CN109276760B - Preparation method of PEEK composite material artificial hip joint suitable for 3D printing - Google Patents
Preparation method of PEEK composite material artificial hip joint suitable for 3D printing Download PDFInfo
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- CN109276760B CN109276760B CN201811026390.4A CN201811026390A CN109276760B CN 109276760 B CN109276760 B CN 109276760B CN 201811026390 A CN201811026390 A CN 201811026390A CN 109276760 B CN109276760 B CN 109276760B
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
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Abstract
The invention provides a preparation method of a PEEK composite material artificial hip joint suitable for 3D printing, which designs the three-dimensional shape of the artificial hip joint by a digital technology, designs the contact surface of the artificial hip joint and human bones into a reticular grooved structure or a honeycomb hole structure, and uses the PEEK composite material artificial hip joint containing CaCO3The PEEK composite material of the whisker is used as a 3D printing material of the artificial hip joint, the artificial hip joint is printed by a special 3D printer according to designed modeling data, and then the contact surface of the artificial hip joint and human bones is subjected to surface treatment and coated with active bone paste, so that the artificial hip joint with excellent performance is obtained. The method can be used for rapidly preparing the personalized artificial hip joint, and the prepared artificial hip joint has good mechanical property and wear resistance, the elastic modulus is similar to that of human skeleton, and simultaneously has good bioactivity and bone inductivity, so that the bone regeneration can be guided, and the joint interface between the artificial hip joint and the human skeleton can be well healed.
Description
Technical Field
The invention relates to a preparation method of an artificial hip joint, in particular to a preparation method of a PEEK composite material artificial hip joint suitable for 3D printing, and belongs to the technical field of preparation of medical materials for orthopedic surgery.
Background
In recent years, with the development of economy and science, the development levels of tissue engineering and regenerative medicine are greatly improved, so that a new choice is provided for repairing bone defects, the bone tissue engineering technology is applied to the treatment of large-area bone defects, and the defects of autologous bone transplantation and allogeneic bone transplantation can be overcome. The bone tissue engineering requires that the artificial bone is made of biological materials with good bone conductivity and bone inductivity, and has good biocompatibility and biodegradability.
With the coming of the population aging society, femoral head necrosis and femoral neck fracture of the old are common orthopedic diseases, and hip joint replacement for the femoral neck fracture of the old as soon as possible is a consensus of numerous scholars. At present, because the cobalt-chromium-molybdenum alloy artificial hip joint is low in price and widely used, in order to improve the wear resistance, a zirconium oxide-aluminum oxide ceramic artificial hip joint is also available on the market, however, whether the cobalt-chromium-molybdenum alloy artificial hip joint or the zirconium oxide-aluminum oxide ceramic artificial hip joint has no bioactivity, is too strong in rigidity and too high in elastic modulus, can generate a shielding phenomenon, and does not meet the requirements of bone tissue engineering materials, so that other materials are hoped to be adopted to prepare the artificial hip joint with good mechanical property, bioactivity and osteogenesis induction function.
Polyetheretherketone (PEEK) is a plastic with high strength, high fracture toughness, and fatigue resistance comparable to that of alloys. The medical PEEK has good biocompatibility, no cytotoxicity, no mutagenicity, no carcinogenicity, no allergy, strong corrosion resistance, hydrolysis resistance and chemical resistance, and good mechanical properties, and is one of the widely researched artificial bone materials. PEEK used in the medical field is the best long-term bone graft material approved by the FDA in the united states and has a glass transition temperature of 145 ℃ and a melting temperature of 334 ℃. PEEK alone is used as an artificial bone material, which has disadvantages in that abrasion resistance is insufficient and an osteogenesis inducing function is lacking. By adjusting the adding proportion of the reinforcing material, the Young modulus of the PEEK composite material can be adjusted to 18-19GPa, which is the closest to that of human skeleton, and the PEEK composite material can coexist with healthy bone for a long time when used as implanted bone, and the skeleton can not be loosened and degraded.
The relevant publications show that calcium carbonate (CaCO) is added3) The wear rate of the PEEK composite material after the whisker is obviously reduced, CaCO3The whisker absorbs energy by means of bridging of the whisker, crack deflection and pull-out effect, and eliminates stress at the tip of the crack, so that stress borne by surrounding matrix materials is reduced, wear resistance is improved, and particles worn out cannot cause foreign matter damage and increase wear resistance. Adding 10-20% of CaCO3The wear rate of the PEEK composite material of the whisker is reduced by 26 times, CaCO3When the whisker content is 15%, the wear rate of the PEEK composite material is reduced by 86 percent relative to pure PEEK, and the PEEK composite material contains 15-20 percent of CaCO3The PEEK whisker composite material has the lowest friction coefficient and wear rate under various pressures and has the optimal antifriction effect.
