CN118252973A - PAEK joint prosthesis with high bonding strength with bone cement and treatment method thereof - Google Patents

PAEK joint prosthesis with high bonding strength with bone cement and treatment method thereof Download PDF

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Publication number
CN118252973A
CN118252973A CN202410249904.1A CN202410249904A CN118252973A CN 118252973 A CN118252973 A CN 118252973A CN 202410249904 A CN202410249904 A CN 202410249904A CN 118252973 A CN118252973 A CN 118252973A
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paek
joint prosthesis
bone cement
coating
treatment
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CN202410249904.1A
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Inventor
林意华
蔡仁钦
曾达
时瑞
周茂丰
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Double Medical Technology Inc
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Double Medical Technology Inc
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Abstract

The invention relates to a PAEK joint prosthesis with high bonding strength with bone cement and a treatment method thereof, comprising the following steps: s1, surface cleaning: placing the PAEK joint prosthesis in a solvent for cleaning, and then drying for later use; s2, surface treatment: performing plasma treatment on the PAEK joint prosthesis interface; s3, preparing a coating: applying a bone cement compatible polymer coating at the PAEK joint prosthesis interface to form a polymer coating; s4, curing the coating: placing the PAEK joint prosthesis into an oven for baking and curing; s5, annealing the coating: annealing the PAEK joint prosthesis to obtain a PAEK joint prosthesis with a precoating coating; the invention converts the interfacial bonding mode between the bone cement and the joint prosthesis into chemical bonding through the precoating, thereby enhancing the interfacial bonding strength between the bone cement and the joint prosthesis and reducing the possibility that the prosthesis loosens and breaks away from the bone cement along with the time.

