CN113082291B

CN113082291B - Polyaryletherketone modifier and preparation method and application thereof

Info

Publication number: CN113082291B
Application number: CN202110363312.9A
Authority: CN
Inventors: 范秀娟; 邓春明; 邓畅光; 刘敏; 胡峰帆
Original assignee: Institute of New Materials of Guangdong Academy of Sciences
Current assignee: Institute of New Materials of Guangdong Academy of Sciences
Priority date: 2021-04-02
Filing date: 2021-04-02
Publication date: 2022-06-03
Anticipated expiration: 2041-04-02
Also published as: CN113082291A

Abstract

The invention discloses a polyaryletherketone modifier and a preparation method and application thereof, belonging to the technical field of materials. The modifier comprises a polyaryletherketone material serving as a substrate, and a first titanium coating, a second titanium coating and a hydroxyapatite coating which are sequentially arranged on the surface of the substrate. The porosity of the second titanium coating is higher than that of the first titanium coating. The first titanium coating in the polyaryletherketone modifier has good bonding strength with the substrate, and can ensure the mechanical integrity, stability and durability of a polyaryletherketone implant system. The second titanium coating imitates the rough porous structure of the human bone structure characteristic, so that the bone growth speed and area can be rapidly increased, and the hydroxyapatite coating imitating the human bone chemical composition on the surface layer can form chemical combination with bone tissues, so that the growth of natural bone tissues is promoted. The composite coating can synergistically and stably enhance the osteointegration of the polyaryletherketone implant. The corresponding preparation method is simple and easy to operate, the conditions are controllable, and the polyaryletherketone modifier capable of stably and permanently enhancing the osseointegration of the implant is favorably obtained.

Description

Polyaryletherketone modifier and preparation method and application thereof

Technical Field

The invention relates to the technical field of materials, in particular to a polyaryletherketone modifier and a preparation method and application thereof.

Background

Polyetheretherketone (PEEK), a thermoplastic polymer, has a modulus of elasticity (3-4GPa) comparable to that of human cortical bone, to the extent that the stress shielding effect of conventional metal-based implants can be reduced or eliminated. In addition, the inert chemical structure and high heat resistance of PEEK make it suitable for use in a variety of sterilization techniques, the radiolucency of PEEK, easy to monitor bone growth and bone healing. The PEEK material can be applied to the fields of injury, spine, joint, plastic and the like.

However, PEEK is a bio-inert material, and after being implanted into a living body, interfacial osteointegration is insufficient due to excessive fibrous tissue generation between the implant and host bone, which limits the use of PEEK as a bone repair material to some extent.

In view of this, the invention is particularly proposed.

Disclosure of Invention

One of the objectives of the present invention includes providing a modified polyaryletherketone, which is beneficial to alleviating or overcoming the problem of insufficient interface osseointegration caused by excessive fibrous tissue generated between the implant and the host bone after polyaryletherketone substances are implanted into organisms.

The second object of the present invention is to provide a method for preparing the modified polyaryletherketone.

The invention also aims to provide application of the polyaryletherketone modifier.

The fourth object of the present invention is to provide a method for preparing an implant, wherein the implant is made of a material comprising the polyaryletherketone modification.

The application can be realized as follows:

in a first aspect, the application provides a polyaryletherketone modifier, which comprises a polyaryletherketone material serving as a substrate and a composite coating, wherein the composite coating comprises a first titanium coating, a second titanium coating and a hydroxyapatite coating which are sequentially arranged on the surface of the polyaryletherketone material.

The porosity of the second titanium coating is higher than the porosity of the first titanium coating.

In an alternative embodiment, the composite coating is appliedThe phase composition of the layer is Ca (PO)₄)₆(OH)₂Phase and Ti phase.

In an alternative embodiment, the first titanium coating has a porosity of < 10% and the second titanium coating has a porosity of > 30%.

In an alternative embodiment, the surface roughness Ra of the second titanium coating is > 30 μm.

In an alternative embodiment, the first titanium coating has a thickness of 30-50 μm and the second titanium coating has a thickness of 100-150 μm.

In an alternative embodiment, the polyaryletherketone material is a polyetheretherketone material.

In alternative embodiments, the polyetheretherketone material is pure polyetheretherketone or polyetheretherketone doped with carbon fibres.

In an alternative embodiment, the surface roughness of the polyetheretherketone material is 10-15 μm.

In an alternative embodiment, the particle size of the hydroxyapatite coating material is in the range 20 to 100 μm, d₅₀＝50μm。

In an alternative embodiment, the hydroxyapatite coating has a thickness of 50 to 60 μm.

In an alternative embodiment, the hydroxyapatite coating has a crystallinity of 68 to 90%, preferably 80 to 90%.

In a second aspect, the present application provides a method for preparing a modified polyaryletherketone as in any of the previous embodiments, comprising the steps of: preparing a composite coating on the surface of the polyaryletherketone material.

In an alternative embodiment, the composite coating is prepared by means of vacuum plasma spraying.

In an alternative embodiment, the starting material for the first titanium coating has a particle size in the range of 10-60 μm, d₅₀The particle size of the raw material of the second titanium coating layer is 30-220 μm, d₅₀＝110μm。

In an alternative embodiment, the raw material of the first titanium coating and the raw material of the second titanium coating are both titanium sponge, preferably irregular titanium sponge.

