CN112704582A - Preparation method of customizable regenerated porous nano-material 3D printed femoral head - Google Patents
Preparation method of customizable regenerated porous nano-material 3D printed femoral head Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/32—Joints for the hip
- A61F2/36—Femoral heads ; Femoral endoprostheses
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2002/30769—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth madreporic
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2/30942—Designing or manufacturing processes for designing or making customized prostheses, e.g. using templates, CT or NMR scans, finite-element analysis or CAD-CAM techniques
- A61F2002/30948—Designing or manufacturing processes for designing or making customized prostheses, e.g. using templates, CT or NMR scans, finite-element analysis or CAD-CAM techniques using computerized tomography, i.e. CT scans
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2/30942—Designing or manufacturing processes for designing or making customized prostheses, e.g. using templates, CT or NMR scans, finite-element analysis or CAD-CAM techniques
- A61F2002/30952—Designing or manufacturing processes for designing or making customized prostheses, e.g. using templates, CT or NMR scans, finite-element analysis or CAD-CAM techniques using CAD-CAM techniques or NC-techniques
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2002/3097—Designing or manufacturing processes using laser
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2002/30985—Designing or manufacturing processes using three dimensional printing [3DP]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00023—Titanium or titanium-based alloys, e.g. Ti-Ni alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00179—Ceramics or ceramic-like structures
- A61F2310/00185—Ceramics or ceramic-like structures based on metal oxides
- A61F2310/00239—Ceramics or ceramic-like structures based on metal oxides containing zirconia or zirconium oxide ZrO2
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00179—Ceramics or ceramic-like structures
- A61F2310/00293—Ceramics or ceramic-like structures containing a phosphorus-containing compound, e.g. apatite
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- Health & Medical Sciences (AREA)
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- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
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- Heart & Thoracic Surgery (AREA)
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Abstract
A preparation method of a customizable regenerative porous nano material 3D printing femoral head. The method comprises the steps of obtaining femoral head image data by CT scanning, establishing a three-dimensional model suitable for a transplanted joint according to the CT image data, respectively using a metal nano composite material and a beta tricalcium phosphate-polypyrrole-biotin composite material as femoral head base materials, printing layer by layer in a body-centered cubic porous structure, adding icaritin-biotin-polylactic acid microspheres for carrying out ball loading treatment, and covering a biological ceramic coating on the surface.
Description
Technical Field
The invention designs a medical implant prosthesis, and particularly relates to a customized reproducible multielement porous multilayer nano composite 3D printing hip joint femoral head.
Background
The hip joint is one of important joints for maintaining daily activities of a human body, and is easy to damage so as to cause diseases, the hip joint replacement is an effective means for treating the hip joint diseases at present, in recent years, with the development of a 3D printing technology, students have great interest in the aspect of the optimized design of an artificial hip joint prosthesis, many experts and students make excellent contributions to the development of the artificial hip joint, and remarkable achievements are obtained, and the artificial hip joint prosthesis is required to have good biocompatibility, flexibility, bearing capacity, stability and small frictional wear. With the continuous progress of material science and biomechanics, the research of the artificial hip joint prosthesis on the aspects of materials, structural shapes, fixing modes, optimized design and the like has great breakthrough.
Clinical hip joint replacement can be divided into three aspects, including the physical condition of a patient, the operation technology of a doctor in the operation process and the artificial hip joint prosthesis, two main factors influencing the long-term stability and the service life of the artificial hip joint prosthesis are bone absorption and aseptic loosening, researches show that the postoperative pain phenomenon is accompanied, and the main reasons are mainly stress concentration and stress shielding generated after the prosthesis is implanted into a human body.
Compared with the traditional method, the hip joint femoral head printed by the invention adopts a body-centered cubic structure for printing, so that the mechanical property, the fatigue resistance and the stability are optimized, the icaritin serving as an osteogenesis inducing active substance is widely loaded in an orthopedic support material, the polyamide 6 has excellent toughness, friction resistance and biocompatibility, the medicine carrying capacity and the slow release performance are improved by adding the icaritin, the bone marrow mesenchymal stem cells can be stimulated to participate in bone repair around a prosthesis, the regeneration of the hip joint femoral head is realized, and the risk of secondary operation is avoided. Also relevant to the present invention are the following documents:
1. liu lutan.3D printing of porous titanium metal implants different porosity on bone ingrowth effect experimental study [ J ]. Anodont college of medicine 2019.09: 1153-.
Mainly describes the evaluation of the influence of different porosities of the porous titanium metal implant on the bone ingrowth effect by observing the bone ingrowth condition of the 3D printed porous titanium metal implant with different porosities in an experiment in a rabbit body.