The 3D printing technology is based on a digital model file, relies on the advanced technologies of various subjects such as information technology, material science, precision machinery and the like, mainly designs model data through Computer Aided Design (CAD) software, guides the data into a specific printer, and constructs an object by using meltable bonding materials such as powdered metal or plastic and the like and heating, melting, extruding and printing layer by layer. At present, the 3D printing technology is gradually applied to the preparation process of bone tissue engineering scaffold materials, and the 3D printing can manufacture artificial hip joints consistent with the human skeleton shape according to CT scanning data or computer design models and manufacture corresponding bionic pores so as to enhance the living activity of the materials. Due to the fact that the PEEK material is high in melting point and high in viscosity, a few 3D printers capable of using the PEEK as a printing material are available in the market at present, an Apium M series 3D printer produced by Germany Apium company is a 3D printer for professional printing and implanting of medical instruments, has the advantages of being high in heating temperature, large in pressure of a sprayer, high in printing resolution and the like, can be suitable for various high-performance polymer materials such as the PEEK, the carbon fiber reinforced PEEK, the PEI 9085 and the POM-C, and cannot influence biocompatibility and sterilization performance of the PEEK material when the PEEK material is used for processing the PEEK material.
In addition, in order to further increase the osteoinductive property and the biological activity, the PEEK composite material artificial hip joint printed by the 3D printer needs to be further surface-treated.
Disclosure of Invention
The invention aims to provide a preparation method of a PEEK composite material artificial hip joint suitable for 3D printing, which is used for quickly preparing a personalized artificial hip joint which has good mechanical strength and bioactivity, has an elastic modulus similar to that of human bones and has an osteogenesis induction effect.
The specific technical scheme of the invention is as follows:
a preparation method of a PEEK composite material artificial hip joint suitable for 3D printing comprises the following steps:
(1) three-dimensional modeling design of artificial hip joint
Acquiring shape data of a hip joint of a patient including a femur and an acetabulum by utilizing a CT scanning technology, constructing a three-dimensional shape of an artificial hip joint by utilizing a computer CAD three-dimensional reconstruction technology according to scanning data, combining the artificial hip joint by an artificial acetabulum and an artificial femoral head insert, and correcting the three-dimensional shape of the artificial hip joint according to the replacement effect of a computer virtual hip joint; and then designing the contact surface of the artificial hip joint and the human bone into a reticular grooved structure or a honeycomb hole structure, wherein the contact surface of the artificial hip joint and the human bone comprises the contact surface of an artificial acetabulum and the human hip bone and the contact surface of an artificial femoral head insert and the human femoral stem.
(2) Preparation of 3D printing material
Taking 85 parts by weight of medical PEEK powder and calcium carbonate (CaCO) with the length of 50-150 mu m3) Mixing 15-20 parts by weight of crystal whisker, adding sufficient glycerol and ethanol, polishing into a suspension in a high-speed polisher, filtering off the glycerol and the ethanol in the suspension by using a suction filter, and drying in a dryer to obtain the crystal whisker containing CaCO3The PEEK composite material of the whisker, regard this PEEK composite material as 3D and print the material for subsequent use.
(3) 3D prints artifical hip joint
Adding the prepared PEEK composite material in the step (2) into a heating cavity of an Apium M series 3D printer produced by the Germany Apium company, guiding the three-dimensional modeling of the artificial acetabulum and the artificial femoral head insert designed in the step (1) into control software of the 3D printer in an STL format and automatically converting the three-dimensional modeling into corresponding layered data, heating and melting the PEEK composite material by the 3D printer, extruding the PEEK composite material from a nozzle, and printing and overlapping the PEEK composite material layer by layer to obtain the artificial acetabulum and the artificial femoral head insert made of the PEEK composite material.
(4) Finishing treatment of socket of artificial acetabulum and ball head of artificial femoral head insert
The surface of a mortar socket of the artificial acetabulum and the surface of a ball head of the artificial femoral head insert are processed by a high-precision grinding machine, so that the accurate matching of the surface of the mortar socket of the artificial acetabulum and the surface of the ball head of the artificial femoral head insert is ensured.
(5) Preparation of surface coating materials
Mixing 40-70 parts by weight of Polycaprolactone (PCL), 15-20 parts by weight of nano hydroxyapatite (nHA) and 15-20 parts by weight of beta-calcium phosphate (beta-TCP), adding sufficient dichloromethane as a solvent, and fully stirring to prepare the spray coating adhesive.
