CN115400264A - Preparation method of ceramic artificial joint opposite grinding pair - Google Patents

Abstract

The invention discloses a preparation method of a ceramic artificial joint opposite grinding pair, which comprises the following steps: firstly, preparing metal-doped porous zirconia toughened alumina (Me-ZTA) ceramic by adopting a rapid hot-pressing sintering method, then modifying the surface by using dopamine hydrochloride (DA) to obtain a PDA-Me-ZTA artificial joint pair grinding pair, and then preparing a Polydopamine (PDA) -polyvinyl alcohol (PVA) composite hydrogel coating on the surface of the PDA-Me-ZTA artificial joint pair grinding pair ceramic by using polyvinyl alcohol (PVA) and Polydopamine (PDA) as raw materials to construct a bionic articular cartilage material. The invention improves the lubricating and wear-resisting properties of the ceramic joint, greatly reduces the contact stress, abrasion and friction noise of the ceramic artificial joint, reduces the incidence of complications such as abrasion, breakage, abnormal sound and the like in the clinical application of the ceramic joint, and improves the quality of the ceramic joint and the comfort of patients.

Description

Preparation method of ceramic artificial joint opposite grinding pair

Technical Field

The invention belongs to the technical field of biological materials and material surface modification, and particularly relates to a preparation method of a ceramic artificial joint grinding pair.

Background

For patients with advanced arthritis and joint loss, joint replacement has become the most effective and ultimate treatment [ see also befosin, the present status and prospect of hip and knee joint replacement in china, china journal of bone and joint 01 (1) (2012) 4-8.]. The artificial joints applied clinically are mainly divided into three types, namely metal (or ceramic) -polymer joints (MoP or CoP), metal-metal (MoM) joints and ceramic-ceramic (CoC) joints according to the types of joint head-joint socket matched pair materials. Currently, the most clinically usable articular joint partners are ceramic-ceramic (CoC) joints, which have low wear rates [ t.m. grupp, m.holderid, m.a. mulliez, r.streller, m.jager, w.blomer, s.utzschilder, biology of a vitamin E-stabilized polyethylene for hip imaging-inflammation of the tissue of anatomical and third-body tissues on the road, acta biomelia 10 (7) (2014) 3068-3078.]Good scratch and Corrosion resistance [ Kocagoz, S.B., underwood, R.J., macDonald, D.W., gilbert, ceramic Heads gradient Metal used by Head-tape freezing and correction, clinical Orthopaedics)&Related Research 474(4) (2016)985-994.][C.Piconi,A.A.Porporati,R.M.Streicher,Ceramics in THR Bearings:Behavior under Off-Normal Conditions,Key Engineering Materials 631(2014)3-7.]The incidence of complications such as osteolysis, prosthesis loosening and infection is significantly reduced [ J.P.Kretzer, U.M.R.Streit, H.Kiefer, J.Reinders, ion release in ceramic bearings for total hip replacement: results from an in vitro and an in vivo study, international Orthopaedics 42 (1) (2017) 1-6 ].][A.Beraudi,S.Stea,D.De Pasquale,B. Bordini,S.Catalani,P.Apostoli,A.Toni,Metal ion release:also a concern for ceramic-on-ceramic couplings,Hip International the Journal of Clinical&Experimental Research on Hip Pathology& Therapy 24(4)(2014)321-326.][R.Sorrentino,A.Cochis,B.Azzimonti,C.Caravaca,J.Chevalier, M.Kuntz,A.A.Porporati,R.M.Streicher,L.Rimondini,Reduced bacterial adhesion on ceramics used for arthroplasty applications,Journal of the European Ceramic Society(2017) S0955221917306763.]Has good market prospect and the market share is increased year by year. Generation 4, derived by Sailantake Germany

The series is the most advanced ceramic joint at present, has the best using effect and the broadest clinical application, has 15 years of successful clinical experience, and has sold more than 800 ten thousand ceramic implant groups (https:// www.ceramtec-medical. Com/en/biolox/implant-material [ 2022.02.23)]][https://www.ceramtec .com.br/materiais-de-ceramica/biolox/delta/[2022.02.23]。