Description

PAEK joint prosthesis with high bonding strength with bone cement and treatment method thereof
Technical Field
The invention relates to a medical device, in particular to a PAEK joint prosthesis with high bonding strength with bone cement and a treatment method thereof.
Background
Joint replacement is an alternative method of treating significant trauma or disease of the joint (arthritis, bone tumors, etc.) to repair diseased or damaged bone, bone-related tissues and/or joints, not only to restore part of the joint function, but also to alleviate the associated pain and discomfort.
Currently, commercially available joint materials mainly include metal-Ultra High Molecular Weight Polyethylene (UHMWPE), ceramic-Ultra High Molecular Weight Polyethylene (UHMWPE), and the like. Although the materials have excellent wear resistance and mechanical strength, the technical problems of prosthesis fixation, stress shielding, potential metal ion harm, ceramic fragmentation, image inspection artifact and the like exist. In order to solve the problems, CN105030383A, CN204709085U and CN204618488U propose a combined all-organic polymer material unicondylar artificial knee joint. CN107982582a proposes an orthopaedic prosthesis joint comprising a joint partner comprising a first bearing surface made of a Polyaryletherketone (PAEK) and a second bearing having a second bearing made of a polymer softer than PAEK, such as UHMWPE. These patents all utilize polyether ether ketone (PEEK) or its derivatives to replace cobalt chromium molybdenum (Co-Cr-Mo) alloy materials to prepare femoral condyles and tibial trays.
PAEK is a high-performance thermoplastic resin, has good processing and molding properties, good biocompatibility, elastic modulus close to bones and ray permeability, has been widely used in the fields of orthopaedics, orthopaedics and the like, and has great application potential in the field of medical instrument raw materials. Although PAEK polymer-UHMWPE support pairs (e.g., PEEK-UHMWPE) have lower wear rates than typical orthopedic support pairs (e.g., metal-UHMWPE), the potential corrosion, allergy, stress shielding problems of metal components may also be addressed. However, the fixation of PAEK joint prostheses to bone is still a problem due to the smooth, dense surface morphology and hydrophobicity of PAEK materials. In implanting a prosthesis, to ensure that the prosthesis is fixed to the bone, two types of fixation are used: bone cement type and non-bone cement type. Bone cement type fixation Polymethylmethacrylate (PMMA) bone cement was used at the bone/implant interface in order to establish a firm connection between the bone cement and the bone and between the bone cement and the implant. However, bone cements are typically applied in a highly viscous dough-like form, with insufficient contact between the joint prosthesis and the bone cement. Furthermore, the surface of PAEK joint prostheses is typically a weak boundary layer. Unfortunately, the formation of good adhesion of PAEK joint prostheses to bone cement is not favored by three factors, such as fewer reactive groups on the surface of the PAEK-like high strength polymeric material, poor surface contact, weak boundary layers, and lack of reactive groups. The implanted joint prosthesis is easy to cause the failure of the prosthesis/bone cement interface due to factors such as mechanical stress, fatigue and the like when supporting and bearing external stress and strain. In order for bone cement to attach the polymeric prosthesis to adjacent bone, there is a prior art method of machining the interface of the prosthesis with the bone cement to rough surfaces or grooves, using mechanical interlocking to enhance the interfacial bond strength.
Although the rough surface or the groove pattern of the contact interface of the PAEK joint prosthesis and cement can improve the bonding strength of the interface to a certain extent, the groove pattern can lead to stress concentration, and meanwhile, the physical interlocking structure can be loosened with the passage of time, so that the bonding strength of the interface and the long-term stability are difficult to obtain satisfactory effects. Therefore, there remains a need for improved interfacial adhesion between PAEK joint prostheses and bone cement, and there is a need for a method of enhancing interfacial adhesion between bone cement and PAEK prostheses to improve reliability and extend service life of the prostheses during service.
Disclosure of Invention
The invention aims to provide a PAEK joint prosthesis with high bonding strength with bone cement and a treatment method thereof, which changes the interface bonding mode between the bone cement and the joint prosthesis from mechanical interlocking to chemical bonding through a precoat, thereby enhancing the interface bonding strength between the bone cement and the joint prosthesis so as to reduce the possibility that the prosthesis loosens and breaks away from the bone cement along with the time.
The invention is realized by the following technical scheme: 1. a PAEK joint prosthesis treatment method with high bonding strength with bone cement, characterized by comprising the following steps:
s1, surface cleaning: placing the PAEK joint prosthesis in a solvent for cleaning, and then drying for later use;
s2, surface treatment: placing the PAEK joint prosthesis interface treated in the step S1 under a rotating gun head of a plasma surface activation machine to carry out surface plasma treatment;
S3, preparing a coating: applying a polymer coating compatible with bone cement to the PAEK joint prosthesis interface after the treatment of S2, and then airing in a fume hood to form a layer of polymer coating tightly combined with the PAEK joint prosthesis interface;