(6) Surface treatment of contact surface between artificial hip joint and human bone
Performing sand blasting treatment on the contact surface of the artificial hip joint and the human bone, observing that whisker heads are exposed on the surface of the PEEK composite material by using a Scanning Electron Microscope (SEM), cleaning with water after the sand blasting treatment, and drying with hot air; and (3) uniformly spraying the spray gun for spraying the glue prepared in the step (5) on the contact surface of the artificial hip joint and the human bone, wherein the thickness of the coating is 100-200 mu m, drying the coating by high-speed hot air after the spraying is finished, so that dichloromethane in the coating is completely volatilized, a large number of micropores are formed on the surface of the coating due to the escape of the dichloromethane, performing secondary sand blasting treatment on the contact surface of the artificial hip joint and the human bone, cleaning the contact surface by water, drying the contact surface by hot air, and sterilizing the contact surface for later use.
(7) Active bone paste is coated on the contact surface of the artificial hip joint and the human bone
Before the replacement operation, a layer of active bone paste is coated in the meshes of the contact surface of the artificial hip joint and the human bone and then the artificial hip joint can be immediately used for the replacement operation; the preparation method of the active bone paste comprises the following steps: collecting 25-70 parts by weight of autologous bone powder generated when a femoral matching hole is drilled, adding 15-25 parts by weight of nHA and 10-30 parts by weight of beta-TCP, adding a proper amount of platelet-rich fibrin (PRF), and stirring together to form paste, namely the active bone paste.
The invention designs the three-dimensional shape of the artificial hip joint by a digital technology, designs the contact surface of the artificial hip joint and human bones into a reticular grooved structure or a honeycomb hole structure, and then uses CaCO-containing material3The PEEK composite material of the whisker is used as a 3D printing material of the artificial hip joint, the artificial hip joint is printed by a special 3D printer according to designed modeling data, and then the contact surface of the artificial hip joint and human bones is subjected to surface treatment and coated with active bone paste, so that the PEEK composite material artificial hip joint with excellent performance is obtained. The method can be used for rapidly preparing the personalized artificial hip joint, and the prepared artificial hip joint has good strengthThe artificial hip joint has the advantages of good chemical property, wear resistance and elastic modulus similar to those of human bones, good biological activity and bone inductivity, and capability of guiding bone regeneration and well healing the joint interface between the artificial hip joint and the human bones.
Drawings
Fig. 1 is a schematic structural view of the artificial hip joint (the contact surface with human bones is a reticular groove) of the invention.
Fig. 2 is a schematic structural view of the artificial hip joint (the contact surface with human bone is a honeycomb hole) of the present invention.
Fig. 3 is a schematic diagram of the application of the artificial bone hip joint of the present invention in hip replacement.
In the figure: 1-artificial acetabulum, 2-artificial femoral head insert, 3-human hip bone, 4-bone nail, and 5-human femoral shaft.
Detailed Description
The preparation method of the PEEK composite material artificial hip joint suitable for 3D printing comprises the following steps:
(1) three-dimensional modeling design of artificial hip joint
Acquiring shape data of a hip joint of a patient including a femur and an acetabulum by utilizing a CT scanning technology, constructing a three-dimensional shape of an artificial hip joint by utilizing a computer CAD three-dimensional reconstruction technology according to scanning data, combining the artificial hip joint by an artificial acetabulum and an artificial femoral head insert, and correcting the three-dimensional shape of the artificial hip joint according to the replacement effect of a computer virtual hip joint; then designing the contact surface of the artificial hip joint and the human bone into a reticular grooved structure or a honeycomb hole structure, wherein the contact surface of the artificial hip joint and the human bone comprises the contact surface of the artificial acetabulum and the human hip bone and the contact surface of the artificial femoral head insert and the human femoral stem, and the contact surfaces are shown in figures 1-3.
When the contact surface of the artificial hip joint and the human bone is designed into a reticular slotted structure, the distance between the slots is 400 plus 500 mu m, the width of the slots is 350 mu m, and the depth is 500 plus 1000 mu m; when the contact surface of the artificial hip joint and the human bone is designed into a honeycomb-shaped hole structure, the distance between the holes is 500 mu m, the aperture is 350 mu m, and the depth of the holes is 500-1000 mu m.