In an alternative embodiment, the plasma gun is moved in a horizontal direction throughout the spraying process.

In a preferred embodiment, the plasma gun is moved intermittently in the horizontal direction, or the sample is moved in rotation and the plasma gun is moved perpendicular to the horizontal direction at a speed less than the rotation of the sample.

In an alternative embodiment, before preparing the composite coating, the method further comprises: placing the polyaryletherketone material in spraying equipment, vacuumizing until the pressure is less than 0.5mbar, filling inert gas until the pressure is more than 40mbar, after a gun is ignited, vacuumizing until the pressure is less than 2mbar, and then preheating the polyaryletherketone material through plasma jet.

In an alternative embodiment, the method further comprises pretreating the surface of the polyaryletherketone material before placing the polyaryletherketone material in the spraying device.

In an alternative embodiment, after the composite coating is prepared, cooling in a vacuum state is further included.

In an alternative embodiment, the process conditions for preparing the first titanium coating include: the spraying pressure is 10-15KPa, the power of the spray gun is 25-35kW, and the current is 550-600A; the flow rate of plasma gas argon is 40-45splm, the flow rate of hydrogen is 2-5slpm, and the powder feeding rate is 10-15 g/min; the spraying distance is 250mm and 300 mm.

In an alternative embodiment, the plasma gun is moved at a speed of 1000mm/s during the spraying of the first titanium coating, and the spraying is carried out 5 to 10 times.

In an alternative embodiment, the process conditions for preparing the second titanium coating include: the spraying pressure is 10-15KPa, the power of the spray gun is 25-30kW, and the current is 500-550A; the flow rate of plasma gas argon is 40-45splm, the flow rate of hydrogen is 2-5slpm, and the powder feeding rate is 15-20 g/min; the spraying distance is 250mm and 300 mm.

In an alternative embodiment, the plasma gun is moved at a speed of 1000mm/s during the spraying of the second titanium coating, and the spraying is carried out 15 to 20 times.

In an alternative embodiment, the process conditions for preparing the hydroxyapatite coating layer include: the spraying pressure is 10-15KPa, the power of the spray gun is 30-35kW, and the current is 550-600A; the flow rate of plasma gas argon is 40-45splm, the flow rate of hydrogen is 3-6slpm, and the powder feeding rate is 10-15 g/min; the spraying distance is 250mm and 300 mm.

In an alternative embodiment, the plasma gun is moved at a speed of 1000mm/s during the spraying of the hydroxyapatite coating, and the spraying is performed 10 to 15 times.

In a third aspect, the present application provides the use of a polyaryletherketone modifier as in any one of the preceding embodiments, for example for the preparation of an implant.

In an alternative embodiment, the implant is an orthopedic implant.

In a fourth aspect, the present application provides an implant made from a material comprising a polyaryletherketone modification according to any of the preceding embodiments.

The beneficial effect of this application includes:

according to the method, a first compact titanium coating layer as a bottom coating layer is arranged on the surface of a substrate, a second titanium coating layer as a middle layer and higher in porosity and ultrahigh in roughness is arranged, and a hydroxyapatite coating layer as a surface layer and high in crystallinity is arranged at last, so that a titanium/rough porous titanium/hydroxyapatite composite coating (Ti/Ti/HA) is formed. The first titanium coating mainly improves the bonding strength of the coating in a mechanical mode, a physical mode and the like; the second titanium coating with higher porosity and ultrahigh roughness is mainly used for increasing the contact area with sclerotin, so that the sclerotin and the surface of the polyaryletherketone modifier (or the implant made of the polyaryletherketone modifier) can be better combined in a staggered manner, the biological fixation effect of the titanium coating is improved, and long-term better osseointegration is realized; the hydroxyapatite coating is mainly used for forming chemical combination with bone tissues, accelerating early osseointegration and promoting the growth of natural bone tissues, and can weaken or eliminate the stress shielding effect of the traditional metal-based implant; the method realizes the maximum improvement of the osseointegration of the polyaryletherketone, especially the polyetheretherketone, by the synergistic coupling of the rough porous structure (Ti) coating imitating the structural characteristics of the human bone and the Hydroxyapatite (HA) coating imitating the chemical composition of the human bone.

The corresponding preparation method is simple, easy to operate and controllable in conditions. The implant prepared from the polyaryletherketone modifier has higher bonding strength between a composite coating and a substrate, so that the osteointegrative performance of the polyaryletherketone modifier and the implant thereof can be stably and permanently enhanced.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a scanning electron microscope surface morphology of Ti powder and HA powder in example 1 of the present application;

FIG. 2 is a surface three-dimensional topography of the Ti/Ti/HA composite coating in example 1 of the present application;

FIG. 3 is a cross-sectional view and a surface topography of the Ti/Ti/HA composite coating in example 1 of the present application;

FIG. 4 is an X-ray diffraction line of the Ti/Ti/HA composite coating in example 1 of the present application;

FIG. 5 is a graph showing the results of the bonding strength between the Ti/Ti/HA composite coating and the substrate in example 1 of the present application;

FIG. 6 is a three-dimensional topographical view of the surface of the Ti/Ti coating layer in example 1 of the present application;

FIG. 7 is a cross-sectional and surface topography of the Ti/Ti coating in example 1 of the present application;

FIG. 8 is an X-ray diffraction line of a Ti/Ti coating layer in example 1 of the present application;

FIG. 9 is a graph showing the results of the bonding strength between the Ti/Ti coating layer and the substrate in example 1 of the present application.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The modified polyaryletherketone provided by the present application, and the preparation method and application thereof are specifically described below.

