Denture with high wear resistance and acid-etch resistance and method for processing thereof

Abstract

The application relates to the field of ceramic materials, and particularly discloses a denture with high wear resistance and acid-erosion resistance and a processing method thereof. The denture with high wear resistance and acid-erosion resistance comprises the following raw materials in parts by weight: 6-9 parts of zirconium oxide, 3-10 parts of yttrium oxide, 2-5 parts of a binder, 3-7 parts of a dispersing agent, 5-10 parts of PMMA resin and 3-6 parts of microcrystalline glass powder. The zirconium oxide is pretreated in the following manner: (1) the zirconium oxide is placed in a polydopamine solution, and is kept in the dark for 20-24 hours, then is washed with deionized water, dried and molded into a blank body; (2) the blank body is immersed in a graphene dispersion solution, and then is sintered at 700-750 DEG C for 1-2 hours and cooled. The denture has the advantages of high hardness and tensile strength, improved wear resistance and surface scratch resistance, improved acid-erosion resistance, inhibited bacterial aggregation and good antibacterial property.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic materials, and more particularly to a denture with high wear resistance and acid corrosion resistance and a processing method thereof. BACKGROUND

[0002] The development of oral medicine depends on the development of material science, and finding better oral materials has been the direction of many oral workers for many years. Dental nanocomposite material is a dental restoration material composed of resin matrix, inorganic filler after surface treatment and initiator system. Organic polymer is the main part of the material, which is a continuous distribution of high molecular organic matter, and its main function is to adhere the components of the composite material together, giving it plasticity, curability and certain strength. Inorganic fillers include nano calcium carbonate, nano silicon dioxide and nano titanium dioxide. Adding inorganic fillers can improve the rigidity of the composite material, but will reduce its elastic modulus and flexural strength. Moreover, the high specific surface area of inorganic fillers leads to high surface energy, which makes them easy to agglomerate and difficult to flow, bringing great difficulties to the processing process. The key to solving this contradiction is to select appropriate inorganic fillers or modify inorganic fillers, and optimize the types of modified substances and inorganic fillers.

[0003] In the prior art, the Chinese patent for invention with the application number CN2014106275440 discloses a calcium carbonate bioceramic for dental implant and a preparation method thereof. The calcium carbonate bioceramic for dental implant includes the following raw materials in parts by weight: calcium carbonate 140-180 parts, magnesium oxide 30-120 parts, zirconium oxide 60-80 parts, yttrium oxide 30-100 parts, sodium dodecyl benzene sulfonate 30-70 parts, polyvinylamide 20-50 parts, and modifier 10-30 parts. The preparation method is as follows: calcium carbonate, magnesium oxide, zirconium oxide and yttrium oxide are ground into powder, sodium dodecyl benzene sulfonate, polyvinylamide and modifier are added and uniformly mixed, and then the mixture is put into a mold for pressure forming; the green body is dried and the green body is fired at 700-800℃; and the pressure sintering is carried out at 1000-1400℃.

[0004] During the process of eating, teeth are in contact with each other and food during chewing, biting, swallowing and other activities, which causes irreversible loss of tooth hard tissue, i.e. tooth wear. Unhealthy oral habits, iatrogenic damage, the presence of poor restorations in the oral cavity and bruxism can all exacerbate tooth wear. In view of the above related technologies, the inventors found that the use of dicalcium phosphate reduces the porosity of bioceramics for dental implants and improves its mechanical properties. However, because the carbonate ions in the added calcium carbonate are easily combined with hydrogen ions in acidic substances, the calcium carbonate is dissolved, causing pores to appear on the surface of the denture and significantly reducing the mechanical properties and wear resistance of the denture. In addition, zirconia itself is brittle, which reduces the wear resistance of the denture. Furthermore, the roughness of the acid-etched surface of the denture is significantly increased, which makes various flora, microorganisms and bacteria in the oral cavity more easily adhere to the surface of the denture, further exacerbating the acid erosion of the denture, and thus causing a series of oral diseases, which seriously endanger the health of patients. SUMMARY

[0005] In order to improve the wear resistance and acid resistance of teeth, the present application provides a denture with high wear resistance and acid resistance and a processing method thereof.

[0006] In a first aspect, the present application provides a denture with high wear resistance and acid resistance, which adopts the following technical solution:

[0007] A denture with high wear resistance and acid resistance comprises the following raw materials by weight: 6-9 parts of zirconia, 3-10 parts of yttrium oxide, 2-5 parts of a binder, 3-7 parts of a dispersing agent, 5-10 parts of PMMA resin and 3-6 parts of microcrystalline glass powder.

[0008] The zirconia is pretreated as follows:

[0009] (1) The zirconia is placed in a polydopamine solution, and is kept in the dark for 20-24 hours. After being taken out, it is washed with deionized water and dried, and is molded into a blank body.