(2) Preparation of 3D printing material
Taking 85 parts by weight of medical PEEK powder and calcium carbonate (CaCO) with the length of 50-150 mu m3) Mixing 15-20 parts by weight of crystal whisker, adding sufficient glycerol and ethanol, polishing into a suspension in a high-speed polisher, filtering off the glycerol and the ethanol in the suspension by using a suction filter, and drying in a dryer to obtain the crystal whisker containing CaCO3The PEEK composite material of the whisker, regard this PEEK composite material as 3D and print the material for subsequent use.
(3) 3D prints artifical hip joint
Adding the prepared PEEK composite material in the step (2) into a heating cavity of an Apium M series 3D printer produced by the Germany Apium company, guiding the three-dimensional modeling of the artificial acetabulum and the artificial femoral head insert designed in the step (1) into control software of the 3D printer in an STL format and automatically converting the three-dimensional modeling into corresponding layered data, heating and melting the PEEK composite material by the 3D printer, extruding the PEEK composite material from a nozzle, and printing and overlapping the PEEK composite material layer by layer to obtain the artificial acetabulum and the artificial femoral head insert made of the PEEK composite material.
(4) Finishing treatment of socket of artificial acetabulum and ball head of artificial femoral head insert
The surface of a mortar socket of the artificial acetabulum and the surface of a ball head of the artificial femoral head insert are processed by a high-precision grinding machine, so that the accurate matching of the surface of the mortar socket of the artificial acetabulum and the surface of the ball head of the artificial femoral head insert is ensured.
(5) Preparation of surface coating materials
Mixing 40-70 parts by weight of Polycaprolactone (PCL), 15-20 parts by weight of nano hydroxyapatite (nHA) and 15-20 parts by weight of beta-calcium phosphate (beta-TCP), adding sufficient dichloromethane as a solvent, and fully stirring to prepare the spray coating adhesive.
(6) Surface treatment of contact surface between artificial hip joint and human bone
Performing sand blasting treatment on the contact surface of the artificial hip joint and the human bone, observing that whisker heads are exposed on the surface of the PEEK composite material by using a Scanning Electron Microscope (SEM), cleaning with water after the sand blasting treatment, and drying with hot air; and (3) uniformly spraying the spray gun for spraying the glue prepared in the step (5) on the contact surface of the artificial hip joint and the human bone, wherein the thickness of the coating is 100-200 mu m, drying the coating by high-speed hot air after the spraying is finished, so that dichloromethane in the coating is completely volatilized, a large number of micropores are formed on the surface of the coating due to the escape of the dichloromethane, performing secondary sand blasting treatment on the contact surface of the artificial hip joint and the human bone, cleaning the contact surface by water, drying the contact surface by hot air, and sterilizing the contact surface for later use.
The sand blasting treatment adopts sodium bicarbonate sand grains with the grain size of 200-300 mu m as sand blasting sand grains.
Tests show that after the mixture of PCL, nHA and beta-TCP materials mixed according to a certain proportion is implanted into tissues, the mixture has good biocompatibility, osteoinduction and bioactivity, no inflammatory reaction, no immunity and cytotoxicity and good effects of promoting human osteoblast adhesion and osteoblast differentiation. Therefore, three materials of PCL, nHA and beta-TCP are mixed by using dichloromethane as a solvent, sprayed on the contact surface of the artificial hip joint and the human bone, and then the dichloromethane in the coating is blown off by high-speed hot air, so that a large number of micropores are formed on the surface of the coating due to the escape of the dichloromethane, and the osteogenic inductivity is further increased.
(7) Active bone paste is coated on the contact surface of the artificial hip joint and the human bone
Before the replacement operation, a layer of active bone paste is coated in the meshes of the contact surface of the artificial hip joint and the human bone and then the artificial hip joint can be immediately used for the replacement operation; the preparation method of the active bone paste comprises the following steps: collecting 25-70 parts by weight of autologous bone powder generated when a femoral matching hole is drilled, adding 15-25 parts by weight of nHA and 10-30 parts by weight of beta-TCP, adding a proper amount of platelet-rich fibrin (PRF), and stirring together to form paste, namely the active bone paste.
The platelet-rich fibrin (PRF) is obtained by centrifuging autologous venous blood into 3 layers, and then taking fibrin gel in the middle layer. When the autologous bone meal cannot be collected or the collected amount is too small, the bone meal can be replaced by the allogeneic bone meal sold on the market, such as Gaoshi Bio-Os bone meal in Switzerland, we do not claim to obtain the autologous bone meal intentionally so as to avoid secondary injury.
After the contact surface of the artificial hip joint and the human bone is coated with the active bone paste, the regeneration of osteoblasts can be promoted, so that the connection interface of the artificial hip joint and the human bone can be well healed.