S4, curing the coating: putting the PAEK joint prosthesis processed in the step S3 into a baking oven for baking and curing;
S5, annealing the coating: and (3) placing the PAEK joint prosthesis treated in the step (S4) in high temperature for annealing treatment, and finally obtaining the PAEK joint prosthesis with the precoating coating.
A PAEK joint prosthesis with high bonding strength with bone cement is prepared by the treatment method.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention changes the interface bonding mode between the bone cement and the joint prosthesis from mechanical interlocking to chemical bonding through the precoating, thereby enhancing the interface bonding strength between the bone cement and the joint prosthesis and reducing the possibility that the prosthesis loosens and breaks away from the bone cement along with the time.
2. The PAEK joint prosthesis with the precoated surface is simple in preparation method, large equipment is not needed, and the surface of a product with a complex shape can be modified.
3. Active groups on the surface of the material after plasma treatment are not only favorable for spreading the coating on the surface, but also can be subjected to chemical reaction with MMA monomers in the curing and annealing processes, so that the interface bonding strength between the coating and the PEAK prosthesis is improved.
4. The bone cement compatible polymer is used as an interface coating material to assist in interface bonding, and the coating material participates in the swelling and curing processes of bone cement under the condition of not affecting the mechanical properties of PAEK. And a certain degree of covalent bond is generated between the bone cement and the coating, so that the bonding strength of the PAEK joint prosthesis and the bone cement interface is improved.
Drawings
FIG. 1 is an electron spectroscopy (EDS) spectrum of PEEK material before plasma treatment in example 1;
FIG. 2 is an electron spectroscopy (EDS) spectrum of PEEK material after plasma treatment in example 1;
FIG. 3 is a schematic view of the water contact angle of PEEK platform surface after plasma treatment of example 1;
FIG. 4 is a schematic view of the water contact angle of PEEK platform surface prior to plasma treatment of example 1;
FIG. 5 is a schematic view of the appearance of a PEEK-P-coating1 tibial plateau of example 1;
FIG. 6 is a schematic view of the appearance of a PEEK tibial plateau;
fig. 7 is a schematic illustration of the ejection force of the modified anterior and posterior PEEK tibial plateau and bone cement.
Fig. 8 is a photograph of a sample block after a PEEK-P-coating1 tibial plateau and bone cement test.
Fig. 9 is a schematic drawing of ejection force of a modified PEEK-P-coating2 tibial plateau and bone cement.
Detailed Description
The invention is described in detail below with reference to the accompanying drawings:
A PAEK joint prosthesis treatment method with high bonding strength with bone cement, comprising the steps of:
s1, surface cleaning: placing the PAEK joint prosthesis in a solvent for cleaning, and then drying for later use;
In S1, the cleaning conditions are as follows: at room temperature, immersing the PAEK joint prosthesis into acetone for ultrasonic cleaning for 5-30 minutes, then immersing the PAEK joint prosthesis into ethanol for ultrasonic cleaning for 5-30 minutes after the PAEK joint prosthesis is taken out, and finally immersing the PAEK joint prosthesis into ultra-pure water for ultrasonic cleaning for 10 minutes.
The PAEK joint prosthesis surface dust, grease and other pollutants can be effectively removed through solvent cleaning conditions.
The drying condition is 80-100 ℃ drying.
S2, surface treatment: placing the PAEK joint prosthesis interface treated in the step S1 under a rotating gun head of a plasma surface activation machine to carry out surface plasma treatment;
The conditions of the plasma treatment in S2 are as follows: the pressure of the spray gun head during treatment is 0.3MPa, the power is 400-800 w, and the treatment time is 5-30 s.
The PAEK joint prosthesis interface can be activated by plasma treatment, so that the bonding strength of a coating formed on the surface and a material is enhanced.
S3, preparing a coating: applying a polymer coating compatible with bone cement to the PAEK joint prosthesis interface after the treatment of S2, and then airing in a fume hood to form a layer of polymer coating tightly combined with the PAEK joint prosthesis interface;
In S3, the thickness of the coating is 10-100 um. Preferably the thickness is 25 to 90um, most preferably 30 to 80um. The application modes include painting, spraying, dip coating, electrostatic coating and the like, and the preferred modes are painting, spraying and dip coating, and the most preferred modes are painting and spraying.
S4, curing the coating: putting the PAEK joint prosthesis processed in the step S3 into a baking oven for baking and curing;
In S4, the baking conditions are as follows: the temperature is 40-100 ℃ and the time is 30-120 min. Preferred baking conditions are: the temperature is 60-90 ℃ and the time is 30-60 min; the most preferred baking conditions are: the temperature is 70-80 ℃ and the time is 30-45 min.
S5, annealing the coating: placing the PAEK joint prosthesis treated in the step S4 in high temperature for annealing treatment to finally obtain the PAEK joint prosthesis with the precoating coating; specifically, the PAEK joint prosthesis treated in the step S4 is annealed at a temperature higher than the glass transition temperature of PMMA;