[0010] (2) The blank body is immersed in a graphene dispersion solution with a concentration of 1-1.5 wt%, and is impregnated at 0.7-0.9 MPa for 9-10 hours. Then, it is sintered at 700-750℃ for 1-2 hours and is cooled.

[0011] By adopting the technical scheme, the denture is prepared by using zirconium oxide, yttrium oxide, microcrystalline glass powder and PMMA resin as raw materials, the microcrystalline glass powder is microcrystalline glass powder with a softening point of 580 DEG C, which is a composite material with uniform distribution of microcrystals and glass bodies prepared by heat treatment of base glass, and has good mechanical strength, surface hardness and biocompatibility, and the zirconium oxide can reduce the crystallization temperature of the microcrystalline glass, strengthen the mechanical strength, the microcrystalline glass powder is heated and softened during the preparation of the denture, the viscosity of the mixed slurry is increased, the density of the denture is improved, the hardness and wear resistance of the denture are improved, in addition, no calcium carbonate, apatite and other minerals are used in the raw materials, the sensitivity of the denture to acidic substances is reduced, thereby the acid corrosion resistance of the denture is improved, the polydopamine has good biocompatibility and adhesion performance, and contains rich hydroxyl functional groups, which is a commonly used biomaterial surface modifier, after the zirconium oxide is placed in the polydopamine solution and treated in the dark, a layer of polydopamine film can be plated on the surface of the zirconium oxide, then the hydroxyl functional groups of the dopamine form hydrogen bonds with the electronegative carboxyl groups on the graphene; the graphene is uniformly dispersed between the zirconium oxide grains, and plays a pinning role on the zirconium oxide, so as to achieve the effect of refining the grains, and the introduction of the graphene can make part of the tetragonal phase change to monoclinic phase, so that microcracks are generated in the material, thereby absorbing the stress of the main crack and preventing the expansion of the crack, thereby playing a toughening effect, the graphene is a sheet structure, has a large specific surface area, and the surface is rough and wrinkled, which can improve the mechanical locking of the zirconium oxide and the graphene, and the stress transmission efficiency between the zirconium oxide and the graphene is improved under the auxiliary action of the polydopamine, after the phase change of the zirconium oxide, the denture expands, and the wrapping and fixing effect of the graphene can support the original structure and absorb the change, thereby improving the wear resistance of the denture, and the graphene as a typical two-dimensional nano material is composed of a hydrophobic plane and a hydrophilic edge, and its special structure determines its excellent antibacterial property, so that the denture has certain antibacterial property, prevents the breeding and reproduction of various pathogenic bacteria in the oral cavity, and affects the oral environment.

[0012] Optionally, during the pretreatment of the zirconium oxide, the mass ratio of the zirconium oxide, the polydopamine and the graphene is 1:0.3-0.5:0.8-1.

[0013] By adopting the technical scheme, the above mass ratio of raw materials can combine more graphene on the surface of the zirconium oxide and between the particles through the polydopamine, thereby connecting different regions of the zirconium oxide, making the zirconium oxide more dense, and making the graphene consume more energy to be pulled out, thereby achieving the toughening and strengthening effect; and the wrapped graphene can inhibit the growth of the zirconium oxide, make the tetragonal phase of the zirconium oxide change to monoclinic phase, generate microcracks to inhibit the expansion of the main cracks, thereby achieving the toughening effect, and enhancing the wear resistance and hardness of the denture.

[0014] Optionally, the pretreatment of the zirconia further comprises step (3): adding fluorinated graphene into dimethyl sulfoxide, adding polyether ether ketone, ultrasonic dispersion, drying to obtain a mixture;

[0015] The product obtained in step (2) is placed in the mixture, soaked and dried.

[0016] By adopting the technical scheme, the polyether ether ketone is a special engineering plastic, which has excellent mechanical properties, high temperature resistance, chemical corrosion resistance, radiation resistance, flame resistance and the like, and has good fatigue resistance to alternating stress, good biocompatibility, potential antibacterial property, similar elastic modulus to bone, and the like, the fluorinated graphene can further reduce the friction coefficient of the polyether ether ketone, enhance the friction performance, improve the strength of the polyether ether ketone, serve as a fulcrum to transfer and disperse pressure, enhance the plastic deformation resistance of the polyether ether ketone, and further enhance the antibacterial property of the denture to bacteria such as Staphylococcus aureus and Escherichia coli, and improve the oral environment; the fluorinated graphene and the polyether ether ketone are soaked on the zirconia embryo formed after sintering, which can further enhance the compactness of the zirconia, and improve the hardness and wear resistance of the zirconia.