Although the ceramic joint greatly reduces the incidence of complications such as osteolysis, prosthesis loosening and infection, due to insufficient toughness of the ceramic material itself, and the cutting of the articular cartilage causes the lubrication state of the friction interface of the ceramic joint to be poor, the cushioning capacity of the joint to be greatly reduced, and the contact stress to be large, the ceramic artificial joint still has wear in practical application [ Walter, w.l., instrument, g.m., walter, w.k.and Tuke, m.a.,2004.Edge loading in third generation articular-on-ceramic bearings: the complications of Stripe wear, journal of arthoplasty, 19 (4), pp.402-413, fracture [ Winter, M., griss, P., scheller, G.and Moser, T.,1992. Ten-to-14-year results of ceramic hip prosthessisi. Clinical Orthopaedics and Related Research,282 (9), pp.73-80 ], abnormal sound [ Walter, W.L., O' Toole, G.C., walter, W.K., ellis, A.and Zicat, B.A., 2007.Squeering in ceramic-nucleus-ceramics, journal of arthoplasty, 22 (4), pp.496-503, and the like, still have a large difference in the function of ceramic joints.

How to make the ceramic artificial joint reach the lubrication and wear-resisting level of the natural joint, improve the buffer capacity of the ceramic joint, lighten the contact stress of a friction interface, and reduce the incidence rate of complications such as abrasion, breakage, abnormal sound and the like existing in the existing ceramic artificial joint for clinical application is the key for improving the quality of the ceramic artificial joint product and further promoting the clinical application of the ceramic joint.

Natural joints possess excellent lubricating and wear-resistant properties, the critical soft tissue coating The articular surfaces of bones — articular cartilage plays a crucial role in reducing friction between bones and cushioning vibrations generated during movement, and can exhibit a very low coefficient of friction at higher Hertz contact pressures (0.0005-0.04) [ Forster, fisher, the inflammation of The loading time and The vibration on The simulation of articular bearings, the Proceedings of The institute of Mechanical Engineers, part H, journal of engineering in medicine 210 (1996) 109-119 ]. The articular cartilage can be divided into 3 layers from top to bottom: a hyaline cartilage layer, a calcified cartilage layer and a subchondral bone layer. Wherein The Hyaline Cartilage layer has a thickness of between 2 and 6 mm and consists essentially of an extracellular matrix consisting of water (70%), collagen fibers (20%) and proteoglycans (5-10%) [ A. Komarraju, S.Goldberg-Stein, R.Pederson, C.Mcrum, A.Chhabra, spectrum of Common and uncompromised customers of Knee Journal carbohydrate regeneration and The pair Key Imaging Features, european Journal of Radiology 129 (January-February (1) (2020) 109097 ], chondrocytes distributed therein with an Elastic modulus of about 1.9 to 15MPa Z.Yning, 2012 W.Fuyu, T.Hongbo, C.guangxing, G.Lin, Y.Liu, of The molecular biology of The carbohydrate of calcium of [ 5. Journal of calcium of L5. J.) (J. L. J. G.Lin, Y.Lid., (III) of The molecular biology of The family of The calcium of The family of The Human tissue of The family L. J. (J. 9. J.),360, G.E.Kempson, the short-term compression properties of adult Human articular capsules, biological-dimensional materials and engineering 4 (3) (1994) 245 ] during Joint movement, hyaline Cartilage absorbs and releases synovial fluid, providing effective lubrication [ G.Li, E.P.Sangg, L.E. Defrate, M.E.Schutzer, L.Ji, T.J.Gill, H.E.RubaH, the cortical thermoplastic distribution in The biological Joint and correction with cortical-to-capsule contact, clinical biomedicines 20 (7) (2005) 736-744 ]; subchondral bone has good mechanical properties with an Elastic modulus as high as 4GPa, Z.Yung, W.Fuyou, T.Hongbo, C.guangxing, G.Lin, Y.Liu, analysis of The Mineral Composition of The Human specified Cartilage Zone, international Journal of Medical Sciences 9 (5) (2012) 353-360. [ P.L. Mente, J.L. Lewis, elastic modulus of calibrated Cartilage an order of magnitude bone of Cartilage free calcium of Cartilage Research 12 (5) (1994) 637-647 ], serving as a support during Joint motion, the elastic modulus is about 0.32gpa, z.ying, w.fuyou, t.hongbo, c.guangxing, g.lin, y.liu, analysis of the Mineral Composition of the Human Calcified Cartilage Zone, international Journal of Medical Sciences 9 (5) (2012) 353-360.] [ lathron, leizhou, zhuangchang, segetsu, research related to the calcification layer of articular Cartilage, china orthopedic surgery Journal 27 (8) (2019) 722-725.], upward connected to hyaline Cartilage through a wavy tide structure, downward connected to subchondral bone through a tight comb-like bond line structure, which increases the contact area between tissue interfaces, strengthens the connection strength between the interfaces 722, allows the Cartilage layer to be strongly fixed under the hyaline Cartilage layer, and simultaneously facilitates the development of Cartilage conduction layer of chinese Cartilage, (2019) transient orthopedic Cartilage bone conduction stress bearing research [ 12-27, 2019 ] for Cartilage conduction stress development of cartilaginous Cartilage, (2019) and transient orthopedic Cartilage repair related to Cartilage.

