CN113289057A - Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant - Google Patents
Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant Download PDFInfo
- Publication number
- CN113289057A CN113289057A CN202110548474.XA CN202110548474A CN113289057A CN 113289057 A CN113289057 A CN 113289057A CN 202110548474 A CN202110548474 A CN 202110548474A CN 113289057 A CN113289057 A CN 113289057A
- Authority
- CN
- China
- Prior art keywords
- tantalum
- coating
- orthopedic implant
- layer
- tantalum coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/08—Coatings comprising two or more layers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Transplantation (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Prostheses (AREA)
Abstract
The invention provides a tantalum coating orthopedic implant material, a preparation method thereof and an orthopedic implant. The tantalum coating orthopedic implant material comprises a substrate layer, a transition layer, a tantalum coating and a tantalum surface functional layer which are sequentially stacked, wherein the substrate layer is titanium or titanium alloy, the melting point of the transition layer is lower than that of tantalum, and the tantalum coating is of a porous structure. The tantalum coating orthopedic implant material improves the binding force of the tantalum coating and the transition layer; on the other hand, the bone ingrowth is enhanced, so that the biocompatibility and the osteoconductivity of the tantalum coating are improved, a microenvironment beneficial to cell growth is generated, further, the bone tissue is promoted to grow towards the inside of the porous tantalum coating to form a unique bone-implant interface, the stability and the function of the tantalum-coated orthopedic implant in the bone tissue are obviously enhanced, the osseointegration of the bone-implant interface is accelerated, in addition, the production cost of the orthopedic implant is low, and the potential hazard of non-tantalum substances is small.
Description
Technical Field
The invention relates to the technical field of orthopedic implants, in particular to a tantalum-coated orthopedic implant material, a preparation method thereof and an orthopedic implant.
Background
The tantalum has good corrosion resistance, the ionization degree of the tantalum is extremely low in an in-vivo environment, so that the tantalum shows extremely low cytotoxicity, and implantation products such as porous tantalum metal acetabular cups and the like are widely applied clinically and have good clinical effects.
The invention patent CN109261958 proposes a preparation method of medical porous titanium or titanium alloy material with a tantalum coating coated on the surface, but the technology is a compact tantalum coating coated on the surface of the porous titanium alloy, so that no pores for bone growth exist after the porous titanium alloy is implanted into a human body, and further bone tissues are difficult to grow into the tantalum coating.
In addition, the Jiemei tantalum trabecular bone implant is processed by adopting a chemical vapor deposition technology, and the technology has multiple process steps and high technical difficulty; in addition, because of the high melting point of tantalum, the tantalum is difficult to process by adopting the traditional powder metallurgy method; the raw material and processing cost of 3D printed metal tantalum are high, particularly, the weight of the implant with the same specification is high due to the high specific gravity of the tantalum, and the problem that the metal tantalum is prone to sinking and the like after being implanted is solved.
Disclosure of Invention
The invention mainly aims to provide a tantalum-coated orthopedic implant material, a preparation method thereof and an orthopedic implant, and aims to solve the problem that bone tissues are difficult to grow into the tantalum-coated orthopedic implant in the prior art.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a tantalum-coated orthopedic implant material, comprising a base layer, a transition layer, a tantalum coating layer and a tantalum surface functional layer, which are sequentially stacked, wherein the base layer is titanium or a titanium alloy, the melting point of the transition layer is lower than that of tantalum, and the tantalum coating layer is a porous structure.
Further, the pore size of the tantalum coating is 10-30 μm, the porosity of the tantalum coating is preferably 30-80%, and the thickness of the tantalum coating is preferably 30-60 μm.
Further, the thickness of the transition layer is 90 to 180 μm.
Further, the functional layer on the tantalum surface is nano-wire-shaped calcium tantalate, the diameter of the nano-wire-shaped calcium tantalate is preferably 20-35 nm, and the length of the nano-wire-shaped calcium tantalate is preferably less than or equal to 500 nm.
Further, the titanium alloy is selected from any one of Ti-6Al-4V, Ti-6Al-17Nb, Ti-13Nb-13Zr and Ti-5Zr-3Mo-15 Nb.
Furthermore, the transition layer is pure titanium or Ti-6 Al-4V.
According to another aspect of the present invention, there is provided a tantalum-coated orthopedic implant comprising the above tantalum-coated orthopedic implant material, the tantalum-coated orthopedic implant being any one of an acetabular cup, an acetabular patch, and a femoral stem.
According to another aspect of the invention, a preparation method of the tantalum-coated orthopedic implant material is provided, the preparation method comprises the steps of sequentially forming a transition layer, a tantalum coating and a tantalum surface functional layer on a substrate layer, the tantalum coating is formed by spraying tantalum particles on the transition layer by a laser cladding method to form the tantalum coating, wherein the power of the laser cladding is less than or equal to 8.0 KW.