[0017] Optionally, the mass ratio of the fluorinated graphene to the polyether ether ketone is 0.1-0.2:1;

[0018] The amount of the dimethyl sulfoxide is 2-3 times the total weight of the fluorinated graphene and the polyether ether ketone;

[0019] The mass ratio of the product obtained in step (2) to the mixture is 1:1.5-2.

[0020] By adopting the technical scheme, the above mass ratio of the components can load the fluorinated graphene and the polyether ether ketone on the surface of the zirconia, improve the wear resistance and hardness of the zirconia, and further enhance the antibacterial property of the zirconia, thereby improving the wear resistance, acid resistance and antibacterial property of the denture.

[0021] Optionally, the PMMA resin is pretreated as follows:

[0022] The POM ball is ultrasonically cleaned with anhydrous ethanol for 20-30 min, and then immersed in a silver nitrate solution, stirred in the dark, sodium borohydride is added, stirred, centrifuged, and a silver-loaded POM ball is prepared, which is laid in a mold, the molten PMMA resin is poured into the mold, and then solidified, demolded, and crushed after being taken out.

[0023] Due to insufficient hardness of PMMA, stress is too large to cause the denture to form cracks or even break, which seriously affects the service life of the denture, and because of the large amount of oral flora, solution ulcer, gingivitis and other denture stomatitis are caused, which brings discomfort to the patient. By adopting the above technical scheme, the polyformaldehyde POM ball has the advantages of high density linearity, high hardness and density, small oxidation resistance and water absorption, high thermal strength, better wear resistance and self-lubricity than most engineering plastics, and the POM ball is reduced by sodium borohydride on the surface of the POM ball, and nano-silver is loaded, so that the POM ball with antibacterial property is obtained, the POM ball is laid in the mold, and the PMMA resin is filled into the mold, the PMMA resin can completely infiltrate the POM ball, and a strong interfacial interaction is formed between the two phases, so that the PMMA resin with the POM ball embedded on the surface is prepared, thereby improving the hardness and antibacterial property of the PMMA resin, and when the PMMA resin is matched with zirconia and other components, the POM ball can be embedded in the denture, the density of the denture is improved, and the wear resistance is improved,

[0024] Optionally, the binder is selected from at least one of hydroxypropyl methylcellulose, polyvinyl alcohol, polyethylene glycol and guar gum.

[0025] By adopting the above technical scheme, the binder can enhance the viscosity between the components such as zirconia and yttria, and improve the density of the denture.

[0026] Optionally, the dispersant is selected from at least one of polyacrylic acid, polyethyleneimine, sodium dodecylbenzenesulfonate and sodium dodecyl sulfate.

[0027] By adopting the above technical scheme, the dispersant can enhance the uniform dispersion of the components such as zirconia and yttria, and improve the texture uniformity of each part of the denture.

[0028] In the second aspect, the application provides a processing method of a denture with high wear resistance and acid corrosion resistance, which adopts the following technical scheme:

[0029] A processing method of a denture with high wear resistance and acid corrosion resistance, comprising the following steps:

[0030] The zirconia is crushed, dispersed into deionized water with glass-ceramic powder and yttria, ground, and then the binder and the dispersant are added after being heated to 70-75 DEG C and stirred uniformly to prepare a slurry;

[0031] The slurry is removed of bubbles under vacuum condition, poured into a mold, and placed to form a preliminary embryo;

[0032] After the preliminary embryo is vacuum frozen for 70-72h, calcined at 500-550 DEG C for 1-2h, and then heated to 1550-1600 DEG C for 2.5-3h, it is cooled to room temperature to prepare a porous preliminary embryo;

[0033] The PMMA resin is added into the mixture of toluene and DMF, the porous embryo is immersed into the solution after stirring and dissolving, and the temperature is kept at 30-40 DEG C for 4-5 days, the temperature is increased to 90-100 DEG C and kept for 20-24 hours, and then the denture is obtained after cooling, polishing and surface cleaning.

[0034] By using the above technical scheme, the zirconium oxide and yttrium oxide are mixed with deionized water, dispersant and binder, the dispersant can improve the dispersibility of the zirconium oxide and yttrium oxide, the binder can increase the viscosity of the slurry, avoid the deposition of the zirconium oxide and yttrium oxide, and play a binding role after vacuum freezing and ice crystal sublimation, so as to avoid the collapse of the initial embryo, the ice crystal is completely removed after vacuum freezing, the dispersant and binder are removed after sintering, and the porous initial embryo with micro-orientation porous structure is obtained, the PMMA resin is dissolved in toluene and DMF, and then the PMMA resin is immersed into the gap of the porous initial embryo by capillary action, so that the denture with high density, good wear resistance and acid corrosion resistance is obtained.