The natural articular cartilage has a multilayer gradient structure, so that the natural articular cartilage has extremely excellent lubricating and wear-resisting properties and can support the normal motion process of a human body for decades without showing signs of wear. If a multilayer gradient structure similar to natural cartilage is constructed on the ceramic artificial joint friction pair, the problems of insufficient interface lubrication, large contact stress and the like of the ceramic joint can be greatly improved, so that the incidence rate of existing complications such as abrasion, breakage, abnormal sound and the like of the ceramic artificial joint is reduced, the service quality of the ceramic joint and the comfort of a patient are improved, and the service life of the ceramic joint is prolonged.

Disclosure of Invention

The invention provides a preparation method of a ceramic artificial joint grinding pair (joint head and joint mortar) with low friction coefficient and low friction noise.

The invention relates to a preparation method of a ceramic artificial joint grinding pair, which comprises the following steps:

step 1: preparation of metal-doped porous zirconia toughened alumina Me-ZTA ceramic.

Dissolving compound powder containing metal elements into absolute ethyl alcohol, adding alumina powder, zirconia powder and yttria powder, mixing for 12-48 hours by using a planetary ball mill to obtain uniform ceramic slurry, drying the ceramic slurry in an oven at 60 ℃, then carrying out heat treatment at 332 ℃, carrying out ball milling and drying on the powder after the heat treatment again to obtain metal-doped zirconia-alumina composite ceramic powder; and (3) putting the uniformly mixed ceramic powder into a graphite mould, sintering in a rapid hot-pressing sintering furnace to obtain metal-doped porous zirconia toughened alumina Me-ZTA, and then machining to prepare the ceramic artificial joint grinding pair.

Step 2: the Me-ZTA ceramic artificial joint modifies dopamine DA on the surface of the grinding pair.

The Me-ZTA ceramic is immersed in a Tris-HCl solution of 2-10 mg/mL dopamine for 10-48 h, and then the redundant dopamine solution is washed away by deionized water to obtain the dopamine surface modified Me-ZTA ceramic, namely the PDA-Me-ZTA artificial joint pair grinding pair.

And 3, step 3: and (3) preparing the hydrogel.