Further, the preparation method comprises the following steps: step S1, spraying titanium powder or titanium alloy particles on the base layer to form a transition layer; step S2, spraying tantalum particles on the transition layer by adopting a laser cladding method to form a tantalum coating; and step S3, carrying out hydrothermal reaction on the tantalum coating, calcium salt and strong alkali solution to obtain the tantalum coating orthopedic implant material.
Further, the sphericity of the tantalum pellet is 0.6 to 1, preferably, the average particle diameter of the tantalum pellet is 5 to 40 μm, and/or the D50 of the tantalum pellet is 20 to 30 μm.
Further, the power of the laser cladding is 4.0-8.0 KW, the diameter of a light spot of the laser cladding is preferably 20-25 mm, the scanning speed of a light beam of the laser cladding is preferably 100-180 mm/min, and inert gas or nitrogen with the flow rate of 8-12L/min is preferably adopted to protect the laser cladding process.
Further, in the step S1, it is preferable that the average particle diameter of the titanium powder or the titanium alloy particles is 70 to 100 μm.
Further, the preparation method further comprises the following steps: surface preparation of the substrate layer, preferably ofThe process of the surface pretreatment comprises the following steps: sequentially polishing the substrate layer to obtain a polished substrate layer; carrying out sand blasting treatment on the polished substrate layer by using alumina particles to obtain a sand blasted substrate layer; performing acid etching treatment on the substrate layer after sand blasting, wherein the average particle size of alumina particles is preferably 350-500 mu m, the pressure of sand blasting treatment is preferably 0.8-1.2 MPa, and the time of sand blasting treatment is preferably 45-90 s; preference is given to using V (H)2O): v (sulfuric acid) and mixed acid of 20:8:4 (hydrochloric acid) and H in sulfuric acid2SO4The mass concentration of the acid etching solution is 40-50%, the mass concentration of HCl in hydrochloric acid is 30-40%, and the time of acid etching treatment is preferably 90-120 s.
By applying the technical scheme of the invention, on one hand, the tantalum coating orthopedic implant material forms a transition layer between the substrate layer and the tantalum coating, thereby reducing the thermal stress between the tantalum coating and the substrate layer and improving the bonding force between the tantalum coating and the transition layer; on the other hand, the porous structure of the tantalum coating provides a space for the growth of bone tissues, the bone growth is enhanced, the biocompatibility and the osteoconductivity of the tantalum coating are improved, a microenvironment beneficial to cell growth is generated, the bone tissues are promoted to grow towards the inside of the porous tantalum coating to form a unique bone-implant interface, the stability and the function of the tantalum-coated bone implant in the bone tissues are obviously enhanced, the osseointegration of the bone-implant interface is accelerated, in addition, the tantalum coating only improves the structure of the tantalum coating, the osseointegration of the bone-implant interface is improved, and compared with a method for pretreating the tantalum coating by introducing a non-tantalum substance, the tantalum-coated bone implant is low in production cost, small in potential hazard of the non-tantalum substance, and has a better application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a scanning electron micrograph of a tantalum-coated acetabular cup provided in example 1;
FIG. 2 shows a micro-nano structure diagram of a surface functional layer of the tantalum coating acetabular cup provided in example 1;
FIG. 3 shows a cross-sectional view of the acetabular cup orthopedic implant provided in example 1; and
fig. 4 shows a partial enlarged view at a of the sectional view of fig. 3.
Wherein the figures include the following reference numerals:
1. a substrate layer; 2. an acid etching layer; 3. a transition layer; 4. a tantalum coating.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background technology, the problems that the tantalum coating orthopedic implant is difficult to manufacture, the tantalum orthopedic implant is high in manufacturing cost, and particularly bone tissues are difficult to grow into the tantalum coating orthopedic implant exist in the prior art, and the tantalum coating orthopedic implant material, the preparation method thereof and the tantalum coating orthopedic implant are provided for solving the problem that the bone tissues are difficult to grow into the tantalum coating orthopedic implant.
In an exemplary embodiment of the present application, there is provided a tantalum-coated orthopedic implant material, comprising a substrate layer, a transition layer, a tantalum coating layer and a tantalum surface functional layer, which are sequentially stacked, wherein the substrate layer is titanium or a titanium alloy, the melting point of the transition layer is lower than that of tantalum, and the tantalum coating layer is a porous structure.
On one hand, the tantalum coating orthopedic implant material forms a transition layer between the substrate layer and the tantalum coating, so that the thermal stress between the tantalum coating and the substrate layer is reduced, and the bonding force between the tantalum coating and the transition layer is improved; on the other hand, the porous structure of the tantalum coating provides a space for the growth of bone tissues, the bone growth is enhanced, the biocompatibility and the osteoconductivity of the tantalum coating are improved, a microenvironment beneficial to cell growth is generated, the bone tissues are promoted to grow towards the inside of the porous tantalum coating to form a unique bone-implant interface, the stability and the function of the tantalum-coated bone implant in the bone tissues are obviously enhanced, the osseointegration of the bone-implant interface is accelerated, in addition, the tantalum coating only improves the structure of the tantalum coating, the osseointegration of the bone-implant interface is improved, and compared with a method for pretreating the tantalum coating by introducing a non-tantalum substance, the tantalum-coated bone implant is low in production cost, small in potential hazard of the non-tantalum substance, and has a better application prospect.