In view of the problem of insufficient interfacial osseointegration resulting from excessive fibrous tissue formation between the current implant and the host bone, the inventors found that: the interaction between the implant and the surrounding tissue environment mainly occurs on the surface of the implant, and the plasma spraying process of the surface coating technology is the best direct and effective way to solve the problem of poor osseointegration effect of the implant.

Based on the above, the present application provides a polyaryletherketone modifier, which comprises a polyaryletherketone material as a matrix and a composite coating. The composite coating (Ti/Ti/HA coating for short) comprises a first titanium coating, a second titanium coating and a hydroxyapatite coating which are sequentially arranged on the surface of the polyaryletherketone material.

Wherein the porosity of the second titanium coating is higher (preferably much higher) than the porosity of the first titanium coating.

In the composite coating, the first titanium coating as a bottom layer is a compact titanium interface layer, the second titanium coating as a middle layer has high porosity and ultrahigh roughness, and the hydroxyapatite coating as a surface layer has high crystallinity. It is worth noting that the above "densification" of the first titanium coating is a relative concept with respect to the "higher porosity" of the second titanium coating, i.e. the densification of the first titanium coating is compared to the porosity of the second titanium coating.

In alternative embodiments, the porosity of the first titanium coating may be controlled to be < 10%, such as 2%, 5%, or 8%, etc., and may be any value within the range of < 10%, to provide a higher degree of densification of the first titanium coating.

The porosity of the second titanium coating can be controlled to be > 30%, such as 30%, 35%, 40%, 45%, 50%, 55%, or 60%, etc., and other porosity values in the range > 30% are also possible.

In an alternative embodiment, the surface roughness Ra of the second titanium coating is > 30 μm, such as 30 μm, 40 μm, 50 μm or 60 μm, etc., but also other roughness values in the range > 30 μm.

In an alternative embodiment, the raw material grain size of the second titanium coating is larger than the raw material grain size of the first titanium coating, and may be, for example: raw material particle size powder of first titanium coatingEnd range of 10-60 μm, d ₅₀32 μm, the particle size of the raw material of the second titanium coating layer is in the range of 30-220 μm, d₅₀＝110μm。

It is worth mentioning that a raw material particle size of the first titanium coating layer higher than 60 μm easily results in a low degree of powder melting, causing an increase in porosity of the coating layer, resulting in a decrease in bonding strength of the coating layer. A raw material particle size of the second titanium coating of less than 30 μm tends to cause a relatively low porosity and roughness of the deposited coating after the powder is accelerated by heating. Particularly, if the raw material particle size of the titanium coating is in a nanometer level, a compact coating can be formed more easily than the first titanium coating in a micrometer level, however, the nanometer powder easily causes the blockage of a spray gun, and the coating thickness is not uniform; the higher porosity ultra high roughness topography cannot be formed for the second titanium coating.

In an alternative embodiment, the raw material of the first titanium coating and the raw material of the second titanium coating can be titanium sponge, preferably irregular titanium sponge, on one hand, the titanium sponge has certain impact resistance and buffering performance and is matched with the mechanical performance of a human body, and on the other hand, the titanium sponge is beneficial to increasing the contact area of the polyaryletherketone modifier and bone.

It is worth to be noted that, in the polyaryletherketone modifier of the present application, the first dense titanium coating mainly improves the bonding strength of the coating in a mechanical and physical manner, and the second titanium coating with large pores and ultrahigh roughness is mainly used for increasing the contact area with the bone, so that the bone and the surface of the polyaryletherketone modifier (or the implant made of the polyaryletherketone modifier) can be better combined in a staggered manner, the biological fixation effect of the implant can be improved, and long-term better bone integration can be achieved.

In an alternative embodiment, the thickness of the first titanium coating may be 30-50 μm, such as 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, etc., or any other thickness value within the range of 30-50 μm.

The thickness of the second titanium coating layer can be 100-150 μm, such as 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm, and can also be any other thickness value within the range of 100-150 μm.

In the application, the polyaryletherketone material is a composite material with polyaryletherketone resin as a matrix. In alternative embodiments, it may be a polyetheretherketone material (PEEK), a polyetherketone material (PEK), a polyetherketoneketone-based composite material (PEKK), or the like.

In some preferred embodiments, the polyetheretherketone material is pure polyetheretherketone or polyetheretherketone doped with carbon fibres.

In alternative embodiments, the surface roughness of the PEEK material may be controlled to be 10-15 μm, such as 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm, and may be any other value within the range of 10-15 μm.

The particle size range of the raw material of the hydroxyapatite coating can be 20-100 mu m, d₅₀＝50μm。

The thickness of the hydroxyapatite coating may be 50-60 μm, such as 50 μm, 55 μm or 60 μm, etc., or may be any other value within the range of 50-60 μm.

In the present application, the crystallinity of the hydroxyapatite coating layer may be 68 to 90%, preferably 80 to 90%.

The hydroxyapatite coating layer is mainly used to form a chemical bond with bone tissue, promote the growth of natural bone tissue, and reduce or eliminate the stress shielding effect of the conventional metal-based implant.