Stirring 1.0-5.0 wt.% of PDA powder, 11.0-15.0 wt.% of PVA powder and 84wt.% of deionized water in a water bath at 90 ℃ for 3 hours to obtain PDA-PVA hydrogel precursor solution; centrifuging the PDA-PVA precursor solution for 5min at 6500pm to remove bubbles, coating the PDA-PVA precursor solution on PDA-Me-ZTA, freezing at-15-60 ℃ for 10-48 h, thawing at room temperature for 8-25 h, and circularly freezing and thawing for 3-6 times to gelatinize the hydrogel; finally, annealing the ceramic/hydrogel sample at 45-90 ℃ for 6-24 h, and then soaking in phosphate buffer PBS for 12-72 h.

Further, in the step 1, the doped metal element of the porous zirconia toughened alumina Me-ZTA is one of Cu, ag, fe and Mn, and the content of the doped metal element is 1.5-10.0 wt.%.

Preferably, in step 2, the Me-ZTA ceramic is immersed in a Tris-HCl solution containing dopamine, wherein the concentration of the dopamine is 2mg/mL, and the immersion time is 12h.

Preferably, the mass fraction of PDA in step 3 is 1.0wt.%, PVA 5.0wt.%, freezing temperature-20 ℃, freezing time 16h, thawing time 8h at room temperature, number of cycles of freezing and thawing 4, ceramic/hydrogel samples annealed at 60 ℃ for 12h, rehydrated in phosphate buffered saline, PBS, for 24h.

Further, the alcoholysis degree of the PVA in the step 3 is 98.0-99.0% (mol/mol), and the viscosity is 54.0-66.0 mPas.

The beneficial technical effects of the invention are as follows:

1. the metal-doped porous zirconia toughened alumina ceramic material can meet the requirement of mechanical properties of human bones and has a supporting effect in a friction process.

2. A hydrogel-gathering cartilage layer is constructed on the surface of a metal-doped porous zirconia toughened alumina ceramic material, and a composite structure formed between the porous surface of the ceramic and the hydrogel realizes strong and stable combination between the porous ceramic substrate and the hydrogel under the synergistic action of connection topology, chemical bonds and a dissipation mechanism.

3. The hydrogel coating has the physical and chemical properties similar to those of articular cartilage, the dynamic response to applied load can improve the lubrication state of a friction interface of a ceramic joint material, reduce the interface friction coefficient and the interface contact stress, reduce the incidence rate of complications such as fracture, abrasion and abnormal sound of the ceramic joint in clinical application, and improve the service quality of the ceramic joint and the comfort of a patient.

Drawings

FIG. 1 shows the present invention.

FIG. 2 is the results of the test of the binding property of the hydrogel prepared in example 1 to the ceramic.

FIG. 3 is a graph showing the coefficient of friction of the ceramic material of the hydrogel/ceramic composite structure prepared in example 1 in a PBS solution.

Detailed Description

The invention is described in further detail below with reference to the figures and the specific embodiments.