[0035] Optionally, before the porous initial embryo is immersed into the PMMA solution, the following pretreatment is carried out: methanol and deionized water are mixed and stirred uniformly, the pH is adjusted to 4-4.5, the silane coupling agent KH570 is added, and then the porous initial embryo is immersed and placed for 20-24 hours, and then taken out and dried.

[0036] By using the above technical scheme, the silane coupling agent KH-570 is used for pretreatment of the porous initial embryo, which can increase the interface bonding between the porous initial embryo and the PMMA, the silane coupling agent KH570 reacts with the hydroxyl groups on the surface of the zirconium oxide through siloxane, and a covalent bond is formed between the two phases, so that the interface is enhanced, the interface action between the PMMA resin and the porous initial embryo is improved, and the wear resistance is improved.

[0037] Optionally, the temperature increasing and cooling process during the calcination of the initial embryo is as follows: the temperature is increased to 500-550 DEG C at a rate of 5 DEG C / min, kept for 1-2 hours, then increased to 1300-1350 DEG C at a rate of 5 DEG C / min, increased to 1400-1450 DEG C at a rate of 3 DEG C / min, increased to 1550-1600 DEG C at a rate of 2 DEG C / min, kept for 2.5-3 hours, then decreased to 1400-1450 DEG C at a rate of 2 DEG C / min, decreased to 1300-1350 DEG C at a rate of 3 DEG C / min, and decreased to room temperature at a rate of 5 DEG C / min.

[0038] In summary, the present application has the following beneficial effects:

[0039] 1. The denture is prepared from microcrystalline glass, PMMA resin, zirconia, etc., and the zirconia is pretreated with polydopamine solution and graphene. The hydroxyl group on polydopamine links with the carboxyl group on graphene, and graphene is coated between the surface and particles of zirconia, thereby improving the toughness and strength of zirconia, and improving its wear resistance, acid corrosion resistance and antibacterial properties.

[0040] 2. In the present application, fluorinated graphene and polyether ether ketone are preferably used to further treat the graphene pretreated zirconia. Fluorinated graphene can further reduce the friction coefficient of polyether ether ketone, and impart certain antibacterial properties to polyether ether ketone, so that the polyether ether ketone attached to the zirconia can further improve the wear resistance and antibacterial properties of the zirconia.

[0041] 3. The present application preferably uses POM balls to improve the toughness and strength of PMMA resin, and loads nano-silver on POMA balls, so that PMMA resin not only has high strength and toughness, but also has good antibacterial properties. Therefore, the antibacterial properties of the denture are improved, and the oral environment is improved.

[0042] 4. In the present application, zirconia, yttrium oxide, dispersant, microcrystalline glass powder, etc. are mixed to form a slurry, then vacuum freeze-dried to sublimate ice crystals, and obtain a porous embryo with a microscopically oriented porous structure. Then the dissolved PMMA resin is immersed in the porous embryo to fully fill the microporous structure, thereby improving the density of the denture, improving the hardness, and improving the wear resistance. DETAILED DESCRIPTION

[0043] EMBODIMENT

[0044] Example 1: A denture with high wear resistance and acid corrosion resistance, the raw material dosage is as follows: 9kg zirconia, 10kg yttrium oxide, 5kg binder, 7kg dispersant, 10kg PMMA resin and 6kg microcrystalline glass powder; the binder is polyvinyl alcohol, the dispersant is sodium dodecyl benzene sulfonate, the PMMA resin is selected from France Arkema, the model is V150, the particle size of yttrium oxide is 50μm, the microcrystalline glass powder is selected from Shijiazhuang Lomat Glass Technology, the model is LMT-Z750J, the softening point is 580℃, and the zirconia is pretreated as follows: (1) The zirconia is placed in a polydopamine solution with a concentration of 2mg / ml, and is placed in the dark for 24h. After taking out, it is washed with deionized water and dried, and is molded into an embryo body;

[0045] (2) The embryo body is immersed in a graphene dispersion solution with a concentration of 1.5wt%, and is immersed at 0.9MPa for 9h, and then is sintered at 700℃ for 2h, and is cooled. The ratio of zirconia, polydopamine and graphene is 1:0.5:1.

[0046] The above-mentioned processing method of the denture with high wear resistance and acid corrosion resistance comprises the following steps:

[0047] S1, crush zirconia to 40 μm, disperse zirconia, yttria, and glass-ceramic powder into deionized water, grind for 30 min, then add binder and dispersant after heating to 70℃, stir uniformly to prepare slurry, the amount of deionized water is 2 times the total weight of zirconia and yttria;

[0048] S2, remove bubbles in the slurry under vacuum, pour into a mold, and stand to form a green body;