In the present application, the phase composition of the composite coating is Ca (PO)₄)₆(OH)₂Phase and Ti phase. It is worth noting that the phase composition of the composite coating in the present application does not contain TiO₂Phase, can be compared with TiO₂Replacing Ti avoids an increase in the brittleness of the coating, reducing the mechanical strength of the coating system in the present application.

In the application, the surface of the substrate is firstly provided with the priming layer-the compact titanium coating, then the middle layer-the titanium coating with higher porosity and ultrahigh roughness is arranged, and finally the surface layer-the high-crystallinity hydroxyapatite coating is arranged to form the titanium/rough porous titanium/hydroxyapatite composite coating (Ti/Ti/HA composite coating), so that the bone-promoting integration of the polyaryletherketone modifier and the implant thereof can be stably and permanently enhanced.

Accordingly, the present application provides a method for preparing the polyaryletherketone modifier, which may comprise the following steps: preparing a composite coating on the surface of the polyaryletherketone material.

It is worth mentioning that the inventors found that: although the composite coating can be prepared by adopting a magnetron sputtering technology, a micro-arc oxidation technology, a sol-gel technology and the like, instruments required by the technologies are complex, the preparation process is complicated, the price is high, and a microstructure coating with high porosity and ultrahigh roughness is difficult to obtain. The plasma spraying process is simple and economical, can realize larger overall yield, and is the simplest and simplest process for realizing the macroporous network and the rough surface of the implant. Therefore, the plasma spraying technique is the most effective preparation process for modifying the osteointegrative property of the polyaryletherketone in terms of cost/benefit. However, the bond strength of coatings prepared by Atmospheric Plasma Spraying (APS) is only 2.8 MPa. The lower bonding strength of the APS sprayed coating may be due to evaporation of the PAEK matrix caused by partial melting of hydroxyapatite particles during spraying to generate a vapor film, which prevents the PAEK matrix from being in close contact with the coating, thereby causing a decrease in bonding strength.

In view of the above, the inventors propose to prepare the above composite coating by Vacuum Plasma Spraying (VPS), which can be performed at relatively low temperature and pressure, reduce damage to the matrix material, maintain the chemical stability of the coating HA, and promote early bone remodeling; avoid the brittleness increase of the coating caused by the oxidation of the Ti coating and ensure that the composite coating has good bonding strength.

In an alternative embodiment, before preparing the composite coating, the method further comprises: placing the polyaryletherketone material in a spraying device, vacuumizing until the pressure is less than 0.5mbar, filling inert gas (such as argon) until the pressure is more than 40mbar, after a gun is ignited, vacuumizing until the pressure is less than 2mbar, and then preheating the polyaryletherketone material by plasma jet.

Preferably, the surface of the polyaryletherketone material may also be pretreated, for example, by sandblasting the surface of the polyaryletherketone material, followed by ultrasonic alcohol cleaning, before being placed in the spraying equipment. Wherein the sand blasting treatment may be grinding with sand paper and then sand blasting until the surface roughness is 10-15 μm.

In an alternative embodiment, the plasma gun is moved in a horizontal direction throughout the spraying process. Preferably, the plasma gun is intermittently moved at a speed of 1000mm/s in the horizontal direction, or the sample is rotationally moved at a speed, and the plasma gun is moved perpendicular to the horizontal direction at a speed less than the rotational speed of the sample, so as to avoid excessive temperature of the sample.

By reference, the process conditions for preparing the first titanium coating may include: the spraying pressure is 10-15KPa (such as 10KPa, 11KPa, 12KPa, 13KPa, 14KPa or 15KPa, etc.), the power of the spray gun is 25-35kW (such as 25kW, 27kW, 30kW, 33kW or 35kW, etc.), and the current is 550-600A (such as 550A, 560A, 570A, 580A, 590A or 600A, etc.); the flow rate of the plasma gas argon is 40-45splm (such as 40splm, 42splm or 45 splm), the flow rate of the hydrogen is 2-5slpm (such as 2slpm, 3slpm, 4slpm or 5 slpm), and the powder feeding rate is 10-15g/min (such as 10g/min, 12g/min or 15 g/min); the spraying distance is 250-300mm (such as 250mm, 280mm or 300 mm).

During the spraying of the first titanium coating, the moving speed of the plasma gun can be 1000mm/s, and the spraying times can be 5-10 times (such as 5 times, 6 times, 7 times, 8 times, 9 times or 10 times).

The preparation process conditions of the second titanium coating layer can comprise the following steps: the spraying pressure is 10-15KPa (such as 10KPa, 11KPa, 12KPa, 13KPa, 14KPa or 15KPa, etc.), the power of the spray gun is 25-30kW (such as 25kW, 28kW or 30kW, etc.), and the current is 500-550A (such as 5000A, 510A, 520A, 530A, 540A or 550A, etc.); the flow rate of plasma gas argon is 40-45splm (such as 40splm, 42splm or 45 splm), the flow rate of hydrogen is 2-5slpm (such as 2slpm, 3slpm, 4slpm or 5 slpm), and the powder feeding rate is 15-20g/min (such as 15g/min, 16g/min, 18g/min or 20 g/min); the spraying distance is 250-300mm (such as 250mm, 260mm, 270mm, 280mm, 290mm or 300 mm).