The research idea of the invention is shown in figure 1, and the invention simulates the multilayer gradient structure (transparent cartilage layer, calcified cartilage layer and subchondral bone layer) of natural cartilage, and designs and prepares the hydrogel-modified metal-doped porous Zirconia Toughened Alumina (ZTA) ceramic artificial joint. Specifically, a porous metal doped zirconia toughened alumina ceramic/hydrogel composite structure is constructed on the basis of preparing the metal doped zirconia toughened alumina ceramic by utilizing a surface modification technology and a biomimetic material design concept, and is applied to a ceramic artificial joint, so that the contact stress, abrasion and friction noise of the ceramic artificial joint are greatly reduced, the incidence rate of complications such as abrasion, breakage, abnormal sound and the like existing in the clinical application of the ceramic joint is reduced, and the quality of the ceramic joint is improved. Firstly, preparing metal-doped porous Zirconia Toughened Alumina (ZTA) ceramic by adopting a rapid hot-pressing sintering method, then preparing a Polydopamine (PDA) -polyvinyl alcohol (PVA) composite hydrogel coating on the surface of the dopamine-modified metal-doped porous Zirconia Toughened Alumina (ZTA) ceramic by taking polyvinyl alcohol (PVA), dopamine hydrochloride (DA) and Polydopamine (PDA) as raw materials, and constructing the bionic articular cartilage material. The metal-doped porous zirconia toughened alumina ceramic matrix at the bottom can meet the requirement of mechanical property of human bones and has the same supporting effect as a subchondral bone layer in the friction process; the hydrogel coating on the top has physical and chemical properties similar to those of the transparent cartilage layer, and the hydrogel dual-phase structure can realize dynamic response to applied load, improve the lubricating performance of the ceramic joint and reduce the contact stress of the ceramic joint; the porous structure of the ceramic can form a connection topology with the surface of the hydrogel, metal ions released by the metal-doped porous ceramic material can coordinate with hydroxyl groups in the hydrogel to form chemical bonds, and the response mechanism of the hydrogel to stress in the friction process can realize energy dissipation. Therefore, the metal-doped porous zirconia toughened alumina is tightly anchored with the carried hydrogel through the synergistic effect of the connection topology, the chemical bond and the dissipation mechanism, as well as the calcified cartilage layer in the natural cartilage, as shown in fig. 2, the contact area between tissue interfaces is increased, the connection strength between the interfaces is enhanced, and meanwhile, the porous surface is also favorable for dispersing the instantaneous stress born by the hydrogel, so that the hydrogel can be strongly fixed on the ceramic substrate. The hydrogel/porous ceramic composite material prepared by the bionic natural cartilage gradient structure design can greatly reduce the contact stress of a ceramic joint friction interface, reduce joint abrasion and enhance interface lubrication, and as shown in figure 3, the hydrogel/porous ceramic composite material effectively reduces the incidence rate of complications such as fracture, abrasion, abnormal sound and the like of the ceramic joint in clinical application and improves the service quality of the ceramic joint and the comfort of a patient.

Example 1

A. Preparing raw materials: polyvinyl alcohol (PVA) powder, dopamine hydrochloride (DA) powder, polydopamine (PDA) powder, tris-HCl buffer solution, phosphate Buffer Solution (PBS), copper nitrate trihydrate powder, aluminum oxide powder, zirconium oxide powder and yttrium oxide powder are used as raw materials, and the mass percent of Cu is 1.5wt.%.

B. Preparation procedure

a) Preparing copper-doped porous zirconia toughened alumina (Cu-ZTA) ceramic;

mixing the copper nitrate trihydrate powder, the alumina powder, the zirconia powder and the yttria powder for 12 hours by using a planetary ball mill, wherein the mass percent of Cu is 1.5wt.%. Then drying at 60 ℃, carrying out heat treatment at 332 ℃, and then carrying out ball milling and drying again. And (3) putting the uniformly mixed ceramic powder into a graphite die, and sintering in a rapid hot-pressing sintering furnace to obtain the copper-doped zirconium oxide toughened alumina (Cu-ZTA).

b) Modification of Dopamine (DA) on the surface of Cu-ZTA;

and (3) immersing the Cu-ZTA ceramic into a Tris-HCl solution of 2mg/mL dopamine for 24h to obtain dopamine surface modified Cu-ZTA ceramic (PDA-Cu-ZTA).

c) Preparing a hydrogel;

(1) stirring 1wt.% of PDA, 15wt.% of PVA and 84wt.% of deionized water in a water bath at 90 ℃ for 3 hours to obtain a PDA-PVA hydrogel precursor solution; (2) coating the PDA-PVA precursor solution on PDA-Cu-ZTA, freezing at-20 deg.C for 16h, thawing at room temperature for 8h, and repeating for four times to gelatinize the hydrogel; (3) finally, annealing at 60 ℃ for 12h, and soaking in Phosphate Buffered Saline (PBS) for 24h.

Specific values of the process parameters in examples 2 to 12 are shown in table 1.

TABLE 1 EXAMPLES 2 TO 12 PROCESS PARAMETERS

Example 13

A. Preparing raw materials: polyvinyl alcohol (PVA) powder, dopamine hydrochloride (DA) powder, polydopamine (PDA) powder, tris-HCl buffer solution, phosphate Buffer Solution (PBS), ferric nitrate nonahydrate powder, aluminum oxide powder, zirconium oxide powder and yttrium oxide powder are used as raw materials, and the mass percent of Fe is 1.5wt.%.