Claims (2)
1. A preparation method of a PEEK composite material artificial hip joint suitable for 3D printing is characterized by comprising the following steps:
(1) three-dimensional modeling design of artificial hip joint
Acquiring shape data of a hip joint of a patient including a femur and an acetabulum by utilizing a CT scanning technology, constructing a three-dimensional shape of an artificial hip joint by utilizing a computer CAD three-dimensional reconstruction technology according to scanning data, combining the artificial hip joint by an artificial acetabulum and an artificial femoral head insert, and correcting the three-dimensional shape of the artificial hip joint according to the replacement effect of a computer virtual hip joint; then designing the contact surface of the artificial hip joint and the human bone into a reticular grooved structure or a honeycomb hole structure, wherein the contact surface of the artificial hip joint and the human bone comprises the contact surface of an artificial acetabulum and the human hip bone and the contact surface of an artificial femoral head insert and the human femoral stem;
when the contact surface of the artificial hip joint and the human bone is designed into a reticular slotted structure, the distance between the slots is 400 plus 500 mu m, the width of the slots is 350 mu m, and the depth is 500 plus 1000 mu m; when the contact surface of the artificial hip joint and the human bone is designed into a honeycomb-shaped hole structure, the distance between the holes is 500 mu m, the aperture is 350 mu m, and the depth of the holes is 500-1000 mu m;
(2) preparation of 3D printing material
Taking 85 parts by weight of medical PEEK powder and calcium carbonate (CaCO) with the length of 50-150 mu m3) Mixing 15-20 parts by weight of crystal whisker, adding sufficient glycerol and ethanol, polishing into a suspension in a high-speed polisher, filtering off the glycerol and the ethanol in the suspension by using a suction filter, and drying in a dryer to obtain the crystal whisker containing CaCO3The PEEK composite material of the crystal whisker is used as a 3D printing material for standby;
(3) 3D prints artifical hip joint
Adding the prepared PEEK composite material in the step (2) into a heating cavity of an Apium M series 3D printer produced by the Germany Apium company, guiding the three-dimensional modeling of the artificial acetabulum and the artificial femoral head insert designed in the step (1) into control software of the 3D printer in an STL format and automatically converting the three-dimensional modeling into corresponding layered data, heating and melting the PEEK composite material by the 3D printer, extruding the PEEK composite material from a nozzle, and printing and overlapping the PEEK composite material layer by layer to form the artificial acetabulum and the artificial femoral head insert made of the PEEK composite material;
(4) finishing treatment of socket of artificial acetabulum and ball head of artificial femoral head insert
Processing the surface of a socket of the artificial acetabulum and the surface of a ball head of the artificial femoral head insert by using a high-precision grinding machine, and ensuring that the surface of the socket of the artificial acetabulum is precisely matched with the surface of the ball head of the artificial femoral head insert;
(5) preparation of surface coating materials
Mixing 40-70 parts by weight of Polycaprolactone (PCL), 15-20 parts by weight of nano hydroxyapatite (nHA) and 15-20 parts by weight of beta-calcium phosphate (beta-TCP), adding sufficient dichloromethane serving as a solvent, and fully stirring to prepare the spray coating adhesive;
(6) surface treatment of contact surface between artificial hip joint and human bone
Performing sand blasting treatment on the contact surface of the artificial hip joint and the human bone, observing that whisker heads are exposed on the surface of the PEEK composite material by using a Scanning Electron Microscope (SEM), cleaning with water after the sand blasting treatment, and drying with hot air; then uniformly spraying the spray gun for spraying the glue prepared in the step (5) on the contact surface of the artificial hip joint and the human bone, wherein the thickness of the coating is 100-;
(7) active bone paste is coated on the contact surface of the artificial hip joint and the human bone
Before the replacement operation, a layer of active bone paste is coated in the meshes of the contact surface of the artificial hip joint and the human bone and then the artificial hip joint can be immediately used for the replacement operation; the preparation method of the active bone paste comprises the following steps: adding 30-70 parts by weight of commercially available bone allograft powder, 15-25 parts by weight of nHA and 10-30 parts by weight of beta-TCP, adding a proper amount of platelet-rich fibrin (PRF), and stirring to form paste, namely the active bone paste.
2. The method for preparing the PEEK composite material artificial hip joint as claimed in claim 1, wherein the method comprises the following steps: in the step (6), the blasting treatment adopts sodium bicarbonate sand grains with the grain size of 200-300 μm as blasting sand grains.
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