[0049] S3, vacuum freeze the green body at 5 Pa for 72 h, then calcine at 500℃ for 2 h, then heat to 1550℃ and calcine for 3 h, and cool to room temperature to obtain a porous green body. The heating and cooling process during calcination of the green body is as follows: heat to 500℃ at a rate of 5℃ / min, keep for 2 h, heat to 1300℃ at a rate of 5℃ / min, heat to 1400℃ at a rate of 3℃ / min, heat to 1550℃ at a rate of 2℃ / min, keep for 3 h, cool to 1400℃ at a rate of 2℃ / min, cool to 1300℃ at a rate of 3℃ / min, and cool to room temperature at a rate of 5℃ / min;

[0050] S4, add PMMA resin to a mixture of toluene and DMF, the volume ratio of toluene to DMF in the mixture is 3:1, to prepare a PMMA solution with a concentration of 5wt%, after stirring and dissolving, immerse the porous green body in the solution, keep at 30℃ for 5 d, heat to 90℃ and keep for 24 h, cool, polish, and clean the surface to obtain a denture.

[0051] Example 2: A denture with high wear resistance and acid resistance, the amounts of raw materials are as follows: 6 kg of zirconia, 3 kg of yttria, 2 kg of binder, 3 kg of dispersant, 5 kg of PMMA resin, and 3 kg of glass-ceramic powder; the binder is polyvinyl alcohol, the dispersant is sodium dodecyl benzene sulfonate, the PMMA resin is selected from France Arkema, and the model is V150; the particle size of yttria is 50 μm; the zirconia is pretreated as follows: (1) place the zirconia in a polydopamine solution with a concentration of 2 mg / ml, avoid light, and stand for 20 h, then rinse with deionized water and dry, and mold into a body;

[0052] (2) immerse the body into a graphene dispersion liquid with a concentration of 1.0wt%, impregnate at 0.7 MPa for 10 h, then sinter at 750℃ for 1 h, and cool; the ratio of zirconia, polydopamine, and graphene is 1:0.3:0.8.

[0053] The processing method of the above-mentioned denture with high wear resistance and acid resistance comprises the following steps:

[0054] S1, zirconia is crushed to 40 pm, and the microcrystalline glass powder, yttrium oxide is dispersed into deionized water, grinded for 30 min, then heated to 75 DEG C, and then the binder and dispersant are added and stirred uniformly to prepare a slurry, and the amount of deionized water is 2 times the total weight of zirconia and yttrium oxide;

[0055] S2, the slurry is removed under vacuum conditions to remove bubbles, poured into a mold, and left to form a green body;

[0056] S3, the green body is vacuum frozen at 5 Pa for 70 h, then calcined at 550 DEG C for 1 h, and then heated to 1600 DEG C for 2.5 h, and then cooled to room temperature to obtain a porous green body. The heating and cooling process during calcination of the green body is as follows: heated to 550 DEG C at a rate of 5 DEG C / min, kept for 1 h, heated to 1350 DEG C at a rate of 5 DEG C / min, heated to 1450 DEG C at a rate of 3 DEG C / min, heated to 1600 DEG C at a rate of 2 DEG C / min, kept for 2.5 h, cooled to 1450 DEG C at a rate of 2 DEG C / min, cooled to 1350 DEG C at a rate of 3 DEG C / min, and cooled to room temperature at a rate of 5 DEG C / min;

[0057] S4, the PMMA resin is added to a mixture of toluene and DMF, the volume ratio of toluene to DMF in the mixture is 3:1, a PMMA solution with a concentration of 5wt% is prepared, after stirring and dissolving, the porous green body is immersed in the solution, kept at 40 DEG C for 4 days, heated to 100 DEG C and kept for 20 h, cooled, polished and cleaned to obtain a denture.

[0058] Example 3: a denture with high wear resistance and acid resistance, the difference from example 1 is that the pretreatment method of zirconia further comprises step (3): adding fluorinated graphene into dimethyl sulfoxide, adding polyether ether ketone, ultrasonic dispersion, drying to obtain a mixture, the mass ratio of fluorinated graphene to polyether ether ketone is 0.2:1, the amount of dimethyl sulfoxide is 3 times the total weight of fluorinated graphene and polyether ether ketone, and the polyether ether ketone is selected from shouweiges 2100, and the fluorinated graphene is selected from zhongkehui fluor, model GEF1.0;

[0059] The product obtained in step (2) is placed in a mixture of 2 times its weight, soaked and dried.

[0060] Example 4: a denture with high wear resistance and acid resistance, the difference from example 1 is that the pretreatment method of zirconia further comprises step (3): adding fluorinated graphene into dimethyl sulfoxide, adding polyether ether ketone, ultrasonic dispersion, drying to obtain a mixture, the mass ratio of fluorinated graphene to polyether ether ketone is 0.1:1, the amount of dimethyl sulfoxide is 2 times the total weight of fluorinated graphene and polyether ether ketone, and the polyether ether ketone is selected from shouweiges 2100, and the fluorinated graphene is selected from zhongkehui fluor, model GEF1.0;

[0061] The product obtained in step (2) is placed in a mixture of 1.5 times its weight, soaked, and dried.