During the spraying of the second titanium coating, the moving speed of the plasma gun is also 1000mm/s, and the spraying times can be 15-20 times (such as 15 times, 16 times, 17 times, 18 times, 19 times or 20 times).

The preparation process conditions of the hydroxyapatite coating can comprise the following steps: the spraying pressure is 10-15KPa (such as 10KPa, 11KPa, 12KPa, 13KPa, 14KPa or 15KPa, etc.), the power of the spray gun is 30-35kW (such as 30kW, 32kW, 33kW or 35kW, etc.), and the current is 550-600A (such as 550A, 580A or 600A, etc.); the flow rate of plasma gas argon is 40-45splm (such as 40splm, 42splm or 45 splm), the flow rate of hydrogen is 3-6slpm (such as 3slpm, 4slpm, 5slpm or 6 slpm), and the powder feeding rate is 10-15g/min (such as 10g/min, 11g/min, 12g/min, 13g/min, 14g/min or 15 g/min); the spraying distance is 250-300mm (such as 250mm, 260mm, 270mm, 280mm, 290mm or 300 mm).

In the process of spraying the hydroxyapatite coating, the movement speed of the plasma gun is also 1000mm/s, and the spraying times can be 10-15 times (such as 10 times, 11 times, 12 times, 13 times, 14 times or 15 times).

In the spraying process, the hydrogen flow mainly influences the heating process of the spraying powder, if the process parameter is lower than 2splm, the titanium powder has low melting degree, so that some particles can not be deposited on a substrate, the deposition rate of a coating is easy to cause to be low, and when the process parameter is higher than 6splm, the particle melting degree is good, on one hand, the surface morphology characteristic of high porosity and ultrahigh roughness is not easy to form, and on the other hand, H₂The increase in flow rate causes an increase in the temperature of the flame stream, which may cause melting of the matrix, easily resulting in a reduction in the mechanical properties of the matrix. The current influences the spraying power, and if the current is higher than 600A and the spraying power is higher than 35kW, the high-heat-flux plasma flame flow can cause the melting of a matrix and the warping of a coating, the physical and chemical stability of the matrix is damaged, and the mechanical stability of a coating system is influenced. The powder feeding amount influences the deposition efficiency of the coating, and for the second titanium coating, if the powder feeding rate is less than 15g/min, the deposition efficiency is very low, which is not favorable for forming the coating with rough and porous morphology characteristics.

Further, after the composite coating is prepared, the composite coating can be cooled to room temperature under the vacuum state in the spraying process.

It should be noted that other steps or operations not mentioned in the preparation process referred to in the present application may refer to the prior art, and are not described in detail herein.

In addition, the application also provides the application of the polyaryletherketone modifier, for example, the polyaryletherketone modifier can be used for preparing implants, preferably orthopedic implants, for bone repair, bone trauma, osteointegration promotion and the like.

Correspondingly, the application also provides an implant, and the preparation material of the implant comprises the polyaryletherketone modifier. The composite coating of the implant HAs higher bonding strength with a matrix, and realizes the maximum improvement of the osteointegration of polyaryletherketone, especially polyetheretherketone, by simulating the cooperative coupling of human bone structure-rough porous characteristic (Ti) and human bone chemical composition-Hydroxyapatite (HA).

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

Selecting PEEK as a matrix, polishing the surface by using 60# SiC, and then using Al₂O₃Sandblasting was performed until the surface roughness Ra was 10-15 μm, and then ultrasonic cleaning was performed with alcohol. The particle diameter of 200g is d ₅₀32 μm and d₅₀Titanium sponge powders having a particle size of about 110 μm were charged into powder feeders, respectively.

Putting the PEEK substrate into a vacuum chamber, closing a cabin door of vacuum plasma equipment, vacuumizing until the pressure is less than 0.5mbar, filling inert gas until the pressure is more than 40mbar, vacuumizing until the pressure is less than 2mbar after igniting a gun, and preheating the polyaryletherketone material by plasma jet.

Adjusting vacuum plasma spraying parameters to prepare a first titanium coating-priming layer: the spraying pressure is 14 KPa; the power of the spray gun is 30kW, and the current is 550A; the Ar gas flow of the working gas is 45splm, H₂The air flow was 4 slpm. After the flame flow is stabilized, the particle size is d at a powder feeding rate of 10g/min₅₀Ti powder of 32 μm was fed into the plasma flame stream. The spraying distance is 280 mm; the plasma gun moves horizontally at the speed of 1000mm/s and is sprayed for 5 times.

Adjusting the vacuum plasma spraying parameters to prepare a second titanium coating, namely a rough porous titanium coating: the spraying pressure is 14KPa, the power of the spray gun is 27.5kw, and the current is 500A; the Ar gas flow of the working gas is 45splm, H₂The air flow was 4 slpm. After the flame flow is stabilized, the particle size d is measured at a powder feeding rate of 15.9g/min₅₀Feeding 110 mu m Ti powder into plasma flame flow, wherein the spraying distance is 300 mm; horizontal movement of plasma gunThe moving speed is 1000mm/s, and the spraying is carried out for 10 times.