In one embodiment of the present application, the pore size of the tantalum coating is 10 to 30 μm, the porosity of the tantalum coating is preferably 30 to 80%, and the thickness of the tantalum coating is preferably 30 to 60 μm.
The tantalum coating with the pore size and the porosity has more pores and larger specific surface area, so that the ingrowth of bone tissue is more facilitated, and the preferable thickness of the tantalum coating is favorable for providing the tantalum coating orthopedic implant with a space for accommodating the bone tissue as much as possible, so that the stability and the biocompatibility of the tantalum coating orthopedic implant in a living body are improved.
In one embodiment of the present application, the thickness of the transition layer is 90 to 180 μm.
The transition layer of the above thickness helps to bind as many tantalum particles as possible, and on the other hand is less likely to fall off the substrate layer.
In order to further improve the biocompatibility of the tantalum coating orthopedic implant material, the functional layer on the tantalum surface is preferably nano-filamentous calcium tantalate, the diameter of the nano-filamentous calcium tantalate is preferably 20-35 nm, and the length of the nano-filamentous calcium tantalate is preferably less than or equal to 500 nm.
In order to further improve the bonding strength of the tantalum-coated orthopedic implant material, the titanium alloy is preferably selected from any one of Ti-6Al-4V, Ti-6Al-17Nb, Ti-13Nb-13Zr and Ti-5Zr-3Mo-15 Nb.
In order to better reduce the thermal stress between the tantalum coating and the substrate layer, the transition layer is preferably pure titanium or Ti-6 Al-4V.
In an exemplary embodiment of the present application, there is provided a tantalum-coated orthopaedic implant comprising the aforementioned tantalum-coated orthopaedic implant material, the tantalum-coated orthopaedic implant being any one of an acetabular cup, an acetabular patch, and a femoral stem.
The tantalum coating orthopedic implant material is favorable for promoting bone tissues to grow towards the inside of the porous tantalum coating to form a unique bone-implant interface, the stability and the function of the tantalum coating orthopedic implant in the bone tissues are obviously enhanced, the osseointegration of the bone-implant interface is accelerated, and the tantalum coating orthopedic implant material has high corrosion resistance.
When the orthopedic implant is an acetabular cup, the effective spherical outer diameter of the acetabular cup is preferably 36-72 mm, the acetabular height of the acetabular cup is preferably 22-50 mm, and the porosity of the tantalum coating is preferably 30-80%.
When the orthopedic implant is a femoral stem, the stem body diameter of the femoral stem is preferably
The CT value of the femoral stem is preferably 100-280 mm, and the porosity of the tantalum coating is preferably 30-80%.
In another exemplary embodiment of the present application, a method for preparing a tantalum-coated orthopedic implant material is provided, the method comprises sequentially forming a transition layer, a tantalum coating and a tantalum surface functional layer on a substrate layer, the tantalum coating is formed by spraying tantalum particles on the transition layer by a laser cladding method to form the tantalum coating, wherein the laser cladding power is less than or equal to 8.0 KW.
The technology combines the traditional spraying technology and the laser cladding technology, laser cladding is creatively used for melting the transition layer, the transition layer is melted through the control of the laser cladding power, the tantalum particles are not melted or are partly melted, and the tantalum particles are bonded on the titanium transition layer in a melting state, so that on one hand, the formation of a gap phase between the tantalum and the titanium is avoided, and the problems that the tantalum metal has high melting point and is difficult to melt and spray are solved. On the other hand, the formed tantalum coating has a porous structure, so that a space is provided for the growth of bone tissues, the bone growth is enhanced, the biocompatibility and the osteoconductivity of the tantalum coating are improved, a microenvironment beneficial to cell growth is generated, the growth of the bone tissues to the inside of the porous tantalum coating is promoted to form a unique bone-implant interface, the stability and the function of the bone-implant in the bone tissues are obviously enhanced, the bone integration of the bone-implant interface is accelerated, meanwhile, the tantalum coating, a calcium salt and a strong alkaline solution are subjected to hydrothermal reaction, the tantalum-coated orthopedic implant material with the tantalum surface functional layer is obtained, and the comprehensive performance of the tantalum-coated orthopedic implant material is further improved. In addition, the preparation process is simple and the cost is low.
In order to further improve the preparation efficiency of the transition layer, the tantalum coating layer and the tantalum surface functional layer, the preparation method preferably comprises the following steps: step S1, spraying titanium powder or titanium alloy particles on the base layer to form a transition layer; step S2, spraying tantalum particles on the transition layer by adopting a laser cladding method to form a tantalum coating; and step S3, carrying out hydrothermal reaction on the tantalum coating, calcium salt and strong alkali solution to obtain the tantalum coating orthopedic implant material.