2. Numerical simulation and experimental study of mechanical properties of a hip prosthesis porous structure printed by Lishubo.3D [ D ] Jilin university 2020,06.
The method mainly describes that 4 different unit body structures are arranged, a geometric model and a finite element model are established, a compression simulation experiment is carried out to carry out finite element simulation analysis, and the difference of mechanical properties of different porous structures is explored.
3. Liu Zn, Du < -bin > -and porous beta tricalcium phosphate-polypyrrole-biotin-icaritin microsphere composite scaffold promotes recruitment of mesenchymal stem cells [ J ]. China tissue engineering research 2020 (34): 5532 and 5537.
Mainly describes that the porous beta tricalcium phosphate-polypyrrole-biotin composite stent further improves the drug loading capacity and the sustained release performance compared with the traditional sustained release stent, has good mechanical strength and possibly has better function of recruiting bone marrow mesenchymal stem cells to participate in the repair of bones around the stent.
4. Preparation of boron-containing Cap bioceramic coating [ D ]. Nanhua university. 2019.05 by laser cladding on surface of titanium alloy
Mainly describes that the CaP biological ceramic coatings with different boron contents are prepared by adopting a laser cladding method, and researches CaB6The influence of the content on the corrosion resistance and the bioactivity of the cladding.
5. Preparation and performance research of Seattle silver/hydroxyapatite/polyamide 6 composite material [ D ] Tai principle chemical university 2018.06
The method mainly describes that Ag/HA/PA6 composite materials with different contents are prepared by different complexing agents through a solution blending method, and the structure, the crystallization property, the mechanical property, the friction property and the like of the composite materials are analyzed and researched.
6. Oshkour A A,Osman N A A,Davoodi M M,et al.Finite element analysis on longitudinal and radial functionally graded femoral prosthesis[J].International Journal for Numerical Methods in Biomedical Engineering,2013,29(12): 1412-1427.
The influence of different geometric parameters on the gradient femoral stem is mainly described, and finite element analysis is carried out on the gradient femoral stem, and the result shows that the strain energy in the prosthesis is increased and the stress shielding phenomenon is reduced by increasing the gradient index.
7. Jetté B,Brailovski V,Dumas M,et al. Femoral stem incorporating a diamond cubic lattice structure:Design,manufacture and testing[J].Journal of the Mechanical Behavior of Biomedical Materials,2018,77:58-72.
The porous hip joint prosthesis is researched by combining a finite element method and an experiment method, and the result shows that the porous hip joint prosthesis can promote bone tissue growth and reduce stress shielding.
8. Lim mahakhun S,O1oyede A,Chantarapanich N,et al.Altemative desgns of load-sharing cobalt chromium graded femoral stems[J],Materials Today Communications,2017,12:1-10.
Mainly discloses a hip joint prosthesis with a gradient pore structure in the middle, and finite element calculation and three-point bending experimental study are carried out on the mechanical property and the stress transmission property of the hip joint prosthesis.
Disclosure of Invention
The invention aims to provide a preparation method of a customizable and renewable porous nano-material 3D printed femoral head, which solves the problems of low utilization rate of artificial skeleton components and insufficient strength, toughness and wear resistance of the femoral head, materials used in a multilayer structure can stimulate the repair and growth of bone cells, so that the product can meet the affinity of human skeleton and reduce the stress concentration and stress shielding of an implant, the product customized and printed by adopting a 3D method better meets the skeleton characteristics of the human body, and the existence of the porous structure not only ensures the mechanical property but also can realize the secondary growth of the skeleton.
The invention is implemented by the following technical scheme:
scanning image data of hip joints on two sides of a human body by using a CT (computed tomography), establishing a three-dimensional model conforming to the femoral head of the hip joint at a damaged position by mirroring according to a CT image, taking a metal nano mixture powder material mixed with silver-hydroxyapatite-polyamide 6 as a 3D printed material 1, taking a beta tricalcium phosphate-polypyrrole-biotin composite material as a 3D printed material 2, respectively carrying out layered printing on femoral head matrixes by using the materials 1 and 2 in a body-centered cubic porous structure, then loading icaritin-biotin-polylactic acid microspheres on the matrixes, and finally covering and polishing a bioceramic coating on the surface of a printed body, wherein the specific scheme is as follows:
1. bone modeling
Three-dimensional scanning is carried out on the hip joint and the damaged part of the hip joint femoral head through CT scanning equipment to obtain image data, and the size and the shape of the implantable femoral head are redesigned by using three-dimensional software according to the damaged hip joint femoral head.
2. Preparation of metal nano-mixture powder material
Taking Ti powder (with the purity of 99.9%), Mg particles (with the purity of 99.8%), Si particles (with the purity of 99.8%), Ca particles and Mo powder according to the molar weight ratio of (30-50): (15-25): (30-40): (10-20): (0.1-0.3) mixing uniformly, and then putting into a high-energy ball mill for processing to obtain the ultrafine metal nano mixture powder material with the grain size of 80-100 nm.
3. Preparation of beta tricalcium phosphate-polypyrrole-biotin composite material
Deionized water, sodium polyacrylate, beta tricalcium phosphate, hydroxymethyl propylene and cellulose are mixed according to the mass fraction ratio of (1-1.2): (0.8-1): (2-5): (1-1.5): (1.2-1.6), mixing and filling into a closed container, adding equal volume of 0.1mol/L pyrrole and 0.2mol/L polyferric chloride, mixing and stirring for 35min, separating the polymer, washing with deionized water, drying the finished product, and putting into a ball mill for treatment to obtain the beta tricalcium phosphate-polypyrrole-biotin composite material with the grain size of 80-100 nm.
The beta tricalcium phosphate-polypyrrole-biotin composite bone has a rough surface and a tight and regular shape, has ridge-shaped bulges, a plurality of pores, good connectivity among the pores and large microscopic surface area, a small amount of metal-like crystal luster can be seen on the surface of the bone under a scanning electron microscope, the polypyrrole and tricalcium phosphate are mixed to endow the whole support with a conductive characteristic, and the surface of the support is suitable for the adhesion and growth of various cells. Through a chemical reaction synthesis method, polypyrrole is used as avidin to form a beta tricalcium phosphate-polypyrrole-biotin structure, and the binding capacity of the biotin multi-target point is utilized to improve the binding capacity of the scaffold and the bone induction factor.
4. Preparation of icaritin-biotin-polylactic acid microspheres
Placing biotin, icaritin, 1-hydroxybenzotriazole and 4-dimethylaminopyridine in equal amount in a polyamino acid solution, stirring at room temperature, cooling to 0 ℃, dehydrating, heating to 24-26 ℃ for full reaction, washing with deionized water, suspending the compound in absolute ethyl alcohol, heating, filtering, washing with hot absolute ethyl alcohol for 2 times, and drying to obtain the icaritin-biotin compound.
Mixing polylactic acid-glycolic acid copolymer, polyamino acid, distilled water, icaritin-biotin compound according to the mass fraction of (24.6-25.3): (24.8-25.4): (1.8-2.6): (4.8-5.3), performing ultrasonic treatment for 15 min, enabling the vibration frequency of a horn to be 40-100kHz, enabling the amplitude to be 30-100 mu m, slowly dropping 10g/L polyvinyl alcohol solution into the mixed solution for emulsification, performing ultrasonic treatment for 15 min to obtain icaritin-biotin/polylactic acid-glycolic acid copolymer multiple emulsion, finally performing high-speed 12000r/min centrifugation for 20min, filtering, washing with phosphate buffer solution for 2 times, performing centrifugation on the obtained suspension, taking out the precipitate, putting the precipitate into a freeze dryer for drying, and obtaining the icaritin-biotin-polylactic acid microspheres, wherein the diameter of the microspheres is 2-20 mu m.
5. Preparation of silver-hydroxyapatite-polyamide 6 composite material
The HA/PA6 composite material is prepared by a complexing agent coordination dissolution method, firstly CaCl is put in a closed drying container2And C2H5OH is mixed and stirred for 10min at the molar ratio of 1:5, the temperature is set at 68-72 ℃, the content of Hydroxyapatite (HA) is set at 40 percent, the mixture is mixed with polyamide 6 (PA 6) and then is placed into the container to be stirred for 20min, the HA/PA6 composite material is obtained, then the HA/PA6 composite material is carried with silver by a plasma reduction method, the silver content is set at 0.6 percent and is mixed with the HA/PA6 composite material, 5-20 percent of glass fiber is added to be mixed and stirred, finally, the finished product is dried and is placed into a ball mill to be treated, and the Ag/HA/PA6 composite material with the grain size of 80-100nm is obtained.
6. Printing femoral head using three-dimensional printing technology
Fully mixing the metal nano mixture powder material and the silver-hydroxyapatite-polyamide 6 composite material powder according to the mass fraction ratio of 3:1, naming the obtained powder material as material 1, naming beta tricalcium phosphate-polypyrrole-biotin powder as material 2, and naming icaritin-biotin-polylactic acid microsphere powder as material 3, so that the preparation work is completed.
Guiding the simulated three-dimensional model into a 3D printer, and adopting selective excitationThe light melting technology (SLM) prints a spherical body with the diameter of 2-2.2cm on an auxiliary support by using a material 1 as a femoral head 'inner core', the diameter of a spray head is set to be 120 plus 150nm, the printing speed is set to be 80-100mm/min, the printing structural form is set to be a body-centered cubic porous structure, the pore size is set to be 600 plus 650 mu m, the porosity is set to be 45-55%, the diameter of a support column is set to be 1000 plus 1200 mu m, then the material 2 is used for continuously printing the thickness of 6-8mm on the basis of the femoral head 'inner core' along with the rotation and movement of the auxiliary support, the material is used as a second layer, the diameter of the spray head is set to be 120 plus 150nm, the printing speed is set to be 80-100mm/min, the body-centered cubic porous structure is used for printing, the pore size is set to be 600 plus 650 mu m, the porosity is set to be 45-55%, the diameter of a support is designed to be 1200 mu m in 1000-plus-one mode, the thickness of the material 1 is printed to be 1-1.2cm on the basis of the material 2 by using an SLM technology, the thickness of the material is used as a third layer, the diameter of a spray head is set to be 150nm in 120-plus-one mode, the printing speed is set to be 80-100mm/min, a body-centered cubic porous structure is adopted for printing, the pore size is set to be 650 mu m in 600-plus-one mode, the porosity is set to be 45-55%, the diameter of the support is designed to be 1200 mu m in 1000-plus-one mode, an ultrasonic vibration amplitude-changing rod is added in the printing process, the vibration frequency is 80-100kHz, the amplitude is 20-150 mu m, and the distance between a tool head and the axis of a laser head is 40-50mm, so far as to finish a semi-finished product, freezing for 24 hr, ball loading femoral head, and mixing Hydroxyapatite (HA), beta tricalcium phosphate and CaB6The powders were mixed with an electronic balance at 47: 48: 5 weighing respectively, mixing the three powders, and grinding with ball mill to obtain HA powder with particle size of 30nm and purity of 99.9%, and CaB6The method comprises the following steps of mixing and stirring 45nm powder granularity, 30nm beta tricalcium phosphate powder granularity and 99.8% purity for 5min by using 0.1% isopropanol as a binder, preparing the mixed powder into a paste with certain viscosity, coating the paste on the surface of femoral head, presetting the layer powder thickness to be 4-6mm, standing for 24h at room temperature, drying for 2h in a vacuum drying box, setting the temperature of the vacuum drying box to be 45 ℃, combining the femoral head and the paste by adopting a laser cladding method, setting the laser power P =1.2KW, scanning speed V =15mm/s, and the spot diameter to be 3.0mm, and overlappingThe bonding rate is 40 percent, the argon flow rate is 10L/min, the biological ceramic coating is prepared, and finally, the formed product is polished to reduce the surface roughness of the material.
Description of the drawings:
fig. 1 is a schematic diagram of a material layer of a hip joint femoral head printed in 3D, and fig. 1 is a metal nanocomposite core; 2 is beta tricalcium phosphate-polypyrrole-biotin composite material; 3 is a metal nanocomposite; and 4, a biological ceramic coating.
The specific implementation mode is as follows:
the first step is as follows: three-dimensional scanning is carried out on the hip joint and the damaged part of the hip joint femoral head through CT scanning equipment to obtain image data, and the size and the shape of the hip joint femoral head which can be transplanted are redesigned by using three-dimensional software according to the damaged hip joint femoral head.
The second step is that: taking Ti powder (with the purity of 99.9%), Mg particles (with the purity of 99.8%), Si particles (with the purity of 99.8%), Ca particles and Mo powder according to the molar weight ratio of (30-50): (15-25): (30-40): (10-20): (0.1-0.3) mixing uniformly, and then putting into a high-energy ball mill for processing to obtain ultrafine composite powder with the grain size of 80-100 nm.
The third step: deionized water, sodium polyacrylate, beta tricalcium phosphate, hydroxymethyl propylene and cellulose are mixed according to the mass fraction ratio of (1-1.2): (0.8-1): (2-5): (1-1.5): (1.2-1.6), mixing and filling into a closed container, adding equal volume of 0.1mol/L pyrrole and 0.2mol/L polyferric chloride, mixing and stirring for 35min, separating the polymer, washing with deionized water, drying the finished product, and putting into a ball mill for treatment to obtain the beta tricalcium phosphate-polypyrrole-biotin composite material with the grain size of 80-100 nm.
The fourth step: placing biotin, icaritin, 1-hydroxybenzotriazole and 4-dimethylaminopyridine in equal amount in a polyamino acid solution, stirring at room temperature, cooling to 0 ℃, dehydrating, heating to 24-26 ℃ for full reaction, washing with deionized water, suspending the compound in absolute ethyl alcohol, heating, filtering, washing with hot absolute ethyl alcohol for 2 times, and drying to obtain the icaritin-biotin compound.
Mixing polylactic acid-glycolic acid copolymer, polyamino acid, distilled water, icaritin-biotin compound according to the mass fraction of (24.6-25.3): (24.8-25.4): (1.8-2.6): (4.8-5.3), performing ultrasonic treatment for 15 min, enabling the vibration frequency of a horn to be 40-100kHz, enabling the amplitude to be 30-100 mu m, slowly dropping 10g/L polyvinyl alcohol solution into the mixed solution for emulsification, performing ultrasonic treatment for 15 min to obtain icaritin-biotin/polylactic acid-glycolic acid copolymer multiple emulsion, finally performing high-speed 12000r/min centrifugation for 20min, filtering, washing with phosphate buffer solution for 2 times, performing centrifugation on the obtained suspension, taking out the precipitate, putting the precipitate into a freeze dryer for drying, and obtaining the icaritin-biotin-polylactic acid microspheres, wherein the diameter of the microspheres is 2-20 mu m.
And a sixth step: the HA/PA6 composite material is prepared by a complexing agent coordination dissolution method, firstly CaCl is put in a closed drying container2And C2H5OH is mixed and stirred for 10min at the molar ratio of 1:5, the temperature is set at 68-72 ℃, the content of Hydroxyapatite (HA) is set at 40 percent, the mixture is mixed with polyamide 6 (PA 6) and then is placed into the container to be stirred for 20min, the HA/PA6 composite material is obtained, then the HA/PA6 composite material is carried with silver by a plasma reduction method, the silver content is set at 0.6 percent and is mixed with the HA/PA6 composite material, 5-20 percent of glass fiber is added to be mixed and stirred, finally, the finished product is dried and is placed into a ball mill to be treated, and the Ag/HA/PA6 composite material with the grain size of 80-100nm is obtained.
The seventh step: the preparation method comprises the following steps of fully mixing a metal nano mixture powder material and a silver-hydroxyapatite-polyamide 6 composite material according to a mass fraction ratio of 3:1, naming obtained powder as a material 1, naming beta tricalcium phosphate-polypyrrole-biotin as a material 2, and naming icaritin-biotin-polylactic acid microspheres as a material 3, so that the preparation work is completed.
Introducing the simulated three-dimensional model into a 3D printer, printing a spheroid with the diameter of 2-2.2cm on an auxiliary support by adopting a Selective Laser Melting (SLM) material 1 as a femoral head 'kernel', setting the diameter of a nozzle to be 150nm in a way of 120-, setting the pore size at 650-55 mu m for 600-one, the porosity at 45-55%, designing the diameter of the strut at 1200 mu m for 1000-one, printing with the material 1 based on the material 2 by SLM technology to form a third layer with the thickness of 1-1.2cm, setting the diameter of the nozzle at 150-one for 120-one, setting the printing speed at 80-100mm/min, printing with a body-centered cubic porous structure, setting the pore size at 650 mu m for 600-one, the porosity at 45-55%, designing the diameter of the strut at 1200 mu m for 1000-one, adding an ultrasonic vibration amplitude-changing rod during the printing process, the vibration frequency at 80-100kHz, the amplitude at 20-150 mu m, and the distance between the tool head and the laser head axis at 40-50mm, thus completing the semi-finished product of the femoral head, taking the semi-finished product femoral head from the auxiliary support, placing the femoral head into a centrifuge tube, adding the suspension of the material 3 and 10% gelatin, centrifuging at low speed for 10min, freezing for 24 hr, and carrying out femoral head ball loading treatment.
Eighth step: stress-relieving the treated femoral head, and treating Hydroxyapatite (HA), beta-tricalcium phosphate and CaB6The powders were mixed with an electronic balance at 47: 48: 5, respectively weighing, mixing the three powders, fully grinding the mixture by using a ball mill to obtain HA powder with the granularity of 30nm, the purity of 99.9 percent and CaB6The method comprises the following steps of mixing and stirring 45nm powder granularity, 30nm beta tricalcium phosphate powder granularity and 99.8% purity for 5min by using 0.1% isopropanol as a binder, preparing the mixed powder into paste with certain viscosity, coating the paste on the surface of femoral head, setting the thickness of a preset layer of powder to be 4-6mm, standing the paste for 24h at room temperature, drying the paste in a vacuum drying box for 2h, setting the temperature of the vacuum drying box to be 45 ℃, combining the femoral head and the paste by adopting a laser cladding method, setting the laser power P =1.2KW, the scanning speed V =15mm/s, the spot diameter to be 3.0mm, the lap joint rate to be 40%, setting the argon gas flow rate to be 10L/min, preparing a biological ceramic coating, and finally polishing a molded product to reduce the material tableSurface roughness.
Claims (4)
1. A preparation method of a customizable regeneration porous nano-material 3D printing femoral head is characterized by comprising the following steps: the method comprises the steps of obtaining femoral head image data by CT scanning, establishing a three-dimensional model suitable for transplanting a joint according to the CT image data, respectively using a metal nano composite material and a beta tricalcium phosphate-polypyrrole-biotin composite material as femoral head base materials, adding icaritin-biotin-polylactic acid microspheres for carrying out ball loading treatment, printing the femoral head layer by layer in a body-centered cubic porous structure, and covering a biological ceramic material on the surface of the femoral head, wherein the femoral head prepared by the method has excellent drug loading capacity, slow release performance, stability and mechanical property, and has good bone regeneration induction and repair effects, and the specific process steps for preparing the femoral head are as follows:
(a) performing three-dimensional scanning on the hip joint and the damaged part of the hip joint by CT scanning equipment to obtain image data, and redesigning the size and the shape of the femoral head of the hip joint which can be transplanted by using three-dimensional software according to the damaged femoral head of the hip joint;
(b) preparing a metal nano composite material: taking Ti powder (with the purity of 99.9%), Mg particles (with the purity of 99.8%), Si particles (with the purity of 99.8%), Ca particles and Mo powder according to the molar weight ratio of (30-50): (15-25): (30-40): (10-20): (0.1-0.3) uniformly mixing, and then putting into a ball mill for processing to obtain ultrafine composite powder with the grain size of 80-100 nm;
(c) preparing a beta tricalcium phosphate-polypyrrole-biotin composite material: deionized water, sodium polyacrylate, beta tricalcium phosphate, hydroxymethyl propylene and cellulose are mixed according to the mass fraction ratio of (1-1.2): (0.8-1): (2-5): (1-1.5): (1.2-1.6), mixing and filling the materials into a closed container, adding equal volume of 0.1mol/L pyrrole and 0.2mol/L polyferric chloride, mixing and stirring for 35min, separating a polymer, washing the polymer by deionized water, drying a finished product, and putting the dried product into a ball mill for treatment to obtain the beta tricalcium phosphate-polypyrrole-biotin composite material with the grain size of 80-100 nm;
(d) placing biotin, icaritin, 1-hydroxybenzotriazole and 4-dimethylaminopyridine in equal amount in a polyamino acid solution, stirring at room temperature, cooling to 0 ℃, performing dehydration treatment, raising the temperature to 24-26 ℃, performing full reaction, washing with deionized water, suspending the compound in absolute ethyl alcohol, heating, filtering, washing with hot absolute ethyl alcohol for 2 times, and drying to obtain an icaritin-biotin compound; lactic acid-glycolic acid copolymer, polyamino acid, distilled water, icaritin-biotin compound (24.6-25.3): (24.8-25.4): (1.8-2.6): (4.8-5.3), performing ultrasonic treatment for 15 min, enabling the vibration frequency of a horn to be 40-100kHz, enabling the amplitude to be 30-100 mu m, slowly dropping 10g/L polyvinyl alcohol solution into the mixed solution for emulsification, performing ultrasonic treatment for 15 min to obtain icaritin-biotin/polylactic acid-glycolic acid copolymer multiple emulsion, finally performing high-speed 12000r/min centrifugation for 20min, filtering, washing with phosphate buffer solution for 2 times, performing centrifugation on the obtained suspension, taking out the precipitate, putting the precipitate into a freeze dryer for drying to obtain icaritin-biotin-polylactic acid microspheres, wherein the diameter of the microspheres is 2-20 mu m;
(e) preparing a silver-hydroxyapatite-polyamide 6 composite material: the HA/PA6 composite material is prepared by a complexing agent coordination dissolution method, firstly CaCl is put in a closed drying container2And C2H5OH is mixed and stirred for 10min at the molar ratio of 1:5, the temperature is set to be 68-72 ℃, the content of Hydroxyapatite (HA) is set to be 40 percent, the mixture is mixed with polyamide 6 (PA 6) and then is placed into the container to be stirred for 20min, HA/PA6 composite material is obtained, then the HA/PA6 composite material is carried with silver by adopting a plasma reduction method, the silver content is set to be 0.6 percent and is mixed with the HA/PA6 composite material, 5-20 percent of glass fiber is added to be mixed and stirred, finally, the finished product is dried and is placed into a ball mill to be processed, and the Ag/HA/PA6 composite material with the grain size of 80-100nm is obtained;
(f) introducing the simulated three-dimensional model into a 3D printer, printing a spheroid with the diameter of 2-2.2cm on an auxiliary support by adopting a Selective Laser Melting (SLM) material 1 as a femoral head 'kernel', setting the diameter of a nozzle to be 150nm in a way of 120-, setting the pore size at 650-55 mu m for 600-one, the porosity at 45-55%, designing the diameter of the strut at 1200 mu m for 1000-one, printing with the material 1 based on the material 2 by SLM technology to form a third layer with the thickness of 1-1.2cm, setting the diameter of the nozzle at 150-one for 120-one, setting the printing speed at 80-100mm/min, printing with a body-centered cubic porous structure, setting the pore size at 650 mu m for 600-one, the porosity at 45-55%, designing the diameter of the strut at 1200 mu m for 1000-one, adding an ultrasonic vibration amplitude-changing rod during the printing process, the vibration frequency at 80-100kHz, the amplitude at 20-150 mu m, and the distance between the tool head and the laser head axis at 40-50mm, thus completing the semi-finished product of the femoral head, taking the semi-finished product femoral head from the auxiliary support, placing the femoral head into a centrifuge tube, adding the suspension of the material 3 and 10% gelatin, centrifuging at low speed for 10min, freezing for 24 hr, and carrying out femoral head ball loading treatment;
(g) stress-relieving the treated femoral head, and treating Hydroxyapatite (HA), beta-tricalcium phosphate and CaB6The powders were mixed with an electronic balance at 47: 48: 5 weighing respectively, mixing the three powders, and grinding with ball mill to obtain HA powder with particle size of 30nm and purity of 99.9%, and CaB6The method comprises the following steps of mixing and stirring 45nm powder granularity, 30nm beta tricalcium phosphate powder granularity and 99.8% purity for 5min by using 0.1% isopropanol as a binder, preparing the mixed powder into paste with certain viscosity, coating the paste on the surface of femoral head, setting the thickness of a preset layer of powder to be 4-6mm, standing the paste for 24h at room temperature, drying the paste in a vacuum drying box for 2h, setting the temperature of the vacuum drying box to be 45 ℃, combining the femoral head and the paste by adopting a laser cladding method, setting the laser power P =1.2KW, the scanning speed V =15mm/s, the spot diameter to be 3.0mm, the lap joint rate to be 40%, setting the argon gas flow rate to be 10L/min, preparing a biological ceramic coating, and finally polishing the molded product to reduce the surface of the materialAnd (4) roughness.
2. The method for preparing the customizable and renewable porous nanomaterial 3D printed femoral head according to claim 1, wherein the natural transition of bone is designed during printing, and the 3D printed porous hip joint femoral head structure is closer to the natural bone structure of human body, has better fatigue resistance and excellent mechanical property, improves biocompatibility and increases the success rate of surgery.
3. The method for preparing the customizable and renewable porous nanomaterial 3D printed femoral head according to claim 1, characterized in that a unique innovation is provided in the design of printing components, the transition and printing of different formula materials are realized in the printing process, mesenchymal stem cells can be stimulated to complete bone repair as soon as possible, secondary operations are avoided, and bone regeneration is realized.
4. The method for preparing the customizable and renewable porous nanomaterial 3D printed femoral head according to claim 1, characterized in that the 3D printing of the renewable porous material is assisted by ultrasound, and the ultrasound-assisted vibration can greatly improve the accuracy of the porous shape and the uniformity of the grain structure, so that the printed self-growing porous coarse structure is beneficial to cell attachment and osteogenic regeneration, has better human affinity and effectively avoids stress shielding.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118403220A (en) * | 2024-07-04 | 2024-07-30 | 上海埃度医疗器械科技有限公司 | Composite material for promoting periosteum repair and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6423796A (en) * | 1995-08-29 | 1997-03-06 | Johnson & Johnson Professional, Inc. | Bone prosthesis with protected coating for penetrating bone intergrowth |
| US20140025181A1 (en) * | 2012-07-20 | 2014-01-23 | Tom Vanasse | Metallic structures having porous regions from imaged bone at pre-defined anatomic locations |
| CN104644289A (en) * | 2015-03-24 | 2015-05-27 | 国家康复辅具研究中心 | Method for preparing artificial bone prosthesis with dual gaps |
| CN104784760A (en) * | 2015-03-25 | 2015-07-22 | 华南协同创新研究院 | Low-elastic-modulus integrated titanium-based femoral handle and preparation method thereof |
| CN105105875A (en) * | 2015-08-04 | 2015-12-02 | 西安交通大学 | Biomimetic artificial hip joint with internal growth function |
| CN106420119A (en) * | 2016-11-29 | 2017-02-22 | 淮阴工学院 | Method for forming high-anti-bacterial-performance titanium-alloy artificial hip joint |
| CN107899083A (en) * | 2017-11-29 | 2018-04-13 | 南宁越洋科技有限公司 | Super abrasive, high tenacity, the preparation method of biologically active artificial hip joint |
| CN108014369A (en) * | 2018-01-24 | 2018-05-11 | 山东建筑大学 | A kind of preparation method of the compound bone material of renewable titanium-based |
| CN108478859A (en) * | 2018-03-06 | 2018-09-04 | 北京科技大学 | A kind of method that the cold printings of 3D prepare hydroxyapatite-biomedical alloy implant |
| CN109316265A (en) * | 2018-11-15 | 2019-02-12 | 西安迈瑞克增材技术有限公司 | A kind of biodegradable neck Invasive lumbar fusion device and preparation method thereof |
| CN109330744A (en) * | 2018-09-27 | 2019-02-15 | 山东建筑大学 | A kind of degradable multi-component multi-layer nano-complex 3D printing justice phalanges of customization |
| CN109771698A (en) * | 2019-03-25 | 2019-05-21 | 石永新 | A kind of bone bracket complex and preparation method thereof |
| CN110403736A (en) * | 2019-08-09 | 2019-11-05 | 常州市第二人民医院 | A kind of super porous titanium alloy of 3D printing facilitates bone surface method of modifying |
| CN111068110A (en) * | 2019-11-25 | 2020-04-28 | 中国科学院长春应用化学研究所 | 3D printing degradable composite stent, preparation method thereof and loading composite stent |
-
2021
- 2021-01-25 CN CN202110096697.7A patent/CN112704582B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6423796A (en) * | 1995-08-29 | 1997-03-06 | Johnson & Johnson Professional, Inc. | Bone prosthesis with protected coating for penetrating bone intergrowth |
| US20140025181A1 (en) * | 2012-07-20 | 2014-01-23 | Tom Vanasse | Metallic structures having porous regions from imaged bone at pre-defined anatomic locations |
| CN104644289A (en) * | 2015-03-24 | 2015-05-27 | 国家康复辅具研究中心 | Method for preparing artificial bone prosthesis with dual gaps |
| CN104784760A (en) * | 2015-03-25 | 2015-07-22 | 华南协同创新研究院 | Low-elastic-modulus integrated titanium-based femoral handle and preparation method thereof |
| CN105105875A (en) * | 2015-08-04 | 2015-12-02 | 西安交通大学 | Biomimetic artificial hip joint with internal growth function |
| CN106420119A (en) * | 2016-11-29 | 2017-02-22 | 淮阴工学院 | Method for forming high-anti-bacterial-performance titanium-alloy artificial hip joint |
| CN107899083A (en) * | 2017-11-29 | 2018-04-13 | 南宁越洋科技有限公司 | Super abrasive, high tenacity, the preparation method of biologically active artificial hip joint |
| CN108014369A (en) * | 2018-01-24 | 2018-05-11 | 山东建筑大学 | A kind of preparation method of the compound bone material of renewable titanium-based |
| CN108478859A (en) * | 2018-03-06 | 2018-09-04 | 北京科技大学 | A kind of method that the cold printings of 3D prepare hydroxyapatite-biomedical alloy implant |
| CN109330744A (en) * | 2018-09-27 | 2019-02-15 | 山东建筑大学 | A kind of degradable multi-component multi-layer nano-complex 3D printing justice phalanges of customization |
| CN109316265A (en) * | 2018-11-15 | 2019-02-12 | 西安迈瑞克增材技术有限公司 | A kind of biodegradable neck Invasive lumbar fusion device and preparation method thereof |
| CN109771698A (en) * | 2019-03-25 | 2019-05-21 | 石永新 | A kind of bone bracket complex and preparation method thereof |
| CN110403736A (en) * | 2019-08-09 | 2019-11-05 | 常州市第二人民医院 | A kind of super porous titanium alloy of 3D printing facilitates bone surface method of modifying |
| CN111068110A (en) * | 2019-11-25 | 2020-04-28 | 中国科学院长春应用化学研究所 | 3D printing degradable composite stent, preparation method thereof and loading composite stent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118403220A (en) * | 2024-07-04 | 2024-07-30 | 上海埃度医疗器械科技有限公司 | Composite material for promoting periosteum repair and preparation method thereof |
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