Adjusting the vacuum plasma spraying parameters to prepare the hydroxyapatite coating: the spraying pressure is 14KPa, the power of a spray gun is 32kW, and the current is 600A; the flow rate of Ar working gas is 45slpm, H₂The air flow was 5 slpm. After the flame flow is stabilized, the particle size d is measured at a powder feeding rate of 10g/min₅₀Feeding hydroxyapatite powder of 50 μm into plasma flame flow, and spraying at a distance of 300 mm; the plasma gun moves horizontally at the speed of 1000mm/s and is sprayed for 10 times. Keeping the low-pressure state until the temperature is cooled to room temperature, and taking out the matrix to obtain the polyaryletherketone modifier with the Ti/Ti/HA composite coating with the thickness of 150 mu m.

Example 2

This example differs from example 1 in that:

adjusting the vacuum plasma spraying parameters to prepare a priming titanium coating: the spraying pressure is 10 KPa; the power of the spray gun is 25kW, and the current is 580A; the Ar gas flow of the working gas is 40splm, H₂The air flow was 2 slpm. After the flame flow is stabilized, the particle size is d at a powder feeding rate of 12g/min₅₀Ti powder of 32 μm was fed into the plasma flame stream. The spraying distance is 250 mm; the plasma gun moves horizontally at a speed of 1000mm/s for 6 times.

Adjusting the vacuum plasma spraying parameters to prepare a rough porous titanium coating: the spraying pressure is 10KPa, the power of the spray gun is 25kw, and the current is 520A; the Ar gas flow of the working gas is 40splm, H₂The gas flow was 2 slpm. After the flame flow is stabilized, the particle size is d at a powder feeding rate of 15g/min₅₀Feeding 110 mu m Ti powder into plasma flame flow, wherein the spraying distance is 250 mm; the plasma gun moves horizontally at a speed of 1000mm/s for 10 spraying.

Adjusting vacuum plasma spraying parameters to prepare a hydroxyapatite coating: the spraying pressure is 10KPa, the power of a spray gun is 30kW, and the current is 550A; the flow rate of Ar working gas is 40slpm, H₂The air flow was 3 slpm. After the flame flow is stabilized, the particle size d is measured at a powder feeding rate of 12g/min₅₀Feeding hydroxyapatite powder of 50 microns into plasma flame flow, and spraying at a distance of 250 mm; the plasma gun moves horizontally at a speed of 1000mm/s for 12 spraying. Maintaining a low pressureCooling to room temperature, taking out the matrix to obtain the polyaryletherketone modifier with the Ti/Ti/HA composite coating with the thickness of 150 mu m.

Example 3

The present example differs from example 1 in that:

adjusting the vacuum plasma spraying parameters to prepare a priming titanium coating: the spraying pressure is 15 KPa; the power of the spray gun is 35kW, and the current is 600A; the flow rate of Ar working gas is 42splm, H₂The air flow was 5 slpm. After the flame flow is stabilized, the particle size is d at a powder feeding rate of 15g/min₅₀Ti powder of 32 μm was fed into the plasma flame stream. The spraying distance is 300 mm; the plasma gun moves horizontally at the speed of 1000mm/s and is sprayed for 10 times.

Adjusting the vacuum plasma spraying parameters to prepare a rough porous titanium coating: the spraying pressure is 15KPa, the power of a spray gun is 30kw, and the current is 550A; the flow rate of Ar working gas is 42splm, H₂The air flow was 5 slpm. After the flame flow is stabilized, the particle size is d at a powder feeding rate of 20g/min₅₀Feeding 110 mu m Ti powder into plasma flame flow, wherein the spraying distance is 280 mm; the plasma gun moves horizontally at the speed of 1000mm/s and is sprayed for 10 times.

Adjusting vacuum plasma spraying parameters to prepare a hydroxyapatite coating: the spraying pressure is 12KPa, the power of the spray gun is 35kW, and the current is 580A; the flow rate of Ar working gas is 42slpm, H₂The air flow was 6 slpm. After the flame flow is stabilized, the particle size is d at a powder feeding rate of 15g/min₅₀Feeding hydroxyapatite powder of 50 microns into plasma flame flow, and spraying at a distance of 280 mm; the plasma gun moves horizontally at the speed of 1000mm/s and is sprayed for 15 times. Keeping the low-pressure state until the temperature is cooled to room temperature, and taking out the matrix to obtain the polyaryletherketone modifier with the Ti/Ti/HA composite coating with the thickness of 150 mu m.

Test examples

The morphology, phase composition and bonding strength of the modified polyaryletherketone are tested, and the results are shown in FIGS. 1 to 5.

Fig. 1 is a morphology of titanium sponge powder with irregular shape for preparing titanium coating and a morphology of hydroxyapatite powder with regular spherical shape for preparing hydroxyapatite coating. Wherein (a) titanium powder is used to prepare a rough porous titanium coating, in particular the porosity and pore size of the coating can be controlled by close or loose packing of the powder. (b) The heating degree of the regular spherical hydroxyapatite powder is nearly the same, the crystallinity of the coating can be well controlled, and the hydroxyapatite coating can be uniformly prepared.

FIG. 2 is a surface three-dimensional topography of the Ti/Ti/HA composite coating, and the results show that: the surface of the composite coating presents a high-low fluctuation appearance, and the surface roughness Ra of the composite coating reaches 32 mu m. The higher roughness of the coating enables the bone and the surface of the prosthesis to be better combined in a staggered way, and the biological fixation effect is improved. The high roughness of the coating surface provides a higher initial stability for prosthesis fixation.

