CN111320847A - Preparation method of 3D printing medical composite bone plate - Google Patents

Preparation method of 3D printing medical composite bone plate Download PDF

Info

Publication number
CN111320847A
CN111320847A CN202010242218.3A CN202010242218A CN111320847A CN 111320847 A CN111320847 A CN 111320847A CN 202010242218 A CN202010242218 A CN 202010242218A CN 111320847 A CN111320847 A CN 111320847A
Authority
CN
China
Prior art keywords
bone plate
printing
hydroxyapatite
bone
polylactic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010242218.3A
Other languages
Chinese (zh)
Inventor
朱沛志
王刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou University
Original Assignee
Yangzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou University filed Critical Yangzhou University
Priority to CN202010242218.3A priority Critical patent/CN111320847A/en
Publication of CN111320847A publication Critical patent/CN111320847A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/028—Other inorganic materials not covered by A61L31/022 - A61L31/026
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Vascular Medicine (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention relates to a preparation method of a 3D printing medical composite bone plate in the technical field of composite materials. Uniformly mixing 5-30 parts by weight of hydroxyapatite powder and 70-95 parts by weight of polylactic acid granules, extruding and drawing the mixture into bone plate wires with uniform diameters by using an extruder, and preparing the required composite material bone plate from the uniform bone plate wires by using a 3D printer; the polylactic acid and hydroxyapatite composite material bone plate prepared by the method can be absorbed in vivo for bone repair, thereby being more beneficial to the growth of bones.

Description

Preparation method of 3D printing medical composite bone plate
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of a 3D printing medical composite material bone plate for bone repair.
Background
With the increase of population and aging, patients with bone defects caused by diseases, accidents and the like are increasing, and the clinical requirements of bone repair treatment are increasing year by year. In the orthopedic repair treatment operation, the damaged bone needs to be fixed by using an implantation instrument such as a bone fracture plate. Accordingly, the demand for bone fixation implant devices has also increased. From the perspective of clinical application and the healing mechanism of the affected part of the bone of a patient, it is required that the degradation rate of the bone fixation implant in vivo is adjustable, that is, at the initial stage when new bone is not generated after the operation is completed, the fixation device has mechanical strength matched with the bone to support and fix the damaged part. In the late postoperative period, after new bone formation to complete recovery, the bone fixation device is required to gradually degrade until it is completely resorbed. However, the existing bone fixation instruments cannot fundamentally solve the problem that the bone fixation instruments have unmatched mechanical properties and degradation rate with bone growth due to the controllability of the degradation rate in vivo.
Meanwhile, the difference of mechanical properties of the bone of a human body and a solid metal bone plate is very large, for example, for a mandible which is stressed frequently in a reciprocating mode, stress is concentrated on a bone nail when the mandible is stressed, so that the problem of stress shielding is caused, bone atrophy can be caused to cause the bone nail to fall off after a long time, and the minimally invasive bone fracture plate setting is a modern internal fixation technology for fracture.
In the prior art, a patent name of a 3D printing medical tibia fixing device and a manufacturing method thereof is disclosed, wherein in an invention patent with an application publication number of CN107397583A and an application publication date of 20171128, a titanium alloy is used as a printing material, the tibia fixing device is printed by using a 3D printing method, the elastic modulus (50 GPa-114 GPa) of the titanium alloy is far higher than that of normal bone (the cortical bone is about 15 GPa), and the tibia fixing device using the titanium alloy can generate stress shielding at a combination part to cause bone absorption and is not beneficial to the repair and growth of human bones.
Disclosure of Invention
The invention provides a preparation method of a 3D printing medical composite bone plate, aiming at the problems that the medical bone plate in the prior art is easy to generate stress shielding and is not beneficial to bone repair.
The invention aims to realize the preparation method of the 3D printing medical composite bone plate, which comprises the following specific steps: 5-30 parts by weight of hydroxyapatite powder and 70-95 parts by weight of polylactic acid granules are uniformly mixed, and then extruded and drawn into bone plate wires with uniform diameters by using an extruder, and the uniform bone plate wires are used for preparing the required composite bone plate by using a 3D printer.