In order to improve the efficiency of the hydrothermal reaction in step S3, the hydrothermal reaction preferably includes: and (4) immersing the material obtained in the step (S2) in 0.2mol/L calcium dihydrogen phosphate and 5mol/L sodium hydroxide solution, continuously carrying out 24-hour hydrothermal reaction at the temperature of 80 ℃, and finally carrying out ultrasonic cleaning by deionized water to obtain the tantalum surface functional layer containing the nano filiform calcium carbonate. Of course, the hydrothermal reaction can be carried out by those skilled in the art by referring to the prior art, and will not be described herein.
In order to increase the porosity of the tantalum coating layer as much as possible, it is preferable that the sphericity of the tantalum pellet is 0.6 to 1, the average particle diameter of the tantalum pellet is 5 to 40 μm, and/or the D50 of the tantalum pellet is 20 to 30 μm. Wherein, the tantalum particles with the particle size can be obtained by screening.
In an embodiment of the application, the power of the laser cladding is 4.0-8.0 KW, the diameter of a laser spot of the laser cladding is preferably 20-25 mm, the scanning speed of a laser beam of the laser cladding is preferably 100-180 mm/min, and inert gas with a flow rate of 8-12L/min is preferably used to protect the laser cladding process, and the inert gas is preferably nitrogen or argon, and in consideration of cost, nitrogen is further selected.
The laser cladding condition can control the transition layer to form a molten state as much as possible, and the tantalum particles are not molten or are at least partially molten, so that the adhesion stability of the tantalum coating with the formed porous pores is improved as much as possible, and the tantalum particles are uniformly bonded on the transition layer with the molten state as low as possible, and the pores of the tantalum coating are enriched as much as possible.
In order to obtain a transition layer capable of reducing the thermal stress between the base layer and the tantalum coating layer as much as possible, it is preferable that the average particle diameter of the titanium powder or the titanium alloy particles is 70 to 100 μm in step S1.
In an embodiment of the present application, the above preparation method further includes: and carrying out surface pretreatment on the substrate layer, wherein the surface pretreatment process comprises the following steps: sequentially polishing the substrate layer to obtain a polished substrate layer; carrying out sand blasting treatment on the polished substrate layer by using alumina particles to obtain a sand blasted substrate layer; performing acid etching treatment on the substrate layer after sand blasting, wherein the average particle size of alumina particles is preferably 350-500 mu m, the pressure of sand blasting treatment is preferably 0.8-1.2 MPa, and the time of sand blasting treatment is preferably 45-90 s; preference is given to using V (H)2O): v (sulfuric acid) and mixed acid of 20:8:4 (hydrochloric acid) and H in sulfuric acid2SO4The mass concentration of the acid etching solution is 40-50%, the mass concentration of HCl in hydrochloric acid is 30-40%, and the time of acid etching treatment is preferably 90-120 s.
The pretreatment is beneficial to improving the surface roughness of the substrate layer, thereby being beneficial to carrying out sand blasting treatment and further improving the efficiency of acid etching treatment. Preferably, the titanium alloy matrix is sequentially polished for 3min by 200-mesh and 800-mesh abrasive paper, and then polished for 5min by 1200-mesh abrasive paper; ultrasonically cleaning the glass substrate in an acetone solution for 5-8 min; then ultrasonically cleaning the mixture for 5min by purified water, and then drying the mixture for standby. Of course, the specific conditions of the polishing process can be adjusted by those skilled in the art as required, and will not be described herein again. The mixed acid composition and the acid etching treatment time are beneficial to controlling the acid etching treatment degree, so that the roughness of the base layer is ensured, and the bonding strength of the base layer and the transition layer is improved.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
The tantalum coating treatment was applied to a Ti-6Al-4V acetabular cup having an effective spherical outer diameter of 52mm and an acetabular height of 44 mm.
Performing surface pretreatment on the outer surface of the acetabular cup: sequentially polishing the outer surface of the acetabular cup with 200-mesh and 800-mesh abrasive paper for 3min, and then polishing with 1200-mesh abrasive paper for 5 min; ultrasonically cleaning in acetone solution for 6 min; ultrasonically cleaning with pure water for 5min, and blow-drying to obtain a polished substrate layer; carrying out sand blasting treatment on the polished acetabulum cup substrate layer by using alumina particles to obtain a sand blasted acetabulum cup substrate layer; carrying out acid etching treatment on the acetabulum cup matrix layer subjected to sand blasting, wherein the average grain diameter of alumina particles is 400 microns, the pressure of sand blasting treatment is 1MPa, and the time of sand blasting treatment is 60 s; by using V (H)2O): acid etching treatment of mixed acid of V (sulfuric acid) and V (hydrochloric acid) at a ratio of 20:8:4 to obtain acid etched layer, and H in sulfuric acid2SO4The mass concentration of (3) was 50%, the mass concentration of HCl in hydrochloric acid was 36%, and the acid etching treatment time was 100 seconds.
