CN113288527A - Ultrasonic-assisted 3D printing medical porous reproducible stemless shoulder joint humeral head with cage - Google Patents

Ultrasonic-assisted 3D printing medical porous reproducible stemless shoulder joint humeral head with cage Download PDF

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CN113288527A
CN113288527A CN202110600133.2A CN202110600133A CN113288527A CN 113288527 A CN113288527 A CN 113288527A CN 202110600133 A CN202110600133 A CN 202110600133A CN 113288527 A CN113288527 A CN 113288527A
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cage
humeral head
ultrasonic
nano
porous
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薛现猛
徐淑波
赵晨浩
张森
倪菲
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Shandong Jianzhu University
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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
    • A61F2/40—Joints for shoulders
    • A61F2/4014—Humeral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic humeral shafts
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • 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]

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  • Manufacturing & Machinery (AREA)
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  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • Prostheses (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention relates to a customized medical porous reproducible stemless shoulder joint humeral head implantable prosthesis with a cage. The invention uses CT to scan the shoulder joint of a patient to obtain the CT tomographic image data of the humerus, and establishes a three-dimensional model according with the scapula-free cage and the humeral head of the shoulder joint according to the CT tomographic image data; under the condition of controlling the grain size with the assistance of ultrasonic equipment, mixing and mixing a plurality of types of medical nano-metals to be used as a base material of the handle-free cage, and printing the porous handle-free cage layer by layer; printing high-strength biological ceramic humeral head with various medical nano biological ceramic powder; and then carrying out electron beam irradiation treatment and adding a strontium-loaded micro-nano coating to finally obtain a finished product. The invention adopts the design of innovative combination of 3D porous material and bone cage technology, thereby realizing the infiltration growth of bone, not needing backbone, being more convenient to implant, avoiding the relevant complications of the humerus component handle in the revision surgery needing to remove the humerus component handle, and improving the success rate of the surgery; the humeral head obtained by the method also has higher strength, corrosion resistance and biocompatibility.

Description

Ultrasonic-assisted 3D printing medical porous reproducible stemless shoulder joint humeral head with cage
Technical Field
The invention relates to an implantable bone-protecting prosthesis, in particular to a medical porous reproducible stemless shoulder joint humerus head with a cage, which has human body affinity and mechanical properties close to those of human bones and is prepared by ultrasonic assistance and customization and is applied to the field of medical implantation.
Background
The replacement of the artificial shoulder joint prosthesis is widely adopted clinically. The existing shoulder joint prosthesis is mostly composed of a humerus head and a humerus handle, the structure design is various, in order to increase the connection stability of the structure, the individual design is particularly complex, the number of components is more, and the high-efficiency operation of the replacement operation is not facilitated. Meanwhile, the shoulder joint prosthesis designed in the prior art has the common problems that the fixation effect is poor after replacement, the shoulder joint prosthesis is loosened and falls off, the service life of the shoulder joint prosthesis is shortened and the like due to the defects of low connection stability with human biological tissues, poor biocompatibility and the like.
The invention provides a preparation method for rapidly preparing a medical porous renewable scapular humeral head without a handle, which has good biological activity, strong corrosion resistance and mechanical property close to that of a human bone, by using an ultrasonic-assisted 3D printing technology. The stemless cage and the humeral head are respectively prepared from two different materials, namely a nano metal material and a biological ceramic material, so that the stress barrier effect is reduced, the stemless cage and the humeral head have excellent mechanical properties of metal and good tissue repair capability of porous ceramic, and can meet the requirements of surgical implantation of a prosthesis, so that the stemless cage and the humeral head are more stable, more durable and more durable.
The porous structure is designed to simulate the wound surface property of cancellous bone, so that the infiltration and growth of bone is realized, a backbone is not needed, the implantation is more convenient, and the operation time and the blood loss are reduced; the porous reproducible stemless shoulder joint humerus head with the cage can keep the backbone of a proximal humerus and avoid complications related to the humerus assembly handle in a revision surgery needing to remove the humerus assembly handle; the medullary cavity does not need to be ground, so that the medullary cavity deformed or closed patient is also suitable for the patient, the operation is simplified, the operation time is reduced, the blood loss is less, the bone retention is more and less, and the risk of fracture in the operation and around the prosthesis after the operation is reduced.