In the method, Hydroxyapatite (HA) is the main inorganic component of human and animal skeletons, HAs good bioactivity and osteoconductivity, can guide the growth of bones, and forms firm osseous combination with bone tissues, but HAs poor mechanical property and can not be directly used as a bone plate supporting material, polylactic acid (PLA) HAs the mechanical comprehensive properties and biocompatibility of impact strength, better mechanical strength, hardness and the like, the invention utilizes the high-temperature melting of an extruder to interact hydroxyl of HA and a molecular chain of PLA to obtain a bone plate wire material (PLA/nHA composite material) through compounding, then utilizes a 3D printing technology to introduce a three-dimensional model according to the required bone plate shape and print the required composite material bone plate (PLA/nHA), the PLA/HA prepared by the invention can well organically combine the biodegradability and the bone inductivity of the bone plate, not only can improve the mechanical property of PLA material and make it meet the mechanical strength requirement of bone implantation substitute material, but also can improve the Ca content after HA is implanted into human body2+And P3+Can be dissociated from the surface of HA, so that HA can be absorbed by body tissue, and can grow new tissue more easily, and HA is alkaline and can neutralize acid generated by acidic degradation of polylactic acidAnd the pain of a patient is relieved, so that the PLA/nHA composite bone plate is a bone implantation substitute material with ideal bone combination capability and biocompatibility.
Further, the method specifically comprises the following steps:
1) preparing hydroxyapatite: preparing hydroxyapatite by coprecipitation of chloride and phosphate;
2) synthetic bone plate material: respectively crushing the hydroxyapatite and the polylactic acid prepared in the step 1), sieving and collecting to obtain hydroxyapatite powder and polylactic acid granules, uniformly mixing 5-30 parts by weight of the hydroxyapatite powder and 70-95 parts by weight of the polylactic acid granules, adding the mixture into an internal mixer for mixing, and then putting the mixture into an extruder for melt extrusion to obtain bone plate wires;
3) 3D printing bone plate: and (3) loading the bone plate wire prepared in the step 2) into a 3D printer, adjusting the printing parameters of the 3D printer, and starting printing after the three-dimensional model of the bone plate is imported to obtain the composite bone plate.
Further, the step 1) specifically comprises the following steps:
1.1) dissolving a proper amount of calcium salt in deionized water to prepare a calcium salt solution, and then dissolving a proper amount of phosphate in the deionized water to prepare a phosphate solution;
1.2) mixing a calcium salt solution and a phosphate solution under the condition of water bath at the temperature of 80-95 ℃ to ensure that the molar mass ratio of P to Ca is 1: 1.5-2, adding a sodium hydroxide solution to adjust the PH to 9-11, fully reacting for 4-10 h, standing and aging for 12-24 h, washing with deionized water, centrifuging, and drying to obtain the hydroxyapatite.
Further, in step 1.1), the calcium salt is calcium chloride or calcium sulfate, and the phosphate is one of sodium hydrogen phosphate, potassium phosphate or diammonium hydrogen phosphate.
Further, the polylactic acid is L-polylactic acid, and the weight average molecular weight is 10-20 ten thousand. In the invention, the polylactic acid has an excessively small weight average molecular weight, ester bonds of the polylactic acid are easy to break, so that the mechanical property of the PLA/nHA composite bone plate is weaker, and the treatment purpose cannot be achieved.
Further, in step 2), the diameter of the bone plate wire is in the range of 1.75mm ± 0.05 mm.
Further, in the step 2), the internal mixer is internally mixed for 10-30 min under the condition of 200-250 ℃, and the extruder is at a melting temperature of 200-230 ℃.
Further, in the step 3), the printing parameters are that the temperature of the spray head is 200-220 ℃, the temperature of the printing bottom plate is 20-40 ℃, the printing speed is 5-10 mm/s, and the rotating speed of the cooling fan is 2000 rpm.
Drawings
Fig. 1 is a sample view of a composite bone plate prepared in example 1.
Fig. 2 is a sample view of the composite bone plate prepared in examples 2 and 3.
Fig. 3 is an X-ray image of a 3D-printed bone plate transplanted rabbit at A, B, C weeks 4, 8, and 12 respectively.
Fig. 4 is a mirco-CT image of 3D printed bone plate transplanted rabbits at 4, 8, and 12 weeks A, B, C, respectively.
FIG. 5 is a graph of the number of new bone formation rates of mirco-CT in 3D-printed bone plate-grafted rabbits.
Fig. 6 is a schematic diagram of a three-point bending tester used for testing the bending strength of the bone plate.
FIG. 7 is a comparison of the mechanical flexural strength tests of comparative example 1 and the same bone plate made in example 1.
FIG. 8 is a comparison of the mechanical flexural strength tests of comparative example 2 and the same bone plate made in example 1.
FIG. 9 is a comparison of the mechanical flexural strength test of comparative example 3 and the same bone plate made in example 1.
FIG. 10 is a comparison of the mechanical flexural strength test of comparative example 4 and the same bone plate made in example 1.