s5, the annealing temperature is 80-170 ℃ and the annealing time is 15-60 min; preferably 100-170 ℃ for 15-45 min; most preferably about 160℃for a period of 30 minutes.
The rate of annealing cooling does not exceed about 1.5 c/min until the coating temperature is below 80 c.
Curing or annealing may ensure that the MMA is fully polymerized and any volatile components are removed from the film. In addition, by heating the film to a temperature above the glass transition temperature of PMMA, any mechanical stresses generated during curing of the film will be eliminated.
Wherein, the polymer coating in S3 comprises the following components by mass percent: methyl methacrylate polymer: 1 to 10 percent; methyl methacrylate: 10-50%; benzoyl peroxide: 0 to 0.1 percent; solvent: the balance.
The methyl methacrylate polymer comprises one of polymethyl methacrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-butyl methacrylate copolymer and methyl methacrylate-styrene copolymer.
The solvent is one or a mixture of more of dichloromethane, chloroform or acetone.
The polymer coating compatible with bone cement is a coating with reactivity, and methyl methacrylate polymer is used as a thickening agent, and methyl methacrylate monomer and an initiator are used as auxiliary materials.
In the present invention, PAEK refers to thermoplastic Polyaryletherketones (PAEKs) and derivatives thereof useful in the preparation of prosthetic implants, including Polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketoneetherketone (PEKK), and the like, preferably Polyetheretherketone (PEEK) and Polyetherketoneketone (PEKK), most preferably Polyetheretherketone (PEEK).
The PAEK joint prosthesis comprises prosthetic components such as a tibial tray, a femoral condyle, an acetabular cup and the like which are matched with ultra-high molecular weight polyethylene.
The PAEK joint prosthesis can be prepared by injection molding, mechanical processing molding, injection-compression molding, hot pressing, additive manufacturing or a combination thereof; preferred preparation methods are injection molding, mechanical processing and compression molding, most preferably injection molding.
A PAEK joint prosthesis with high bonding strength with bone cement is prepared by the treatment method.
Preferred embodiments of the present invention are further illustrated by the following specific examples. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the following examples, "%" means weight percent and parts means parts by weight unless otherwise specified.
And analyzing the change condition of the main elements on the PEEK surface before and after plasma treatment by adopting an electron spectrometer (EDS).
The contact angle change of the sample surface before and after plasma treatment was measured using a water contact angle meter.
The appearance of the precoat was visually evaluated and classified into class a and class B. The A level is that the coating is uniform and complete; the B grade is coating with small area shrinkage cavity and orange peel.
And testing the pulling-out force of the PEEK sample, the PEEK sample with the precoated layer and the sample after the PEEK sample is adhered to the bone cement by using a universal material testing machine.
Cytotoxicity test was as follows: section 5 according to GB/T16886.5-2017 medical device biological evaluation: in vitro cytotoxicity test (MTT) method is adopted, OD value of each hole is measured at 490nm wavelength, relative proliferation rate of each hole cell is calculated, and potential cytotoxicity of the sample is evaluated.
Example 1
The present embodiment describes the present invention in detail using a polyether ether ketone (PEEK) tibial plateau as an example, but the present invention is not limited to a polyether ether ketone (PEEK) tibial plateau.
S1, surface cleaning: and immersing the PEEK tibial plateau prepared by injection molding into acetone for ultrasonic cleaning for 15 minutes at 25 ℃, taking out, immersing into ethanol for ultrasonic cleaning for 10 minutes, and immersing into ultrapure water for ultrasonic cleaning for 10 minutes. Subsequently, the mixture was dried in an oven at 80℃for further use.
S2, surface treatment: and (3) placing the PEEK tibial plateau interface (the area to be bonded with the bone cement) treated in the step (S1) under a rotating gun head of a plasma surface activation machine, and treating for 10S under the condition that the gun head pressure of the gun is 0.3MPa and the power is 500 w.
S3, preparing a coating: 3% of polymethyl methacrylate by weight; 25% methyl methacrylate; 0.05% benzoyl peroxide, adding the components into the rest chloroform, and fully stirring and dissolving to obtain the methyl methacrylate polymer coating for standby.
A polymer coating was applied by painting to the back of the S2 plasma treated PEEK tibial plateau. And (3) adjusting the thickness of the coating after coating, and airing in a fume hood to obtain a polymer coating, wherein the thickness of the coating is about 50um.
S4, curing the coating: and (3) placing the PEEK tibial plateau treated in the step (S3) into an oven, and baking at the temperature of 70 ℃ for 45min to solidify the coating.
S5, annealing the coating: and (3) placing the PEEK tibial plateau treated in the step (S4) in a 160 ℃ oven for 30min, cooling to room temperature at an annealing rate of 1 ℃/min, and obtaining the PEEK tibial plateau with the precoating layer, wherein a sample is denoted as PEEK-P-coating1.