[0062] Example 5: A denture with high wear resistance and acid resistance, which is different from example 3 in that no fluorinated graphene is added.

[0063] Example 6: A denture with high wear resistance and acid resistance, which is different from example 3 in that an equal amount of PMMA resin is used instead of polyether ether ketone, and the PMMA resin is selected from Arcomax, France, model V150.

[0064] Example 7: A denture with high wear resistance and acid resistance, which is different from example 3 in that the PMMA resin is pretreated as follows:

[0065] The POM balls are ultrasonically cleaned with anhydrous ethanol for 30 min, dried, and then immersed in a silver nitrate solution with a concentration of 2 mol / l, stirred in the dark, and then sodium borohydride is added. After stirring and centrifugation, silver-loaded POM balls are obtained. The silver-loaded POM balls are evenly laid in a mold, and the PMMA resin is melted and poured into the mold. After solidification, demolding is performed, and the product is crushed. The molar ratio of sodium borohydride to silver nitrate is 2:1, the mass ratio of silver nitrate to POM balls is 1:3, and the mass ratio of PMMA to silver-loaded POM balls is 1:0.3.

[0066] Example 8: A denture with high wear resistance and acid resistance, which is different from example 3 in that the PMMA resin is pretreated as follows:

[0067] The POM balls are ultrasonically cleaned with anhydrous ethanol for 30 min, dried, and then evenly laid in a mold. The PMMA resin is melted and poured into the mold. After solidification, demolding is performed, and the product is crushed. The mass ratio of PMMA resin to POM balls is 1:0.3.

[0068] Example 9: A denture with high wear resistance and acid resistance, which is different from example 7 in that, when preparing the denture, the porous embryo obtained in step S3 is immersed in a PMMA solution before being pretreated as follows: 1.8 kg of methanol and 0.2 kg of deionized water are mixed and stirred uniformly. Ice acetic acid is used to adjust the pH to 4. 0.5 kg of silane coupling agent KH570 is added and stirred uniformly to prepare a treatment solution. The porous embryo is immersed in the treatment solution and left to stand for 24 h. After taking it out, it is dried.

[0069] Comparative example

[0070] Comparative example 1: A denture with high wear resistance and acid resistance, which is different from example 1 in that no microcrystalline glass powder is added.

[0071] Comparative Example 2: A denture with high wear resistance and acid-etching resistance, which is different from Example 1 in that the zirconia is not pretreated.

[0072] Comparative Example 3: A denture with high wear resistance and acid-etching resistance, which is different from Example 1 in that no polydopamine solution is added when the zirconia is pretreated.

[0073] Comparative Example 4: A denture with high wear resistance and acid-etching resistance, which is different from Example 1 in that no graphene dispersion liquid is used when the zirconia is pretreated.

[0074] Comparative Example 5: A calcium carbonate bioceramic for dental implants, which comprises the following raw materials in parts by weight: calcium carbonate 160 parts, magnesium oxide 80 parts, zirconia 70 parts, yttrium oxide 60 parts, sodium dodecyl benzene sulfonate 50 parts, polyvinylamide 40 parts, and modifier 20 parts, the modifier being a propylene-butadiene-styrene copolymer, and the particle size of the yttrium oxide being 50 μm.

[0075] A method for preparing a calcium carbonate bioceramic for dental implants, which comprises the following steps: grinding calcium carbonate, magnesium oxide, zirconia, and yttrium oxide into powder, adding sodium dodecyl benzene sulfonate, polyvinylamide, and modifier, mixing uniformly, and then pressure forming in a mold; drying the green body, and firing the green body at 750°C; and pressure sintering at 1200°C, with a pressure of 65 kPa during sintering.

[0076] Performance detection test

[0077] The dentures are prepared according to the above method, and the performance is detected according to the following method, and the detection results are recorded in Table 1.

[0078] 1. Vickers hardness: the prepared dentures are detected for Vickers hardness using a microhardness (MH-5-VM) instrument, 10 points are detected for each sample, and the average value is taken;

[0079] 2. Tensile strength: the tensile strength is tested using an AGS-XSKN tester, 5 points are tested for each sample, the average value is taken, the sample is fixed on the tester, and the test is performed at a speed of 0.5 mm / min, the computer display shows the fracture process and the tensile strength, and the calculation formula of the tensile strength is: w = F / (b x d), wherein F is the maximum load, b is the sample width, and d is the sample thickness.