Detailed Description
Example 1 (PLA/nHA composite bone plate in 10%: 90% mass ratio)
Preparing hydroxyapatite by a coprecipitation method: 185.4 g of calcium chloride and 380 g of sodium phosphate dodecahydrate are dissolved in 1L of water, respectively. Adding sodium phosphate solution into calcium chloride solution under the conditions of water bath at 90 ℃ and stirring, adjusting the pH to 9 by using sodium hydroxide solution and hydrochloric acid, and continuously stirring for 4 hours. Standing and aging for 12 hours. And after aging, washing to remove a byproduct sodium chloride, and drying to obtain the nano-hydroxyapatite.
The hydroxyapatite and the high molecular plastic are crushed into 200-mesh fine powder. Mixing the components in a mass ratio of 10%: mixing 90% of hydroxyapatite fine powder with PLA granules, and adding into an internal mixer 200oC, mixing for 10 min. And putting the mixed materials into an extruder, drawing wires, controlling the melting temperature to be 200-230 ℃, and extruding and drawing wires to form uniform 3D printing consumables with the diameter range of about 1.75 mm.
The consumables are loaded into an FDM type 3D printer, and parameters are adjusted to enable the temperature of a printing nozzle to be controlled at 210 ℃ in the bone plate printing process; the temperature of the printing bottom plate is controlled to be 30 ℃; the printing speed is controlled to be 10 mm/s; the cooling fan speed was controlled at 2000rpm and printing was started after introducing the three-dimensional model of the bone plate, as shown in fig. 1, depending on the desired bone plate shape.
Example 2 (20% by weight: 80% PLA/nHA composite bone plate)
Preparing hydroxyapatite by a coprecipitation method: 92.7 g of calcium chloride and 190 g of sodium phosphate dodecahydrate were dissolved in 500mL of water, respectively. Adding sodium phosphate solution into calcium chloride solution under the conditions of water bath at 90 ℃ and stirring, adjusting the pH value to 10 by using sodium hydroxide solution and hydrochloric acid, and continuously stirring for 4 hours. Standing and aging for 12 hours. And after aging, washing to remove a byproduct sodium chloride, and drying to obtain the nano-hydroxyapatite.
The hydroxyapatite and the high molecular plastic are crushed into 200-mesh fine powder. Mixing the components in a mass ratio of 20%: 80% of hydroxyapatite fine powder and PLA granules are mixed and added into an internal mixer 200oC, mixing for 10 min. And putting the mixed materials into an extruder, drawing wires, controlling the melting temperature to be 200-230 ℃, and extruding and drawing wires to form uniform 3D printing consumables with the diameter range of about 1.75 mm.
The consumables are loaded into an FDM type 3D printer, and parameters are adjusted, so that the temperature of a printing nozzle in the bone plate printing process is controlled to be 200 ℃; the temperature of the printing bottom plate is controlled to be 20 ℃; the printing speed is controlled to be 5 mm/s; the speed of the cooling fan should be controlled at 2000rpm, and printing is started after the three-dimensional model of the bone plate is introduced according to the required bone plate shape, so that the composite bone plate is obtained.
Example 3 (30% by weight PLA/nHA composite bone plate)
Preparing hydroxyapatite by a coprecipitation method: 92.7 g of calcium chloride and 190 g of sodium phosphate dodecahydrate were dissolved in 500mL of water, respectively. Adding sodium phosphate solution into calcium chloride solution under the conditions of water bath at 90 ℃ and stirring, adjusting the pH to 11 by using sodium hydroxide solution and hydrochloric acid, and continuously stirring for 4 hours. Standing and aging for 12 h. And after aging, washing to remove a byproduct sodium chloride, and drying to obtain the nano-hydroxyapatite.
The hydroxyapatite and the high molecular plastic are crushed into 200-mesh fine powder. Mixing the following components in a mass ratio of 30%: 70 percent of hydroxyapatite fine powder is mixed with PLA granules and added into an internal mixer 200oC, mixing for 10 min. And putting the mixed materials into an extruder, drawing wires, controlling the melting temperature to be 200-230 ℃, and extruding and drawing wires to form uniform 3D printing consumables with the diameter range of about 1.75 mm.
The consumables are loaded into an FDM type 3D printer, and parameters are adjusted to control the temperature of a printing nozzle to be 220 ℃ in the bone plate printing process; the temperature of the printing bottom plate is controlled to be 40 ℃; the printing speed is controlled to be 10 mm/s; the speed of the cooling fan should be controlled at 2000rpm, and printing is started after the three-dimensional model of the bone plate is introduced according to the required bone plate shape, so that the composite bone plate is obtained.
As shown in fig. 2, A, B, C, D, E samples of fig. 2, examples 1, 2, and 3, were all prepared, except that the three-dimensional models were set differently.