Passing EDS test, plasma treating PEEK material before and after plasma treatment; the O content of the PEEK material surface was increased by 18% from 15% (shown in fig. 1) (shown in fig. 2). This demonstrates the successful introduction of reactive functional groups on the PEEK tibial plateau surface by plasma treatment.
Hydrophilicity test of surface precoated PEEK tibial plateau (PEEK-P-coating 1) and PEEK tibial plateau performance; the PEEK platform surface water contact angle after plasma treatment (shown in figure 3) is smaller than the PEEK surface water contact angle without surface modification (shown in figure 4). The water drop angle of the PEEK material surface is reduced from 82.3 degrees to 30.4 degrees before and after treatment, which shows that the PEEK material surface energy is changed, and the active functional groups improve the hydrophilicity of the PEEK material surface.
PEEK-P-coating1 tibial plateau (as shown in FIG. 5) and PEEK tibial plateau appearance (as shown in FIG. 6), the appearance of the coating was visually evaluated and PEEK-P-coating1 appearance was grade A.
The ejection force of the pre-coated PEEK tibial plateau (PEEK-P-coating 1) with bone cement and the ejection force of the PEEK tibial plateau with bone cement were measured under static load (as shown in fig. 7), and the PEEK tibial plateau was prepared for the comparative example (PEEK-P-coating) in fig. 7. In the preparation of the sample, the bone cement used was HeraeusMV+G. And (3) uniformly mixing the powder and the liquid at the temperature of 23 ℃, applying the bone cement on the surface to be measured of the precoated PEEK tibial plateau through a die, and compacting to ensure that the bone cement is completely contacted with the surface to be measured and embedded and fixed. After curing for 2 hours, a test sample block of bone cement embedding the prosthesis is obtained. During testing, the bone cement test sample block embedded with the prosthesis is installed on a test tool, compression testing is carried out at 50mm/min by using a 5mm connecting rod until the tibia platform is separated from the bone cement sample block, and the maximum ejection force is recorded. The ejection force of the pre-coating PEEK tibial plateau (PEEK-P-coating 1) and bone cement is 132N and is 2.12 times of that of the PEEK tibial plateau and bone cement (62N), which shows that the interface bonding strength of the PEEK joint prosthesis and the bone cement can be greatly improved through plasma treatment and surface pre-coating of PMMA polymer coating. Photographs of the modified tibial plateau and post-bone cement test coupons (as shown in fig. 8).
The cell viability of the leaching solution culture of the PEEK tibial plateau and the precoated PEEK tibial plateau is above 80%, which shows that the two samples have no cytotoxicity.
Example 2
S1, surface cleaning: step S1 of example 1.
S2, surface treatment: step S2 of example 1.
S3, preparing a coating:
5% of methyl methacrylate-styrene copolymer; 20% methyl methacrylate; 0.05% benzoyl peroxide, adding the components into the rest methylene dichloride, and fully stirring and dissolving to obtain the methyl methacrylate polymer coating for standby.
A polymer coating was applied by spraying to the back of the plasma treated PEEK tibial plateau. And (3) adjusting the thickness of the sprayed coating subjected to numerical control, and placing the coating in a fume hood for airing to obtain a polymer coating, wherein the thickness of the coating is about 50um.
S4, curing the coating: step S4 of example 1.
S5, annealing the coating: step S5 of example 1. The sample was designated PEEK-P-coating2.
The ejection force of the precoated PEEK tibial plateau (PEEK-P-coating 2) with bone cement was measured under static load and the test results are shown in FIG. 5. The ejection force of the precoated PEEK tibial plateau (PEEK-P-coating 2) and bone cement was 139N, while the ejection force of the PEEK tibial plateau and bone cement was about 62N.
The ejection force of PEEK-P-coating2 and bone cement is improved by about 124% over PEEK tibial plateau.
Comparative example
S1, surface cleaning: step S1 of example 1.
S2, surface treatment: no plasma treatment was performed.
S3, preparing a coating: as in example 1.
S4, curing the coating: step S4 of example 1.
S5, annealing the coating: step S5 of example 1. The sample was designated PEEK-coating.
The coated appearance grade of the precoated PEEK tibial plateau (PEEK-coating) is grade B.
The ejection force of the precoated PEEK tibial plateau (PEEK-coating 2) with bone cement was measured under static load and the test results are shown in FIG. 9. The ejection force of the pre-coating PEEK tibial plateau (PEEK-coating 2) and the bone cement is about 100N, which is about 61% higher than that of the PEEK-coating and the bone cement. This shows that the interfacial adhesion between PEEK material surface and bone cement can also be improved by directly pre-coating PMMA polymer coating on PEEK tibial plateau, but because the PEEK surface has smaller surface energy, the coating spreads less well on the surface, resulting in a certain degree of defect on the prepared coating surface, and the bonding strength of the coating is not good after plasma treatment.
It should be noted that the foregoing description is only a preferred embodiment of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood that modifications, equivalents, improvements and modifications to the technical solution described in the foregoing embodiments may occur to those skilled in the art, and all modifications, equivalents, and improvements are intended to be included within the spirit and principle of the present invention.