[0080] 3. Bacteriostasis: staphylococcus aureus strains preserved on a slope are taken with a sterilized inoculation ring at room temperature, and are inoculated on a sterilized flat plate culture medium, and are cultured in a 37°C constant temperature box for 24 h, and are transferred once every 24 h, not more than 2 weeks, and fresh bacteria are selected within 24 h; a small amount of cultured staphylococcus aureus and escherichia coli are dispersed in a container containing culture solution, and the concentration of the diluted bacterial solution is 8 x 10 5CFU / ml; the denture was sterilized, 0.2 ml of the bacterial solution was dropped on the sample, during the test, the sterilized covering film was evenly contacted with the sample, the sample was placed in a sterilized culture dish, and was cultured in a 37°C constant temperature box for 2 h, then the sample was taken out, the film was clamped, the surface of the sample was repeatedly washed with 20 ml of eluent, after shaking, a small amount was inoculated on agar medium, and after being cultured in a 37°C constant temperature box for 24 h, the bacterial colonies were counted, R(%)=(B-C) / B*100, R is the antibacterial rate, B is the number of bacteria in the control group, and C is the number of bacteria in the test group; the control group was a commercially available denture selected from the market.

[0081] 4. Acid erosion resistance: a 1 mmol / l citric acid solution (pH=3.2) was prepared with deionized water, 50 ml of the citric acid solution was taken, and the temperature was kept at 37°C; the denture was placed in the solution with the occlusal surface facing up, and was magnetically stirred to simulate the oral saliva flow environment; after 3 min of acid erosion treatment, the denture was taken out, repeatedly washed with deionized water, and dried at room temperature; and the Vickers hardness was detected by using a microhardness (MH-5-VM) instrument.

[0082] 5. Wear volume: a friction and wear testing machine (UMT-TriboLab, BRUKER, USA) was used for detection, a spherical contact mode was used, the flat sample was a tooth, the spherical counterpart was a TC4 titanium alloy ball with a diameter of 10 mm, the test was carried out at room temperature, the medium was deionized water, the normal load was 1 N, the reciprocating displacement was 1 mm, the frequency was 2 Hz, and the cycle number was 500 times.

[0083] Table 1: Performance detection of the denture

[0084]

[0085]

[0086] According to the data in Table 1 and Examples 1-2, in Examples 1 and 2, different amounts of raw materials were used, and the zirconia was pretreated, the obtained dentures had high Vickers hardness and tensile strength, small wear volume, and the antibacterial property needed to be improved, and after acid erosion, the Vickers hardness decreased little, and the acid erosion resistance was good.

[0087] Compared with Example 1, in Examples 3 and 4, the zirconia was pretreated, and graphene fluoride and polyether ether ketone were also used, and it was detected that the dentures prepared in Examples 3 and 4 had better wear resistance and acid erosion resistance than those in Example 1, and the antibacterial property was significantly increased.

[0088] In Example 5, no graphene fluoride was added, compared with Example 3, the Vickers hardness of the denture was reduced, the antibacterial ability was weakened, the tensile strength was reduced, and the wear volume was increased.

[0089] The PMMA resin is used to replace polyether ether ketone in Example 6, compared with Example 3, the wear volume is increased, the Vickers hardness is decreased, and the tensile strength is weakened.

[0090] Example 7 is compared with Example 3, and the silver-loaded POM ball is also used to pretreat the PMMA resin, the denture prepared in Example 7 has high Vickers hardness and antibacterial property, and the wear resistance is improved.

[0091] In Example 8, silver ions are not loaded on the POMA ball, compared with Example 3, the antibacterial ability of the denture prepared in Example 8 is weakened.

[0092] In Example 9, on the basis of Example 7, the porous embryo is pretreated with silane coupling agent KH570 when the denture is prepared, the tensile strength of the denture prepared in Example 9 is improved, and the wear resistance is improved.

[0093] In Comparative Example 1, compared with Example 1, no glass-ceramic powder is added to the denture, the tensile strength of the denture prepared in Comparative Example 1 is weakened, the wear resistance is reduced, and the acid resistance is weakened.

[0094] In Comparative Example 2, the zirconia is not pretreated, compared with Example 1, the antibacterial ability of the denture prepared in Comparative Example 2 is weakened, the wear resistance and the acid resistance are reduced.

[0095] In Comparative Example 3, the zirconia is pretreated without adding polydopamine solution, and in Comparative Example 4, the zirconia is pretreated without adding graphene dispersion liquid, compared with Example 1, the antibacterial property of the denture in Comparative Example 3 changes little, but the wear resistance and the acid resistance are weakened; the hardness and the wear resistance of the denture in Comparative Example 4 are reduced, the antibacterial property is weakened, and the acid resistance is reduced.

[0096] Comparative Example 5 is a bioceramic prepared by the prior art, which has strong initial Vickers hardness, but after wear, the wear volume is large, and after acid etching, the Vickers hardness is significantly reduced, and the acid resistance needs to be improved.