And carrying out titanium powder thermal spraying on the acetabulum cup subjected to the acid etching treatment to obtain a transition layer, wherein the average particle size of the titanium powder selected by the thermal spraying is 80 microns, and the thickness of the transition layer after the thermal spraying is 110 microns.
Carrying out laser cladding on the acetabulum cup subjected to titanium powder thermal spraying to form a tantalum coating: the sphericity of the tantalum pellet used was 0.8, and the average particle diameter of the spherical tantalum pellet was 28 μm (25 μm for D50 of the tantalum pellet). The laser cladding power is 5KW, the diameter of a light spot is 22mm, the laser cladding light beam scanning speed is 110mm/min, nitrogen with the flow rate of 9L/min is adopted to protect the laser cladding process, the acetabular cup tantalum coating with the tantalum coating thickness of 40 microns, the pore size of 16 microns and the porosity of 60% is obtained, and a scanning electron microscope photo of the tantalum coating of the acetabular cup tantalum coating is shown in figure 1.
Immersing the acetabular cup tantalum coating in 0.2mol/L calcium dihydrogen phosphate and 5mol/L sodium hydroxide solution at the temperature of 80 ℃ for 24 hours of hydrothermal reaction, finally performing ultrasonic cleaning by using deionized water to obtain the acetabular cup orthopedic implant with a surface functional layer of nano-filamentous calcium tantalate (the diameter of the nano-filamentous calcium tantalate is 25nm and the length of the nano-filamentous calcium tantalate is 450nm), wherein the micro-nano structure of the surface functional layer is shown in a scanning electron microscope photograph of figure 2, the cross-sectional view of the acetabular cup orthopedic implant is shown in figure 3, as can be seen from figure 3, the acetabular cup orthopedic implant comprises a substrate layer 1, an acid etching layer 2, a transition layer 3 and a tantalum coating 4, wherein the nano-filamentous calcium tantalate distributed on the tantalum coating 4 is of a micro-nano structure and needs to be observed under an electron microscope (as in figure 2), and a partial enlarged view of a part A of the cross-sectional view of figure 3 is shown in figure 4, it is clear from fig. 4 that the tantalum coating is porous.
Example 2
Example 2 differs from example 1 in that,
the sphericity of the tantalum particles is 0.6, and finally the acetabular cup orthopedic implant is obtained.
Example 3
Example 3 differs from example 1 in that,
the sphericity of the tantalum particles is 1, and finally the acetabular cup orthopedic implant is obtained.
Example 4
Example 4 differs from example 1 in that,
the sphericity of the tantalum particles is 0.5, and finally the acetabular cup orthopedic implant is obtained.
Example 5
Example 5 differs from example 1 in that,
the mean particle size of the tantalum pellet was 5 μm and the D50 of the tantalum pellet was 6 μm, resulting in an acetabular cup orthopedic implant.
Example 6
Example 6 differs from example 1 in that,
the mean particle size of the tantalum pellet was 40 μm and the D50 of the tantalum pellet was 35 μm, resulting in an acetabular cup orthopedic implant.
Example 7
Example 7 differs from example 1 in that,
the tantalum pellet has a D50 of 20 μm and an average diameter of 22 μm, resulting in an acetabular cup orthopedic implant.
Example 8
Example 8 differs from example 1 in that,
the tantalum pellet had a D50 of 30 μm and an average diameter of 35 μm, resulting in an acetabular cup orthopedic implant.
Example 9
Example 9 differs from example 1 in that,
the tantalum pellet has a D50 of 15 μm and an average diameter of 20 μm, resulting in an acetabular cup orthopedic implant.
Example 10
Example 10 differs from example 1 in that,
the tantalum pellet had a D50 of 35 μm and an average particle size of 40 μm, resulting in an acetabular cup orthopedic implant.
Example 11
Example 11 differs from example 1 in that,
the power of laser cladding is 4.0KW, the diameter of a laser spot of the laser cladding is 20mm, the scanning speed of a laser beam of the laser cladding is 100mm/min, inert gas or nitrogen with the flow rate of 8L/min is adopted to protect the laser cladding process, the average grain diameter of alumina particles is 350 mu m, the pressure of sand blasting is 0.8MPa, and the time of sand blasting is 45 s; finally obtaining the acetabular cup orthopedic implant.
Example 12
Example 12 differs from example 1 in that,
the power of laser cladding is 8.0KW, the diameter of a laser spot of the laser cladding is 25mm, the scanning speed of a laser beam of the laser cladding is 180mm/min, inert gas or nitrogen with the flow rate of 12L/min is adopted to protect the laser cladding process, the average grain diameter of alumina particles is 500 mu m, the pressure of sand blasting is 1.2MPa, and the time of sand blasting is 90 s; finally obtaining the acetabular cup orthopedic implant.
Example 13
Example 13 differs from example 1 in that,
the average grain diameter of the titanium powder selected by thermal spraying is 70 μm, and finally the acetabular cup orthopedic implant is obtained.