The electron beam irradiation treatment 3D printing prepares the surface with a micron and nanometer multistage micropore composite structure, can stimulate the reaction activity of surrounding tissues, has good adhesion and extension of osteoblasts, has better human affinity, effectively avoids stress shielding, is beneficial to combination with bone tissues and shortens the healing time; the strontium-doped nano hydroxyapatite coating can be successfully constructed on the surface by a magnetron sputtering method, and the strontium-doped nano hydroxyapatite coating prepared by magnetron sputtering can realize the sustained and slow release of strontium; is beneficial to improving osteogenic differentiation activity, strengthening intercellular connection and further improving the in vitro biological activity of osteoblasts.
Disclosure of Invention
The invention aims to provide a medical porous renewable scapular humeral head without a handle, which has good biological activity, strong corrosion resistance and mechanical property close to human bone, aiming at various complications caused by a shoulder scapular humeral stem currently used in the medical field and aiming at reducing mismatching between an implant and peripheral bone tissues and realizing efficient performance of an artificial shoulder scapular humeral replacement operation.
The technical scheme of the invention is as follows: CT is used for scanning shoulder joints of patients to obtain CT tomographic image data of humerus heads, a humerus three-dimensional model conforming to the shoulder joints is established according to the CT tomographic image data and is led into a 3D printer, and medical nano titanium magnesium composite material powder mixed in different proportions is printed into the humerus heads layer by the 3D printer under the auxiliary control of ultrasonic equipment. Then the humeral head is subjected to electron beam irradiation treatment and a strontium-loaded micro-nano coating is prepared by a magnetron sputtering technology. The specific scheme is as follows:
1. building a three-dimensional model
Firstly, scanning the bone tissue structure of a part of a human body needing bone replacement through CT scanning equipment, obtaining the size and the shape of a humerus head by utilizing three-dimensional reconstruction software, then obtaining the size and the dimension of a handle-free cage through three-dimensional design software, and establishing a three-dimensional structure data model of the bone tissue structure of the part.
2. Preparation of a Nanometered Metal powder
Metal Ti powder, Mg particles, Si particles, Ca particles, Cu particles and Ag particles are mixed according to the molar weight ratio: (25-50): (15-30): (20-40): (5-10): (3-6): (5-10) after uniformly mixing and preparing, carrying out high-energy ball milling treatment on the mixture to ensure that the maximum ball diameter is not more than 100nm, thus obtaining the ultrafine powder. And (3) carrying out irradiation preheating on the powder, continuously stirring the mixed material within 30 minutes, heating the raw material to 150 ℃ at a constant speed, and preserving heat for later use. Magnetic stirring is adopted in the stirring operation, and a preheating heat source is a radiation heat source.
3. Preparation of bioceramic mixed powder
Zirconium oxide, silicon dioxide, diatom ooze, montmorillonite, titanium oxide, graphite and hydroxylamine hydrochloride are mixed according to the weight ratio of (6-10): (5-8): (2-3): (2-6): (2-5): (2-4): (1-3) adding the mixture into a high-speed ball mill, carrying out high-energy ball milling treatment to ensure that the maximum ball diameter of the mixture is not more than 100nm, and sieving and sorting the obtained powder mixture for later use. Adding the obtained sieved powder into a vacuum reaction kettle, adding magnesium sulfate, polyphenylene sulfide, epoxidized soybean oil, an initiator and an auxiliary agent according to the weight ratio (1-3): (3-7): (4-8): (2-5): (2-5), heating to 70-75 ℃, introducing nitrogen to remove oxygen, then raising the temperature to 80-85 ℃ again, continuously preserving the heat for reaction for 6-10 h, returning the air pressure in the furnace to normal pressure after the reaction is finished, cooling the reactant for later use, keeping the nitrogen pressure at 5Mpa, taking lauroyl peroxide as an initiator and zinc stearate as an auxiliary agent; adding the reactant into a vacuum suction filter, washing with sterile water for 3 times, and drying the suction-filtered product in a vacuum drying oven at 65 ℃ for 30-60 min; vacuum filtration pressure 5X 10-8Mpa; adding the dried substance and a dispersing agent into an ultrasonic oscillator, and performing ultrasonic dispersion with ultrasonic oscillation power of 500W and ultrasonic time of 80min, wherein the dispersing agent is sodium pyrophosphate; injecting the ultrasonic dispersion product into a freezing spray dryer, powdering the material, and drying to obtain the nano biological ceramic mixed powder, wherein the freezing spray drying parameter is coldFreezing at-25 deg.C, cold trap at-80 deg.C, and spraying under 0.5 Mpa;
4. machining forming method for 3D printing of nano porous handle-free cage
And adding the prepared nano mixed powder into a laser 3D printing system, and processing the mixed material into a nano porous handle-free cage respectively by the laser 3D printing system according to a three-dimensional structural data model of the size and dimension of the handle-free cage obtained by three-dimensional design software. The porosity of the 3D printed hole model is ensured to be 50% -80%, and the hole diameter is 100-600 um.