B. Preparation steps

a) Preparation of iron-doped porous zirconia toughened alumina (Fe-ZTA) ceramic

Mixing ferric nitrate nonahydrate powder, aluminum oxide powder, zirconium oxide powder and yttrium oxide powder for 12h by using a planetary ball mill, wherein the mass percent of Fe is 1.5wt.%. Then drying at 60 ℃, carrying out heat treatment at 332 ℃, and then carrying out ball milling and drying again. And (3) putting the uniformly mixed ceramic powder into a graphite die, and sintering in a rapid hot-pressing sintering furnace to obtain the iron-doped zirconia toughened alumina (Fe-ZTA).

b) Fe-ZTA surface Dopamine (DA) modification

And (3) immersing the Fe-ZTA ceramic into a Tris-HCl solution of 2mg/mL dopamine for 24h to obtain the dopamine surface modified Fe-ZTA ceramic (PDA-Fe-ZTA).

c) Preparation of hydrogels

(1) Stirring 1wt.% of PDA, 15wt.% of PVA and 84wt.% of deionized water in a water bath at 90 ℃ for 3 hours to obtain a PDA-PVA hydrogel precursor solution; (2) coating the PDA-PVA precursor solution on PDA-Fe-ZTA, freezing at-20 deg.C for 16h, thawing at room temperature for 8h, and repeating for four times to form hydrogel; (3) finally, annealing at 60 ℃ for 12h, and soaking in Phosphate Buffered Saline (PBS) for 24h.

Specific values of the process parameters in examples 14 to 24 are shown in Table 2.

TABLE 2 EXAMPLES 14 TO 24 PROCESS PARAMETERS

Example 25

A. Preparing raw materials: polyvinyl alcohol (PVA) powder, dopamine hydrochloride (DA) powder, polydopamine (PDA) powder, tris-HCl buffer solution, phosphate Buffer Solution (PBS), manganese nitrate tetrahydrate powder, aluminum oxide powder, zirconium oxide powder and yttrium oxide powder are used as raw materials, and the mass percent of Mn is 1.5wt.%.

B. Preparation procedure

a) Preparation of manganese-doped porous zirconia toughened alumina (Mn-ZTA) ceramic

Mixing manganese nitrate tetrahydrate powder, aluminum oxide powder, zirconium oxide powder and yttrium oxide powder for 12 hours by using a planetary ball mill, wherein the mass percent of Mn is 1.5wt.%. Then drying at 60 ℃, carrying out heat treatment at 332 ℃, and then carrying out ball milling and drying again. And (3) putting the uniformly mixed ceramic powder into a graphite die, and sintering in a rapid hot-pressing sintering furnace to obtain the manganese-doped zirconium oxide toughened alumina (Mn-ZTA).

b) Modification of Mn-ZTA surface with Dopamine (DA)

And (3) immersing the Mn-ZTA ceramic into a Tris-HCl solution of 2mg/mL dopamine for 24h to obtain the dopamine surface modified Mn-ZTA ceramic (PDA-Mn-ZTA).

c) Preparation of hydrogels

(1) Stirring 1wt.% of PDA, 15wt.% of PVA and 84wt.% of deionized water in a water bath at 90 ℃ for 3 hours to obtain a PDA-PVA hydrogel precursor solution; (2) coating the PDA-PVA precursor solution on PDA-Mn-ZTA, freezing at-20 deg.C for 16h, thawing at room temperature for 8h, and repeating for four times to gelatinize the hydrogel; (3) finally, annealing at 60 ℃ for 12h, and soaking in Phosphate Buffered Saline (PBS) for 24h.

Specific values of the process parameters in examples 26 to 37 are shown in Table 3.