Example 14
Example 14 differs from example 1 in that,
the average grain diameter of the titanium powder selected by thermal spraying is 100 mu m, and finally the acetabular cup orthopedic implant is obtained.
Example 15
Example 15 differs from example 1 in that,
the average grain diameter of the titanium powder selected by thermal spraying is 60 mu m, and finally the acetabular cup orthopedic implant is obtained.
Example 16
Example 16 differs from example 1 in that,
the average grain diameter of the titanium powder selected by thermal spraying is 110 μm, and finally the acetabular cup orthopedic implant is obtained.
Example 17
Example 17 differs from example 1 in that,
the matrix layer is Ti-5Zr-3Mo-15Nb, and finally the acetabular cup orthopedic implant is obtained.
Example 18
Example 18 differs from example 1 in that the selected titanium alloy material was Ti-5Zr-3Mo-15Nb, and the product was a femoral stem.
The tantalum coating treatment is carried out on the femoral stem of Ti-5Zr-3Mo-15Nb, and the stem body diameter of the femoral stem is
The CT value of the femoral stem is 160 mm.
Performing surface pretreatment on the outer surface of the femoral stem: sequentially polishing the outer surface of the femoral stem with 200-mesh and 800-mesh abrasive paper for 3min, and then polishing with 1200-mesh abrasive paper for 5 min; ultrasonically cleaning in acetone solution for 6 min; ultrasonically cleaning with pure water for 5min, and blow-drying to obtain a polished substrate layer; carrying out sand blasting treatment on the polished femoral stem substrate layer by using aluminum oxide particles to obtain a femoral stem substrate layer subjected to sand blasting; performing acid etching treatment and oxidation on the femoral stem substrate layer after sand blastingThe average grain diameter of the aluminum particles is 400 mu m, the pressure of sand blasting is 1MPa, and the time of sand blasting is 60 s; by using V (H)2O): acid etching treatment of mixed acid of V (sulfuric acid) and V (hydrochloric acid) at a ratio of 20:8:4 to obtain acid etched layer, and H in sulfuric acid2SO4The mass concentration of (3) was 50%, the mass concentration of HCl in hydrochloric acid was 36%, and the acid etching treatment time was 100 seconds.
And carrying out titanium powder thermal spraying on the femoral stem subjected to the acid etching treatment to obtain a transition layer, wherein the average particle size of the titanium powder selected by the thermal spraying is 80 microns, and the thickness of the transition layer after the thermal spraying is 110 microns.
Performing laser cladding on the femoral stem after titanium powder thermal spraying to form a tantalum coating: the sphericity of the tantalum pellet used was 0.8, and the average particle diameter of the spherical tantalum pellet was 28 μm (25 μm for D50 of the tantalum pellet). The laser cladding power is 5KW, the spot diameter is 22mm, the laser cladding beam scanning speed is 110mm/min, nitrogen with the flow rate of 9L/min is adopted to protect the laser cladding process, and the femoral stem tantalum coating with the tantalum coating thickness of 40 microns, the pore size of 16 microns and the porosity of 60% is obtained.
Immersing the femoral stem tantalum coating in 0.2mol/L calcium dihydrogen phosphate and 5mol/L sodium hydroxide solution at the temperature of 80 ℃, continuously carrying out 24-hour hydrothermal reaction, and finally carrying out ultrasonic cleaning by using deionized water to obtain the femoral stem orthopedic implant with the surface functional layer of nano-wire calcium tantalate (the diameter of the nano-wire calcium tantalate is 25nm, and the length of the nano-wire calcium tantalate is 450 nm).
Comparative example 1
Comparative example 1 is different from example 1 in that,
the power of laser cladding is 8.5KW, and finally the acetabular cup orthopedic implant is obtained.
The pore sizes of the tantalum coatings of the orthopedic implants obtained in examples 1 to 18 and comparative example 1 were respectively measured according to YY/T0988.14-2016, and the coating porosity, the thickness of the tantalum coating, and the thickness of the transition layer of the tantalum coatings of the orthopedic implants obtained in examples 1 to 18 and comparative example 1 were respectively measured by scanning electron microscopy, and the results of the measurements are shown in Table 1.
TABLE 1
As can be seen from Table 1 above, the acetabular cup orthopaedic implant of comparative example 1 was prone to sloughing from bone tissue, thereby reducing the useful life of the acetabular cup orthopaedic implant as compared to the examples.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
on one hand, the tantalum coating orthopedic implant material forms a transition layer between the substrate layer and the tantalum coating, so that the thermal stress between the tantalum coating and the substrate layer is reduced, and the bonding force between the tantalum coating and the transition layer is improved; on the other hand, the porous structure of the tantalum coating provides a space for the growth of bone tissues, the bone growth is enhanced, the biocompatibility and the osteoconductivity of the tantalum coating are improved, a microenvironment beneficial to cell growth is generated, the bone tissues are promoted to grow towards the inside of the porous tantalum coating to form a unique bone-implant interface, the stability and the function of the tantalum-coated bone implant in the bone tissues are obviously enhanced, the osseointegration of the bone-implant interface is accelerated, in addition, the tantalum coating only improves the structure of the tantalum coating, the osseointegration of the bone-implant interface is improved, and compared with a method for pretreating the tantalum coating by introducing a non-tantalum substance, the tantalum-coated bone implant is low in production cost, small in potential hazard of the non-tantalum substance, and has a better application prospect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by 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 (13)
1. The tantalum coating orthopedic implant material comprises a substrate layer, a transition layer, a tantalum coating and a tantalum surface functional layer which are sequentially stacked, and is characterized in that the substrate layer is made of titanium or titanium alloy, the melting point of the transition layer is lower than that of tantalum, and the tantalum coating is of a porous structure.