Fig. 3 is a cross-sectional view and a surface topography of the Ti/HA composite coating, wherein, a left image (a) is a cross-sectional view of the Ti/HA composite coating, and a right image (b) is a surface enlarged topography of a dotted-line frame region in the left image. The results show that: the composite coating exhibits three distinct layers: the bottom layer compact priming titanium coating can improve the bonding strength of the coating, the middle coarse porous titanium coating can improve the integration of the prosthesis and sclerotin, and the surface hydroxyapatite coating can promote the growth of natural bone tissues and increase the initial stability of the prosthesis.

FIG. 4 is an X-ray diffraction line of the Ti/Ti/HA composite coating, the result of which shows: the phase composition of the composite coating is Ca (PO)₄)₆(OH)₂Phase and Ti phase. Namely, the spraying under the vacuum atmosphere avoids impurity phases generated by titanium oxidation, simultaneously ensures the crystallinity of HA, and improves the chemical stability of HA.

FIG. 5 is a graph showing the results of the bonding strength between the Ti/Ti/HA composite coating and the substrate, wherein the results are summarized in the following table, wherein the numbers 1 to 4 correspond to the numbers 1#, 2#, 3# and 4# from left to right in FIG. 5, respectively:

serial number	1	2	3	4
					Bonding Strength (MPa)	35	32	31	30

The results show that: the average bonding strength of the coating is 32MPa, and the requirement of FDA > 22MPa is met. The high bonding strength between the composite coating and the matrix ensures the mechanical integrity, stability and durability of the coating system and ensures the success of implantation application.

In addition, before the hydroxyapatite coating is arranged, the PEEK-Ti/Ti coating prepared on the surface of the substrate is subjected to the test of the appearance, the phase composition and the bonding strength, and the results are shown in FIGS. 6 to 9.

FIG. 6 is a surface three-dimensional topography of a PEEK-Ti/Ti coating, showing the results: the PEEK-Ti/Ti coating has a surface roughness Ra of up to 48 μm (specifically 48.165 μm). The ultra-high roughness of the coating will improve the stability between the bone and the prosthesis.

FIG. 7 is a cross-sectional view and a surface topography of a PEEK-Ti/Ti coating, wherein the left figure is a cross-sectional view of the PEEK-Ti/Ti coating, and the right figure is a surface enlarged topography of a dashed-line frame region in the left figure. The results show that: the coating consists of a dense priming titanium coating and a rough porous titanium coating. The porosity of the underlying titanium coating is less than 10%, and the porosity of the rough porous titanium coating is up to 40% (specifically 40.29%). The priming titanium coating improves the bonding strength of the coating, ensures the stability of the mechanical property of the coating and provides support for the osseointegration of the rough porous titanium coating.

FIG. 8 is an X-ray diffraction line of a PEEK-Ti/Ti coating showing the results: the coating only consists of a pure Ti phase and has no impurity phases such as oxides and the like. The vacuum atmosphere avoids oxidation of the titanium.

FIG. 9 is a graph showing the results of the bonding strength between the PEEK-Ti/Ti coating and the substrate, which can be summarized in the following table, wherein the numbers 1 to 4 correspond to the numbers 1#, 2#, 3# and 4# from left to right in FIG. 9, respectively:

serial number	1	2	3	4
					Bonding Strength (MPa)	29	31	32	29

The results show that: the average bonding strength of the coating is 30MPa, and is more than FDA & gt 22 MPa. The higher bonding strength of the coating ensures the system integrity of the coating modified PEEK implant.

Comparative example 1

The same vacuum plasma spraying process as in example 1 was used to deposit the HA coating only on the PEEK substrate (i.e. only distinguished from example 1 by the fact that no two titanium coatings were provided), and the test was carried out under the same test conditions, which showed that: the bonding strength between the coating and the substrate is only 7.5 MPa.

Comparative example 2

Using the same vacuum plasma spray process as in example 1, the deposition of the underlying titanium coating and the HA coating on the PEEK substrate only (i.e., the only difference from example 1 is that the rough porous titanium coating is not provided), and the same test conditions were used for testing, and the results show that: the bonding strength between the coating and the substrate was 20.9 MPa.

Comparative example 3

Using the same vacuum plasma spray process as in example 1, a rough porous titanium coating and HA coating were deposited only on the PEEK substrate (i.e., only different from example 1 in that no underlying titanium coating was provided), and the same test conditions were used for testing, and the results showed: the bonding strength between the coating and the substrate was 25 MPa.

Comparative example 4

This comparative example differs from example 1 only in that: the first titanium coating and the second titanium coating were made of titanium dioxide, and the results showed that: the bonding strength between the coating and the substrate was 18 MPa.

Comparative example 5

The result of depositing a 200 μm thick HA coating on a PEEK substrate using an atmospheric plasma spray process shows: the bonding strength between the coating and the substrate is only 2.8 MPa.

Comparative example 6

This comparative example differs from example 1 only in that: the composite layer is prepared by adopting an atmospheric plasma spraying process, and the result shows that: the bonding strength between the coating and the substrate was 9 MPa.

Therefore, the composite structure of the special structural layer and the vacuum plasma spraying process can obviously improve the bonding strength between the coating and the substrate.