[0097] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, as long as the modifications are within the scope of the claims of the present application, and are protected by the patent law.

Claims

1. A denture having high abrasion resistance and acid-etch resistance, characterized by, The raw materials include the following weight parts: 6-9 parts of zirconium oxide, 3-10 parts of yttrium oxide, 2-5 parts of a binder, 3-7 parts of a dispersing agent, 5-10 parts of PMMA resin, and 3-6 parts of microcrystalline glass powder; the zirconium oxide is pretreated as follows: (1) The zirconium oxide is placed in a polydopamine solution and kept in the dark for 20-24 hours, then washed with deionized water and dried, and then molded into a body; (2) The body is immersed in a graphene dispersion solution with a concentration of 1-1.5 wt% at 0.7-0.9 MPa for 9-10 hours, and then sintered at 700-750°C for 1-2 hours, and cooled; when the zirconium oxide is pretreated, the mass ratio of zirconium oxide, polydopamine, and graphene is 1:0.3-0.5:0.8-1; The processing method of the denture with high wear resistance and acid corrosion resistance comprises the following steps: The zirconium oxide is crushed, dispersed with the microcrystalline glass powder and yttrium oxide in deionized water, ground, heated to 70-75°C, and then the binder and the dispersing agent are added and stirred uniformly to prepare a slurry; The slurry is degassed in a vacuum condition, poured into a mold, and left to stand to form a preliminary embryo; The preliminary embryo is vacuum frozen for 70-72 hours, calcined at 500-550°C for 1-2 hours, then heated to 1550-1600°C for calcination for 2.5-3 hours, and then cooled to room temperature to prepare a porous preliminary embryo; The PMMA resin is added to a mixture of toluene and DMF, stirred and dissolved, and then the porous preliminary embryo is immersed therein, incubated at 30-40°C for 4-5 days, heated to 90-100°C for 20-24 hours, and then cooled, polished, and cleaned to prepare the denture.

2. The denture having high wear resistance and acid-etch resistance according to claim 1, characterized by, The pretreatment of the zirconium oxide further comprises step (3): fluorinated graphene is added to dimethyl sulfoxide, polyether ether ketone is added, ultrasonic dispersion is performed, and then drying is performed to obtain a mixture, and the product obtained in step (2) is placed in the mixture for soaking and drying.

3. The denture having high wear resistance and acid-etch resistance according to claim 2, characterized by, The mass ratio of the fluorinated graphene and the polyether ether ketone is 0.1-0.2:1; The amount of the dimethyl sulfoxide is 2-3 times the total weight of the fluorinated graphene and the polyether ether ketone; The mass ratio of the product obtained in step (2) to the mixture is 1:1.5-2.

4. The denture having high wear resistance and acid-etch resistance according to claim 1, characterized by, The PMMA resin is pretreated as follows: The POM balls are ultrasonically cleaned with anhydrous ethanol for 20-30 minutes, dried, and then immersed in a silver nitrate solution, stirred in the dark, and then sodium borohydride is added, stirred, and centrifuged to prepare silver-loaded POM balls, which are laid in a mold, and then molten PMMA resin is poured into the mold, left to stand for solidification, demolded, and then crushed.

5. The denture having high wear resistance and acid-etch resistance according to claim 1, characterized by, The binder is selected from at least one of hydroxypropyl methyl cellulose, polyvinyl alcohol, polyethylene glycol, and guar gum.

6. The denture having high wear resistance and acid-etch resistance according to claim 1, characterized by, The dispersing agent is selected from at least one of polyacrylic acid, polyethyleneimine, sodium dodecylbenzenesulfonate, and sodium dodecyl sulfate.

7. The denture having high wear resistance and acid-etch resistance according to claim 1, characterized by, Before the porous preliminary embryo is immersed in the PMMA solution, the following pretreatment is performed: methanol and deionized water are mixed and stirred uniformly, the pH is adjusted to 4-4.5, silane coupling agent KH570 is added, stirred uniformly, and then the porous preliminary embryo is immersed, left to stand for 20-24 hours, taken out, and dried.

8. The denture having high wear resistance and acid-etch resistance according to claim 1, characterized by, The temperature rising and cooling process of the primary embryo during calcination is as follows: rising the temperature to 500-550℃ at a rate of 5℃ / min, keeping the temperature for 1-2h, then rising the temperature to 1300-1350℃ at a rate of 5℃ / min, rising the temperature to 1400-1450℃ at a rate of 3℃ / min, rising the temperature to 1550-1600℃ at a rate of 2℃ / min, keeping the temperature for 2.5-3h, then lowering the temperature to 1400-1450℃ at a rate of 2℃ / min, lowering the temperature to 1300-1350℃ at a rate of 3℃ / min, and lowering the temperature to room temperature at a rate of 5℃ / min.

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