2. The tantalum-coated orthopedic implant material according to claim 1, wherein the tantalum coating has a pore size of 10-30 μm, preferably the tantalum coating has a coating porosity of 30-80%, and preferably the tantalum coating has a thickness of 30-60 μm.
3. The tantalum-coated orthopedic implant material of claim 1 or 2, wherein the transition layer has a thickness of 90-180 μm.
4. The tantalum-coated orthopedic implant material according to any one of claims 1 to 3, wherein the tantalum surface functional layer is a nano-wire-shaped calcium tantalate, preferably the diameter of the nano-wire-shaped calcium tantalate is 20-35 nm, preferably the length of the nano-wire-shaped calcium tantalate is less than or equal to 500 nm.
5. The tantalum-coated orthopedic implant material of claim 1, wherein the titanium alloy is selected from any one of Ti-6Al-4V, Ti-6Al-17Nb, Ti-13Nb-13Zr, Ti-5Zr-3Mo-15 Nb.
6. The tantalum-coated orthopedic implant material of claim 1, wherein the transition layer is pure titanium or Ti-6 Al-4V.
7. A tantalum-coated orthopaedic implant comprising the tantalum-coated orthopaedic implant material of any one of claims 1 to 6, wherein the tantalum-coated orthopaedic implant is any one of an acetabular cup, an acetabular patch, a femoral stem.
8. A method for preparing the tantalum-coated orthopedic implant material according to any one of claims 1 to 7, the method comprises sequentially forming a transition layer, a tantalum coating and a tantalum surface functional layer on a substrate layer, wherein the tantalum coating is formed by spraying tantalum particles on the transition layer by a laser cladding method to form the tantalum coating, wherein the power of the laser cladding is less than or equal to 8.0 KW.
9. The method of manufacturing according to claim 8, comprising:
step S1, spraying titanium powder or titanium alloy particles on the base layer to form the transition layer;
step S2, spraying tantalum particles on the transition layer by adopting the laser cladding method to form the tantalum coating;
and step S3, carrying out hydrothermal reaction on the tantalum coating, calcium salt and strong alkali solution to obtain the tantalum coating orthopedic implant material.
10. The method of claim 8 or 9, wherein the tantalum pellet has a sphericity of 0.6 to 1, preferably an average particle diameter of 5 to 40 μm, and/or a D50 of 20 to 30 μm.
11. The preparation method according to claim 8 or 9, wherein the power of the laser cladding is 4.0-8.0 KW, the diameter of a light spot of the laser cladding is preferably 20-25 mm, the scanning speed of a light beam of the laser cladding is preferably 100-180 mm/min, and inert gas or nitrogen with the flow rate of 8-12L/min is preferably used for protecting the laser cladding process.
12. The method according to claim 9, wherein in step S1, the titanium powder or the titanium alloy particles each independently have an average particle diameter of 70 to 100 μm.