Claims (10)

1. A PAEK joint prosthesis treatment method with high bonding strength with bone cement, characterized by comprising the following steps:
s1, surface cleaning: placing the PAEK joint prosthesis in a solvent for cleaning, and then drying for later use;
s2, surface treatment: placing the PAEK joint prosthesis interface treated in the step S1 under a rotating gun head of a plasma surface activation machine to carry out surface plasma treatment;
S3, preparing a coating: applying a polymer coating compatible with bone cement to the PAEK joint prosthesis interface after the treatment of S2, and then airing in a fume hood to form a layer of polymer coating tightly combined with the PAEK joint prosthesis interface;
S4, curing the coating: putting the PAEK joint prosthesis processed in the step S3 into a baking oven for baking and curing;
S5, annealing the coating: and (3) placing the PAEK joint prosthesis treated in the step (S4) in high temperature for annealing treatment, and finally obtaining the PAEK joint prosthesis with the precoating coating.
2. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: the polymer coating in the S3 comprises the following components in percentage by mass: methyl methacrylate polymer: 1 to 10 percent; methyl methacrylate: 10-50%; benzoyl peroxide: 0to 0.1 percent; solvent: the balance.
3. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: in S1, the cleaning conditions are as follows: at room temperature, immersing the PAEK joint prosthesis into acetone for ultrasonic cleaning for 5-30 minutes, then immersing the PAEK joint prosthesis into ethanol for ultrasonic cleaning for 5-30 minutes after the PAEK joint prosthesis is taken out, and finally immersing the PAEK joint prosthesis into ultra-pure water for ultrasonic cleaning for 10 minutes;
in S1, the drying condition is 80-100 ℃ drying.
4. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: the conditions of the plasma treatment in S2 are as follows: the pressure of the spray gun head during treatment is 0.3MPa, the power is 400-800 w, and the treatment time is 5-30 s.
5. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: in S3, the methyl methacrylate polymer includes one of polymethyl methacrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-butyl methacrylate copolymer and methyl methacrylate-styrene copolymer;
the solvent is one or a mixture of more of dichloromethane, chloroform or acetone.
6. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: in S1, the solvent comprises one or a mixture of more of dichloromethane, chloroform or acetone.
7. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: in S3, the thickness of the coating is 10-100 um.
8. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: in S4, the baking conditions are as follows: the temperature is 40-100 ℃ and the time is 30-120 min.
9. A PAEK joint prosthesis treatment method with high adhesion strength to bone cement according to claim 1, characterized in that: s5, the annealing temperature is 80-170 ℃ and the annealing time is 15-60 min;
the rate of annealing cooling does not exceed 1.5 ℃/min until the coating temperature is below 80 ℃.
10. PAEK joint prosthesis with high adhesion strength to bone cement, characterized in that it is produced by the treatment process according to any one of claims 1 to 9.
CN202410249904.1A 2024-03-05 2024-03-05 PAEK joint prosthesis with high bonding strength with bone cement and treatment method thereof Pending CN118252973A (en)

Priority Applications (1)

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CN202410249904.1A CN118252973A (en) 2024-03-05 2024-03-05 PAEK joint prosthesis with high bonding strength with bone cement and treatment method thereof

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CN202410249904.1A CN118252973A (en) 2024-03-05 2024-03-05 PAEK joint prosthesis with high bonding strength with bone cement and treatment method thereof

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CN118252973A true CN118252973A (en) 2024-06-28

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