5. Ultrasound device assisted control
An external magnetic field and ultrasonic impact auxiliary equipment are applied to the 3D printing device, grains are refined through the interaction of the electromagnetic field and the ultrasonic impact, and the comprehensive mechanical property of the skeleton is improved.
Laser power when laser 3D printing system moves is 300W, and scanning speed is 1500mm/s, and the scanning interval is 50um, and the laser facula is 60 um. The ultrasonic impacting device impacts the formed layer for 2-3min at an impacting speed of 0.1-0.3 m/min. The external magnetic field is electrified through the exciting coil to generate an alternating magnetic field on the sample, the maximum current applied by the electronic voltage regulator is 20A, and the generated large alternating magnetic field is 66.1 mT.
Sequentially ultrasonically cleaning the nano porous handle-free cage for 20min by using an acetone solution, absolute ethyl alcohol and deionized water, and then drying.
6. 3D printing biological ceramic humerus head processing and forming method
Adding the prepared nano biological ceramic mixed powder into a laser 3D printing system, and processing and forming the mixed material by the laser 3D printing system according to a three-dimensional structure data model of the size and the shape of the humeral head obtained by three-dimensional reconstruction software to obtain the ceramic humeral head.
Ultrasonic impact auxiliary equipment is applied to the 3D printing device, crystal grains are refined under the action of ultrasonic impact, and comprehensive mechanical properties of bones are improved.
Laser power when laser 3D printing system moves is 300W, and scanning speed is 1500mm/s, and the scanning interval is 60um, and the laser facula is 80 um. The ultrasonic impacting device impacts the formed layer for 2-3min at an impacting speed of 0.1-0.3 m/min.
7. Electron beam irradiation treatment
A Nadezhda-2 type high-current pulse electron beam system is used for processing the porous stemless cage and the humeral head, so that a large number of micron-sized and submicron-sized holes with the size of 0.5-5 mu m are generated on the surface on the basis of the original recess. The main parameter ranges are that the accelerating voltage is 25keV, the pulse width is 2.5 mu m, the pulse interval is 10s, the target pole distance is 80mm, the pulse frequency is 15 times, the surface with the micron and nanometer multistage micropore composite structure is prepared, the reaction activity of surrounding tissues can be stimulated, and the osteoblasts are well adhered and stretched.
Placing the skeleton in a mixed solution of 3% calcium chloride, 10% hydrochloric acid, 60% sulfuric acid and water (balance), treating for 2min at 130 deg.C to form smaller nanometer holes on the inner wall and ridge of the existing hole, taking out the sample, ultrasonic cleaning in deionized water, and oven drying.
8 magnetron sputtering technology for preparing strontium-doped nano hydroxyapatite coating
Mixing anhydrous trisodium phosphate (Na)3PO3) Calcium nitrate (Ca (NO)3）2·4H2O), strontium nitrate (Sr (NO)3)2) Dissolving the mixture in deionized water, stirring the mixture until the mixture is fully dissolved, and preparing a sodium phosphate solution, a calcium nitrate solution and a strontium nitrate solution respectively. According to the ratio of strontium: uniformly mixing calcium nitrate and strontium nitrate solutions with a calcium atomic ratio of 0.5:9.5 respectively, then dropwise adding the mixed solution into a sodium phosphate solution according to a molar ratio of 10:6, stirring for 20min, placing the mixed solution in an environment of 150 ℃ for reaction for 5 h, stopping the reaction, washing with deionized water and absolute ethyl alcohol for several times, performing suction filtration to obtain white precipitates, drying at a constant temperature of 50 ℃ for 24 h, grinding to obtain strontium-doped nano-hydroxyapatite with the strontium content of 5%, preparing a target material with the thickness of 75mm by adopting the cold pressing pressure of 20MPa, baking at the temperature of 1100 ℃ under high vacuum for 2h, and cooling for later use.
The target material of hot ground 75mm is loaded into a vacuum chamber, the target base distance is adjusted to 50mm, and the substrate is not heated. Vacuum pumping is carried out to 10-4 And Pa, filling Ar, adjusting the air pressure to 2.0Pa, adjusting the power to 200W, rotating the sample disc for 10r/min, starting glow and stabilizing, adjusting the air pressure to about 0.5Pa, and sputtering for 8 h. Sputtering, placing in a tube heating furnace, and heating at room temperature at 5 deg.C/minHeating to 400 ℃, annealing, keeping the temperature for 4 hours, and cooling to room temperature along with the furnace to finally obtain a finished product.
The positive progress effects of the invention are as follows:
1. the 3D printing of the porous handle-free shoulder joint humerus head structure with the cage is closer to the natural skeleton of a human body, the size of crystal grains is controlled with the assistance of ultrasonic equipment, the comprehensive mechanical property of the skeleton is improved, the complexity of the operation is simplified, and the success rate of the operation is improved.
2. The porous reproducible stemless shoulder joint humerus head with the cage can keep the backbone of a proximal humerus and avoid complications related to the humerus assembly handle in a revision surgery needing to remove the humerus assembly handle; simplifies the operation, reduces the operation time, reduces the blood loss, and has more and lower bone retention and risk of peri-prosthetic fractures during and after the operation.
3. This patent is the innovation of 3D porous material and bone cage technique combines, and porous structure is designed into the surface of a wound nature of simulation cancellous bone, realizes the infiltration growth of sclerotin, does not need diaphysis moreover, and it is more convenient to implant, has reduced operation time and blood loss.
4. The stemless cage and the humeral head are respectively prepared from two different materials, namely a nano metal material and a biological ceramic material, so that the stress barrier effect is reduced, the stemless cage and the humeral head have excellent mechanical properties of metal and good tissue repair capability of porous ceramic, and can meet the requirements of surgical implantation of a prosthesis, so that the stemless cage and the humeral head are more stable, more durable and more durable.
5. The electron beam irradiation treatment 3D printing prepares the surface with the micron and nanometer multistage micropore composite structure, can stimulate the reaction activity of surrounding tissues, has good adhesion and extension of osteoblasts, has better human affinity, effectively avoids stress shielding, is beneficial to combination with bone tissues and shortens the healing time.
6. The strontium-doped nano hydroxyapatite coating can be successfully constructed on the surface by a magnetron sputtering method, and the strontium-doped nano hydroxyapatite coating prepared by magnetron sputtering can realize the sustained and slow release of strontium; is beneficial to improving osteogenic differentiation activity, strengthening intercellular connection and further improving the in vitro biological activity of osteoblasts.
Drawings
Fig. 1 is a schematic structural diagram of components of a medical porous reproducible stemless shoulder humeral head with a cage, wherein 1 is a matrix prepared by 3D printing of a porous humeral head from biological ceramic powder; 2 is a strengthening layer treated by electron beam irradiation; 3, preparing the strontium-doped nano hydroxyapatite coating by magnetron sputtering technology.
Fig. 2 is a schematic structural diagram of a medical porous renewable stemless shoulder joint humerus, in which fig. 1 is a porous cage structure printed with nano metal powder; 2 preparing the porous humeral head by using the biological ceramic powder.
Fig. 3 is a cross-sectional view of a medical porous, regenerative stemless shoulder joint humeral structure.
Detailed Description
The first step is as follows: building a three-dimensional model
Firstly, scanning the bone tissue structure of a part of a human body needing bone replacement through CT scanning equipment, obtaining the size and the shape of a humerus head by utilizing three-dimensional reconstruction software, then obtaining the size and the dimension of a handle-free cage through three-dimensional design software, and establishing a three-dimensional structure data model of the bone tissue structure of the part.
The second step is that: preparation of a Nanometered Metal powder
Metal Ti powder, Mg particles, Si particles, Ca particles, Cu particles and Ag particles are mixed according to the molar weight ratio: (25-50): (15-30): (20-40): (5-10): (3-6): (5-10) after uniformly mixing and preparing, carrying out high-energy ball milling treatment on the mixture to ensure that the maximum ball diameter is not more than 100nm, thus obtaining the ultrafine powder. And (3) carrying out irradiation preheating on the powder, continuously stirring the mixed material within 30 minutes, heating the raw material to 150 ℃ at a constant speed, and preserving heat for later use. Magnetic stirring is adopted in the stirring operation, and a preheating heat source is a radiation heat source.
The third step: preparation of bioceramic mixed powder
Zirconium oxide, silicon dioxide, diatom ooze, montmorillonite, titanium oxide, graphite and hydroxylamine hydrochloride are mixed according to the weight ratio of (6-10): (5-8): (2-3): (2-6): (2-5): (2-4): (1-3) adding highAnd (3) carrying out high-energy ball milling treatment in a speed ball mill to ensure that the maximum ball diameter of the high-energy ball mill is not more than 100nm, and sieving and sorting the obtained powder mixture for later use. Adding the obtained sieved powder into a vacuum reaction kettle, adding magnesium sulfate, polyphenylene sulfide, epoxidized soybean oil, an initiator and an auxiliary agent according to the weight ratio (1-3): (3-7): (4-8): (2-5): (2-5), heating to 70 ℃, introducing nitrogen to remove oxygen, then raising the temperature to 80 ℃ again, continuously preserving the heat for reaction for 8 hours, returning the air pressure in the furnace to normal pressure after the reaction is finished, cooling the reactant for later use, wherein the nitrogen pressure is 5Mpa, the initiator is lauroyl peroxide, and the auxiliary agent is zinc stearate; adding the reactant into a vacuum suction filter, washing with sterile water for 3 times, and drying the suction-filtered product in a vacuum drying oven at 65 ℃ for 40 min; vacuum filtration pressure 5X 10-8Mpa; adding the dried substance and a dispersing agent into an ultrasonic oscillator, and performing ultrasonic dispersion with ultrasonic oscillation power of 500W and ultrasonic time of 80min, wherein the dispersing agent is sodium pyrophosphate; injecting the ultrasonic dispersion product into a freezing spray dryer, and powdering and drying the material to obtain nano biological ceramic mixed powder, wherein the freezing spray drying parameters are that the freezing temperature is-25 ℃, the cold trap temperature is-75 ℃, and the spray pressure is 0.5 Mpa;
the fourth step: machining forming method for 3D printing of nano porous handle-free cage
And adding the prepared nano mixed powder into a laser 3D printing system, and processing the mixed material into a nano porous handle-free cage respectively by the laser 3D printing system according to a three-dimensional structural data model of the size and dimension of the handle-free cage obtained by three-dimensional design software. The porosity of the 3D printed hole model is ensured to be 50% -80%, and the hole diameter is 100-600 um.
The fifth step: ultrasound-assisted device control
An external magnetic field and ultrasonic impact auxiliary equipment are applied to the 3D printing device, grains are refined through the interaction of the electromagnetic field and the ultrasonic impact, and the comprehensive mechanical property of the skeleton is improved.
Laser power when laser 3D printing system moves is 300W, and scanning speed is 1500mm/s, and the scanning interval is 50um, and the laser facula is 60 um. The ultrasonic impacting device impacts the forming layer for 2min at an impacting speed of 0.2 m/min. The external magnetic field is electrified through the exciting coil to generate an alternating magnetic field on the sample, the maximum current applied by the electronic voltage regulator is 20A, and the generated large alternating magnetic field is 66.1 mT.
Sequentially ultrasonically cleaning the nano porous handle-free cage for 20min by using an acetone solution, absolute ethyl alcohol and deionized water, and then drying.
And a sixth step: 3D printing biological ceramic humerus head processing and forming method
Adding the prepared nano biological ceramic mixed powder into a laser 3D printing system, and processing and forming the mixed material by the laser 3D printing system according to a three-dimensional structure data model of the size and the shape of the humeral head obtained by three-dimensional reconstruction software to obtain the ceramic humeral head.
Ultrasonic impact auxiliary equipment is applied to the 3D printing device, crystal grains are refined under the action of ultrasonic impact, and comprehensive mechanical properties of bones are improved.
Laser power when laser 3D printing system moves is 300W, and scanning speed is 1500mm/s, and the scanning interval is 60um, and the laser facula is 80 um. The ultrasonic impacting device impacts the forming layer for 2min at an impacting speed of 0.2 m/min.
The seventh step: electron beam irradiation treatment
A Nadezhda-2 type high-current pulse electron beam system is used for processing the porous stemless cage and the humeral head, so that a large number of micron-sized and submicron-sized holes with the size of 0.5-5 mu m are generated on the surface on the basis of the original recess. The main parameter ranges are that the accelerating voltage is 25keV, the pulse width is 2.5 mu m, the pulse interval is 10s, the target pole distance is 80mm, the pulse frequency is 15 times, the surface with the micron and nanometer multistage micropore composite structure is prepared, the reaction activity of surrounding tissues can be stimulated, and the osteoblasts are well adhered and stretched.
Placing the skeleton in a mixed solution of 3% calcium chloride, 10% hydrochloric acid, 60% sulfuric acid and water (balance), treating for 2min at 130 deg.C to form smaller nanometer holes on the inner wall and ridge of the existing hole, taking out the sample, ultrasonic cleaning in deionized water, and oven drying.
Eighth step: preparation of strontium-doped nano hydroxyapatite coating by magnetron sputtering technology
Mixing anhydrous trisodium phosphate (Na)3PO3) Calcium nitrate (Ca (NO)3）2·4H2O), strontium nitrate (Sr (NO)3)2) Dissolving the mixture in deionized water, stirring the mixture until the mixture is fully dissolved, and preparing a sodium phosphate solution, a calcium nitrate solution and a strontium nitrate solution respectively. According to the ratio of strontium: uniformly mixing calcium nitrate and strontium nitrate solutions with a calcium atomic ratio of 0.5:9.5 respectively, then dropwise adding the mixed solution into a sodium phosphate solution according to a molar ratio of 10:6, stirring for 20min, placing the mixed solution in an environment of 150 ℃ for reaction for 5 h, stopping the reaction, washing with deionized water and absolute ethyl alcohol for several times, performing suction filtration to obtain white precipitates, drying at a constant temperature of 50 ℃ for 24 h, grinding to obtain strontium-doped nano-hydroxyapatite with the strontium content of 5%, preparing a target material with the thickness of 75mm by adopting the cold pressing pressure of 20MPa, baking at the temperature of 1100 ℃ under high vacuum for 2h, and cooling for later use.
The target material of hot ground 75mm is loaded into a vacuum chamber, the target base distance is adjusted to 50mm, and the substrate is not heated. Vacuum pumping is carried out to 10-4And Pa, filling Ar, adjusting the air pressure to 2.0Pa, adjusting the power to 200W, rotating the sample disc for 10r/min, starting glow and stabilizing, adjusting the air pressure to about 0.5Pa, and sputtering for 8 h. After sputtering, the mixture is put in a tubular heating furnace, the temperature is raised to 400 ℃ from room temperature at the rate of 5 ℃/min for annealing treatment, the temperature is kept for 4h, and the mixture is cooled to room temperature along with the furnace, and finally a finished product is obtained.

Claims (5)

1. Customizing an implantable prosthesis of a medical porous renewable scapular-free shoulder humeral head, which is characterized in that: CT scanning the shoulder joint of a patient to obtain CT tomographic image data of the humerus, and establishing a three-dimensional model according with the shoulder joint stemless cage and the humeral head according to the CT tomographic image data; mixing various medical nano metals to serve as a base material of the handle-free cage, and printing the porous handle-free cage layer by layer; printing high-strength biological ceramic humeral head with various medical nano biological ceramic powder; and then carrying out electron beam irradiation treatment and adding a strontium-loaded micro-nano coating to finally obtain a finished product, wherein the specific process scheme is as follows:
(1) establishing a three-dimensional model: firstly, scanning a bone tissue structure of a part of a human body needing bone replacement through CT scanning equipment, obtaining the size and the shape of a humerus head by utilizing three-dimensional reconstruction software, then obtaining the size and the dimension of a handle-free cage through three-dimensional design software, and establishing a three-dimensional structure data model of the bone tissue structure of the part;
(2) preparation of the nanometal metal powder: metal Ti powder, Mg particles, Si particles, Ca particles, Cu particles and Ag particles are mixed according to the molar weight ratio: (25-50): (15-30): (20-40): (5-10): (3-6): (5-10) after uniformly mixing and preparing, carrying out high-energy ball milling treatment on the mixture to ensure that the maximum ball diameter of the mixture is not more than 100nm to obtain superfine powder; carrying out irradiation preheating on the powder, continuously stirring the mixed material within 30 minutes, simultaneously heating the raw material to 150 ℃ at a constant speed, and keeping the temperature for later use; magnetic stirring is adopted in the stirring operation, and a preheating heat source is a radiation heat source;
(3) preparing the mixed bioceramic powder: zirconium oxide, silicon dioxide, diatom ooze, montmorillonite, titanium oxide, graphite and hydroxylamine hydrochloride are mixed according to the weight ratio of (6-10): (5-8): (2-3): (2-6): (2-5): (2-4): (1-3) adding the mixture into a high-speed ball mill, performing high-energy ball milling treatment to ensure that the maximum ball diameter of the mixture is not more than 100nm, and sieving and sorting the obtained powder mixture for later use; adding the obtained sieved powder into a vacuum reaction kettle, adding magnesium sulfate, polyphenylene sulfide, epoxidized soybean oil, an initiator and an auxiliary agent according to the weight ratio (1-3): (3-7): (4-8): (2-5): (2-5), heating to 70-75 ℃, introducing nitrogen to remove oxygen, then raising the temperature to 80-85 ℃ again, continuously keeping the temperature for reaction for 6-10 h, returning the air pressure in the furnace to normal pressure after the reaction is finished, and cooling the reactant for later use; adding the reactant into a vacuum suction filter, washing with sterile water for 3 times, and drying the suction-filtered product in a vacuum drying oven at 65 ℃ for 30-60 min; adding the dried substance and a dispersing agent into an ultrasonic oscillator, and performing ultrasonic dispersion with ultrasonic oscillation power of 500W and ultrasonic time of 80 min; injecting the ultrasonic dispersion product into a freezing spray dryer, and powdering and drying the material to obtain nano biological ceramic mixed powder;
(4) 3D printing of the nano porous handle-free cage: adding the prepared nano mixed powder into a laser 3D printing system, and respectively processing the mixed materials into a nano porous handle-free cage by the laser 3D printing system according to a three-dimensional structural data model of the size and dimension of the handle-free cage obtained by three-dimensional design software; ensuring that the porosity of the 3D printed hole model is 50-80% and the pore diameter is 100-600 um; sequentially ultrasonically cleaning the nano porous handle-free cage for 20min by using an acetone solution, absolute ethyl alcohol and deionized water, and then drying;
(5) 3D printing biological ceramic humeral head processing and forming: adding the prepared nano biological ceramic mixed powder into a laser 3D printing system, and processing and forming the mixed material by the laser 3D printing system according to a three-dimensional structure data model of the size and the shape of the humeral head obtained by three-dimensional reconstruction software to obtain a ceramic humeral head;
(6) electron beam irradiation treatment: treating the porous stemless cage and the humeral head by using a Nadezhda-2 type high-current pulse electron beam system to enable the surface to generate a large number of micron and submicron-level holes with the size of 0.5-5 mu m on the basis of the original recess; placing the skeleton in a mixed solution of 3% calcium chloride, 10% hydrochloric acid, 60% sulfuric acid and water (balance), treating for 2min at 130 deg.C to form smaller nanometer holes on the inner wall and ridge of the existing hole, taking out the sample, ultrasonic cleaning in deionized water, and oven drying;
(7) preparing a strontium-doped nano hydroxyapatite coating by a magnetron sputtering technology: mixing anhydrous trisodium phosphate (Na)3PO3) Calcium nitrate (Ca (NO)3） 2·4H2O), strontium nitrate (Sr (NO)3)2) Dissolving the mixture in deionized water, stirring the mixture until the mixture is fully dissolved, and respectively preparing a sodium phosphate solution, a calcium nitrate solution and a strontium nitrate solution; according to the ratio of strontium: uniformly mixing calcium nitrate and strontium nitrate solutions with a calcium atomic ratio of 0.5:9.5 respectively, then dropwise adding the mixed solution into a sodium phosphate solution according to a molar ratio of 10:6, stirring for 20min, placing the mixed solution in an environment of 150 ℃ for reaction for 5 h, stopping the reaction, washing with deionized water and absolute ethyl alcohol for several times, performing suction filtration to obtain white precipitate, drying at a constant temperature of 50 ℃ for 24 h, grinding to obtain strontium-doped nano-hydroxyapatite with the strontium content of 5%, preparing a target material with the thickness of 75mm by adopting the cold pressing pressure of 20MPa, baking at the temperature of 1100 ℃ under high vacuum for 2h, and cooling for later use; loading 75mm of target material into a vacuum chamber, adjusting the target base distance to 50mm, and not heating the substrate; is vacuumized to 10-4Pa, filling Ar, adjusting the air pressure to 2.0Pa, adjusting the power to 200W, rotating the sample disc for 10r/min, starting glow and stabilizing, adjusting the air pressure to about 0.5Pa, and sputtering for 8 h; after sputtering, the mixture is heated to 400 ℃ from room temperature at the speed of 5 ℃/min in a tubular heating furnace for annealing treatment, the temperature is kept for 4h, and the mixture is cooled to room temperature along with the furnace, thus obtaining the finished product finally.