13. The production method according to claim 8 or 9, characterized by further comprising:
carrying out surface pretreatment on the substrate layer,
preferably, the surface pretreatment process comprises:
sequentially polishing the substrate layer to obtain a polished substrate layer;
carrying out sand blasting treatment on the polished substrate layer by using alumina particles to obtain a sand blasted substrate layer;
carrying out acid etching treatment on the substrate layer after sand blasting,
preferably, the average particle size of the alumina particles is 350-500 μm, the pressure of the sand blasting treatment is 0.8-1.2 MPa, and the time of the sand blasting treatment is 45-90 s;
preference is given to using V (H)2O): v (sulfuric acid) and V (hydrochloric acid) 20:8:4, wherein H in the sulfuric acid is subjected to the acid etching treatment2SO4The mass concentration of the acid etching solution is 40-50%, the mass concentration of HCl in hydrochloric acid is 30-40%, and the time of the acid etching treatment is preferably 90-120 s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110548474.XA CN113289057B (en) | 2021-05-19 | 2021-05-19 | Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110548474.XA CN113289057B (en) | 2021-05-19 | 2021-05-19 | Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113289057A true CN113289057A (en) | 2021-08-24 |
| CN113289057B CN113289057B (en) | 2022-10-14 |
Family
ID=77322823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110548474.XA Active CN113289057B (en) | 2021-05-19 | 2021-05-19 | Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113289057B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114099777A (en) * | 2021-11-19 | 2022-03-01 | 湖南普林特医疗器械有限公司 | Multi-layer active coating for orthopedic implant and preparation method thereof |
| CN114686871A (en) * | 2022-03-30 | 2022-07-01 | 中国兵器科学研究院宁波分院 | Preparation method of biological porous coating based on powder oxygenation design |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040191106A1 (en) * | 2002-11-08 | 2004-09-30 | Howmedica Osteonics Corp. | Laser-produced porous surface |
| CN102409195A (en) * | 2011-12-02 | 2012-04-11 | 苏州大学 | Preparation method of porous tantalum and device applied to same |
| CN102644078A (en) * | 2012-05-16 | 2012-08-22 | 西安交通大学 | Preparation technology of porous calcium gluconate tantalite/nono-funicular hydroxylapatite bioactive coating |
| US20140086962A1 (en) * | 2012-02-07 | 2014-03-27 | The Regents Of The University Of California | Products of manufacture having tantalum coated nanostructures, and methods of making and using them |
| CN106693069A (en) * | 2017-02-22 | 2017-05-24 | 华中科技大学 | Method for preparing medical porous titanium-tantalum artificial bone and artificial joint, and products thereof |
-
2021
- 2021-05-19 CN CN202110548474.XA patent/CN113289057B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040191106A1 (en) * | 2002-11-08 | 2004-09-30 | Howmedica Osteonics Corp. | Laser-produced porous surface |
| CN102409195A (en) * | 2011-12-02 | 2012-04-11 | 苏州大学 | Preparation method of porous tantalum and device applied to same |
| US20140086962A1 (en) * | 2012-02-07 | 2014-03-27 | The Regents Of The University Of California | Products of manufacture having tantalum coated nanostructures, and methods of making and using them |
| CN102644078A (en) * | 2012-05-16 | 2012-08-22 | 西安交通大学 | Preparation technology of porous calcium gluconate tantalite/nono-funicular hydroxylapatite bioactive coating |
| CN106693069A (en) * | 2017-02-22 | 2017-05-24 | 华中科技大学 | Method for preparing medical porous titanium-tantalum artificial bone and artificial joint, and products thereof |
Non-Patent Citations (1)
| Title |
|---|
| 丁玎: "骨植入体表面钽基涂层的制备和生物学性能研究", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114099777A (en) * | 2021-11-19 | 2022-03-01 | 湖南普林特医疗器械有限公司 | Multi-layer active coating for orthopedic implant and preparation method thereof |
| CN114686871A (en) * | 2022-03-30 | 2022-07-01 | 中国兵器科学研究院宁波分院 | Preparation method of biological porous coating based on powder oxygenation design |
| CN114686871B (en) * | 2022-03-30 | 2023-07-25 | 中国兵器科学研究院宁波分院 | Preparation method of biological porous coating based on powder oxygenation design |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113289057B (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sasikumar et al. | Surface modification methods for titanium and its alloys and their corrosion behavior in biological environment: a review | |
| Zhu et al. | Advances in implant surface modifications to improve osseointegration | |
| Alla et al. | Surface roughness of implants: a review | |
| JP2578419B2 (en) | Ceramic treated metal implant | |
| CN113289057B (en) | Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant | |
| EP2014319A1 (en) | A bone tissue implant comprising strontium ions | |
| US7998523B2 (en) | Open-pore biocompatible surface layer for an implant, methods of production and use | |
| KR100751505B1 (en) | Hydroxyapatite coatings with excellent bio-compatibility and preparation method thereof | |
| Harun et al. | Hydroxyapatite-based coating on biomedical implant | |
| JP2000503571A (en) | Surface modification of medical implants | |
| JPH072180B2 (en) | Buried body coating | |
| Swain et al. | Effect of surface roughness on titanium medical implants | |
| CN112999414B (en) | 3D printing titanium alloy and preparation method thereof | |
| Fouziya et al. | Surface modifications of titanium implants–The new, the old, and the never heard of options | |
| KR101933701B1 (en) | Biocompatible ceramics coating layer, titanium substrate comprising coating layer and manufacturing method thereof | |
| TW201602420A (en) | Titanium or titanium alloy having antibacterial surface and method for manufacturing the same | |
| KR101134977B1 (en) | Implant surface treatment method and implant treated by the method | |
| CN111467577B (en) | Medical metal bone implant material | |
| CN112620626B (en) | Forming method of bone induction type titanium alloy bone implant with high antibacterial property | |
| CN111363995B (en) | Preparation method of medical metal bone implant material | |
| EP3195825B1 (en) | Dental implant | |
| Hadipour et al. | Preparation and characterization of plasma-sprayed nanostructured-merwinite coating on Ti-6Al-4V | |
| Chandra et al. | Implant surface modifications: A review | |
| KR101092227B1 (en) | Metal surface treatment method and the metal treated thereby | |
| KR100453289B1 (en) | Electrolyte solution for implant surface treatment and method of implant surface treatment using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |