) comprises an embedding groove (730) provided at one end of an arc-shaped convex strip (72) away from its chamfered end and a protrusion (731) provided at another end of the arc-shaped convex strip (72) away from its chamfered end, and a toggle plate (732) is installed in the embedding groove (730), and the toggle plate (732) is hingedly connected to the arc-shaped convex strip (72) and is used to press one end to drive the toggle plate (732) to leave the embedding groove (730).

Images