2. The method for preparing a custom medical porous renewable stemless shoulder humeral head with a cage according to claim 1, wherein: in the technical scheme (3), the pressure of nitrogen is 5Mpa, the initiator is lauroyl peroxide, the auxiliary agent is zinc stearate, and the vacuum filtration pressure is 5 multiplied by 10-8Mpa, dispersant is sodium pyrophosphate, freezing temperature is-25 deg.C, cold trap temperature is-75 deg.C, and spray pressure is 0.5 Mpa.
3. The method for preparing a custom medical porous renewable stemless shoulder humeral head with a cage according to claim 1, wherein: in the technical scheme (4), an external magnetic field and ultrasonic impact auxiliary equipment are applied to the 3D printing device, and grains are refined and the comprehensive mechanical property of the skeleton is improved through the interaction of the electromagnetic field and the ultrasonic impact; the laser power of the laser 3D printing system during operation is 300W, the scanning speed is 1500mm/s, the scanning interval is 50um, and the laser spot is 60 um; the ultrasonic impact device performs impact treatment on the forming layer for 2-3min at the impact speed of 0.1-0.3 m/min; the external magnetic field is electrified through the exciting coil to generate an alternating magnetic field on the sample, the maximum current applied by the electronic voltage regulator is 20A, and the generated large alternating magnetic field is 66.1 mT.
4. The method for preparing a custom medical porous renewable stemless shoulder humeral head with a cage according to claim 1, wherein: in the process scheme (5), ultrasonic impact auxiliary equipment is applied to the 3D printing device, crystal grains are refined under the action of ultrasonic impact, and the comprehensive mechanical property of the skeleton is improved; the laser power of the laser 3D printing system during operation is 300W, the scanning speed is 1500mm/s, the scanning interval is 60um, and the laser spot is 80 um; the ultrasonic impacting device impacts the forming layer for 2min at an impacting speed of 0.2 m/min.
5. The method for preparing a custom medical porous renewable stemless shoulder humeral head with a cage according to claim 1, wherein: the main parameter ranges in the process scheme (6) are that the accelerating voltage is 25keV, the pulse width is 2.5 mu m, the pulse interval is 10s, the target pole distance is 80mm, the pulse frequency is 15 times, the surface with the micron and nanometer multistage micropore composite structure is prepared, the reaction activity of surrounding tissues can be stimulated, and the adhesion and the extension of osteoblasts are good.
CN202110600133.2A 2021-05-31 2021-05-31 Ultrasonic-assisted 3D printing medical porous reproducible stemless shoulder joint humeral head with cage Withdrawn CN113288527A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114225114A (en) * 2021-12-22 2022-03-25 西南大学 High-strength flexible wear-resistant bionic composite joint material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114225114A (en) * 2021-12-22 2022-03-25 西南大学 High-strength flexible wear-resistant bionic composite joint material and preparation method thereof
CN114225114B (en) * 2021-12-22 2022-07-26 西南大学 High-strength flexible wear-resistant bionic composite joint material and preparation method thereof

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