TABLE 3 Process parameters 26 to 36

The result of the test on the binding performance of the hydrogel and the ceramic of the embodiment of the invention is shown in fig. 2, and the result shows that the interface binding force of the hydrogel for surface modification of the metal-doped porous zirconia-toughened alumina ceramic is superior to that of the traditional hydrogel for surface modification of the zirconia-toughened alumina ceramic.

The friction test result of the ceramic material with the hydrogel/ceramic composite structure in the PBS solution of the embodiment of the invention is shown in FIG. 3, and the result shows that the friction coefficient of the ceramic material with the hydrogel/ceramic composite structure is lower than that of the zirconia toughened alumina ceramic material.

Claims (5)

1. The preparation method of the ceramic artificial joint opposite grinding pair is characterized by comprising the following steps of:

step 1: preparing metal-doped porous zirconia toughened alumina Me-ZTA ceramic;

dissolving compound powder containing metal elements into absolute ethyl alcohol, then adding alumina powder, zirconia powder and yttria powder, mixing for 12-48 h by using a planetary ball mill to obtain uniform ceramic slurry, drying the ceramic slurry in an oven at 60 ℃, then carrying out heat treatment at 332 ℃, carrying out ball milling and drying on the powder after heat treatment again to obtain metal-doped zirconia-alumina composite ceramic powder; putting the uniformly mixed ceramic powder into a graphite die, sintering in a rapid hot-pressing sintering furnace to obtain metal-doped porous zirconia toughened alumina Me-ZTA, and then machining to prepare a ceramic artificial joint grinding pair;

and 2, step: modifying the DA of the dopamine on the surface of the grinding pair by the Me-ZTA ceramic artificial joint;

soaking the Me-ZTA ceramic into a Tris-HCl solution of 2-10 mg/mL dopamine for 10-48 h, and then flushing redundant dopamine solution by using deionized water to obtain the dopamine surface modified Me-ZTA ceramic, namely a PDA-Me-ZTA artificial joint pair grinding pair;

and step 3: preparing a hydrogel;

stirring 1.0-5.0 wt.% of PDA powder, 11.0-15.0 wt.% of PVA powder and 84wt.% of deionized water in a water bath at 90 ℃ for 3 hours to obtain PDA-PVA hydrogel precursor solution; centrifuging the PDA-PVA precursor solution for 5min at 6500pm to remove bubbles, coating the PDA-PVA precursor solution on PDA-Me-ZTA, freezing at-15-60 ℃ for 10-48 h, thawing at room temperature for 8-25 h, and circularly freezing and thawing for 3-6 times to gelatinize the hydrogel; finally, annealing the ceramic/hydrogel sample at 45-90 ℃ for 6-24 h, and then soaking in phosphate buffer PBS for 12-72 h.

2. The method for preparing the ceramic artificial joint grinding pair according to claim 1, wherein the porous zirconia toughened alumina Me-ZTA in step 1 is doped with one of Cu, ag, fe and Mn, and the content of the doped metal element is 1.5-10.0 wt.%.

3. The method for preparing the ceramic artificial joint grinding pair according to claim 1, wherein in the step 2, the Me-ZTA ceramic is immersed in a Tris-HCl solution containing dopamine, the concentration of the dopamine is 2mg/mL, and the immersion time is 12h.

4. The method for preparing the ceramic artificial joint grinding pair according to claim 1, wherein in the step 3, the mass fraction of PDA is 1.0wt.%, the mass fraction of PVA is 15.0wt.%, the freezing temperature is-20 ℃, the freezing time is 16h, the thawing time at room temperature is 8h, the number of times of cyclic freezing and thawing is 4, and the ceramic/hydrogel sample is annealed at 60 ℃ for 12h and rehydrated in phosphate-buffered saline (PBS) for 24h.

5. The method for preparing a ceramic artificial joint grinding pair according to claim 1, wherein the alcoholysis degree of PVA in the step 3 is 98.0-99.0% (mol/mol) and the viscosity is 54.0-66.0 mPa-s.

Images