In conclusion, the existing PEEK surface is directly sprayed with the hydroxyapatite coating or the titanium coating/hydroxyapatite coating in a vacuum plasma spraying mode, the mode that the compact titanium coating is firstly prepared on the PEEK surface to improve the bonding strength of the coating, the rough porous titanium coating is then prepared to improve the osseointegration property, and finally the hydroxyapatite coating is prepared to improve the early osseointegration fixation of the bone is changed. The Ti/Ti/HA composite coating is constructed to improve the bonding strength between the coating and the PEEK, and realize that the PEEK osseointegration is improved to the maximum extent by the synergistic coupling of the rough porous structure titanium coating imitating the characteristics of human bones and the hydroxyapatite coating imitating the chemical components of the human bones.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A polyaryletherketone modifier is characterized by comprising a polyaryletherketone material serving as a base body and a composite coating, wherein the composite coating comprises a first titanium coating, a second titanium coating and a hydroxyapatite coating which are sequentially arranged on the surface of the polyaryletherketone material;

the porosity of the second titanium coating is higher than the porosity of the first titanium coating;

the phase composition of the composite coating is Ca (PO)₄)₆(OH)₂A phase and a Ti phase;

the porosity of the first titanium coating is less than 10%, the porosity of the second titanium coating is more than 30%, and the surface roughness Ra of the second titanium coating is more than 30 mu m; the thickness of the first titanium coating is 30-50 μm, and the thickness of the second titanium coating is 100-150 μm;

the surface roughness of the polyaryletherketone material is 10-15 mu m;

the particle size range of the raw material of the hydroxyapatite coating is 20-100 mu m, d₅₀=50 μm; the thickness of the hydroxyapatite coating is 50-60 mu m; the crystallinity of the hydroxyapatite coating is 68-90%;

the polyaryletherketone modifier is prepared by the following steps: preparing the composite coating on the surface of the polyaryletherketone material in a vacuum plasma spraying manner;

the particle size range of the raw material of the first titanium coating used for spraying is 10-60 mu m, d₅₀=32 μm, of the second titanium coatingThe particle size of the raw material is 30-220 μm, d₅₀=110 μm; the raw materials of the first titanium coating and the second titanium coating are both titanium sponge;

the preparation process conditions of the first titanium coating comprise the following steps: the spraying pressure is 10-15kPa, the power of the spray gun is 25-35kW, and the current is 550-600A; the flow rate of plasma gas argon is 40-45splm, the flow rate of hydrogen is 2-5slpm, and the powder feeding rate is 10-15 g/min; the spraying distance is 250-300 mm;

the preparation process conditions of the second titanium coating comprise the following steps: the spraying pressure is 10-15kPa, the power of the spray gun is 25-30kW, and the current is 500-550A; the flow rate of plasma gas argon is 40-45splm, the flow rate of hydrogen is 2-5slpm, and the powder feeding rate is 15-20 g/min; the spraying distance is 250-300 mm;

the preparation process conditions of the hydroxyapatite coating comprise: the spraying pressure is 10-15kPa, the power of the spray gun is 30-35kW, and the current is 550-600A; the flow rate of plasma gas argon is 40-45splm, the flow rate of hydrogen is 3-6slpm, and the powder feeding rate is 10-15 g/min; the spraying distance is 250mm and 300 mm.

2. The polyaryletherketone modifier of claim 1, wherein the polyaryletherketone material is a polyetheretherketone material.

3. The polyaryletherketone modifier of claim 2, wherein the polyetheretherketone material is pure polyetheretherketone or polyetheretherketone doped with carbon fibers.

4. The polyaryletherketone modifier of claim 1, wherein the hydroxyapatite coating layer has a crystallinity of 80-90%.

5. The method of preparing a modified polyaryletherketone of any of claims 1-4, comprising the steps of: and preparing the composite coating on the surface of the polyaryletherketone material in a vacuum plasma spraying manner.

6. The method of claim 5, wherein the plasma torch is moved in a horizontal direction throughout the spraying process.

7. The method of claim 6, wherein the plasma gun is intermittently moved in a horizontal direction, or the sample is rotationally moved at a maximum speed and the plasma gun is moved perpendicular to the horizontal direction at a speed less than the rotation of the sample.

8. The method according to claim 5, wherein before the preparing the composite coating, the method further comprises: and (2) placing the polyaryletherketone material in spraying equipment, vacuumizing until the pressure is less than 0.5mbar, filling inert gas until the pressure is more than 40mbar, igniting a gun, vacuumizing until the pressure is less than 2mbar, and then preheating the polyaryletherketone material through plasma jet.

9. The method of claim 8, further comprising pre-treating the surface of the polyaryletherketone material prior to being placed in the spray coating device.

10. The method according to claim 5, wherein the step of cooling under vacuum is further included after the step of preparing the composite coating.

11. A method according to claim 5, characterized in that the first titanium coating is applied 5-10 times with a plasma gun movement speed of 1000 mm/s.

12. A method according to claim 5, wherein the second titanium coating is applied by moving the plasma gun at a speed of 1000mm/s for 15-20 passes.

13. The method according to claim 5, wherein the hydroxyapatite coating is sprayed at a moving speed of 1000mm/s by a plasma gun for 10-15 times.

14. Use of a polyaryletherketone modifier according to any of claims 1-4, wherein the polyaryletherketone modifier is used for the preparation of an implant.

15. The use of claim 14, wherein the implant is an orthopedic implant.

16. An implant made of a material comprising the polyaryletherketone modification of any of claims 1-4.