Comparative example 1
Preparing hydroxyapatite by a coprecipitation method: 185.4 g of calcium chloride and 380 g of sodium phosphate dodecahydrate are dissolved in 1L of water, respectively. Adding sodium phosphate solution into calcium chloride solution under the conditions of water bath at 90 ℃ and stirring, adjusting the pH value to 10 by using sodium hydroxide solution and hydrochloric acid, and continuously stirring for 4 hours. Standing and aging for 12 hours. And after aging, washing to remove a byproduct sodium chloride, and drying to obtain the nano-hydroxyapatite.
The hydroxyapatite and the high molecular plastic are crushed into 200-mesh fine powder. Mixing the following components in a mass ratio of 30%: 70 percent of hydroxyapatite fine powder is mixed with PLA granules and added into an internal mixer 200oC, mixing for 10 min. And putting the mixed materials into an extruder, drawing wires, controlling the melting temperature to be 200-230 ℃, and extruding and drawing wires to form uniform 3D printing consumables with the diameter range of about 1.75 mm.
The consumables are loaded into an FDM type 3D printer, and parameters are adjusted to control the temperature of a printing nozzle to be 230 ℃ in the bone plate printing process; the temperature of the printing bottom plate is controlled to be 30 ℃; the printing speed is controlled to be 10 mm/s; the cooling fan speed should be controlled at 2000rpm, printing is started after the three-dimensional model of the bone plate is introduced, the surface of the obtained composite bone plate is rough and is slightly yellow, and polylactic acid is poor in melt deposition and is slightly denatured due to the high temperature of a printing spray head.
Comparative example 2
Preparing hydroxyapatite by a coprecipitation method: 92.7 g of calcium chloride and 190 g of sodium phosphate dodecahydrate were dissolved in 500mL of water, respectively. Adding sodium phosphate solution into calcium chloride solution under the conditions of water bath at 90 ℃ and stirring, adjusting the pH to 11 by using sodium hydroxide solution and hydrochloric acid, and continuously stirring for 4 hours. Standing and aging for 12 hours. And after aging, washing to remove a byproduct sodium chloride, and drying to obtain the nano-hydroxyapatite.
The hydroxyapatite and the high molecular plastic are crushed into 200-mesh fine powder. Mixing the following components in a mass ratio of 30%: 70 percent of hydroxyapatite fine powder is mixed with PLA granules and added into an internal mixer 200oC, mixing for 10 min. And putting the mixed materials into an extruder, drawing wires, controlling the melting temperature to be 200-230 ℃, and extruding and drawing wires to form uniform 3D printing consumables with the diameter range of about 1.75 mm.
The consumables are loaded into an FDM type 3D printer, and parameters are adjusted, so that the temperature of a printing nozzle in the bone plate printing process is controlled to be 190 ℃; the temperature of the printing bottom plate is controlled to be 30 ℃; the printing speed is controlled to be 10 mm/s; the rotating speed of the cooling fan is controlled to be 2000rpm, printing is started after the three-dimensional model of the bone plate is introduced, the obtained composite bone plate is incomplete, and due to the fact that the printing nozzle is low in temperature, polylactic acid cannot be completely melted, and deposition is poor.
Comparative example 3
Preparing hydroxyapatite by a coprecipitation method: 92.7 g of calcium chloride and 190 g of sodium phosphate dodecahydrate were dissolved in 500mL of water, respectively. Adding sodium phosphate solution into calcium chloride solution under the conditions of water bath at 90 ℃ and stirring, adjusting the pH to 9 by using sodium hydroxide solution and hydrochloric acid, and continuously stirring for 4 hours. Standing and aging for 12 hours. And after aging, washing to remove a byproduct sodium chloride, and drying to obtain the nano-hydroxyapatite.
The hydroxyapatite and the high molecular plastic are crushed into 200-mesh fine powder. Mixing the following components in a mass ratio of 30%: 70 percent of hydroxyapatite fine powder is mixed with PLA granules and added into an internal mixer 200oC, mixing for 10 min. And putting the mixed materials into an extruder, drawing wires, controlling the melting temperature to be 200-230 ℃, and extruding and drawing wires to form uniform 3D printing consumables with the diameter range of about 1.75 mm.
The consumables are loaded into an FDM type 3D printer, and parameters are adjusted to enable the temperature of a printing nozzle to be controlled at 210 ℃ in the bone plate printing process; the temperature of the printing bottom plate is controlled to be 10 ℃; the printing speed is controlled to be 5 mm/s; the rotating speed of the cooling fan is controlled to be 2000rpm, printing is started after the three-dimensional model of the bone plate is introduced, the obtained composite bone plate is incomplete, polylactic acid cannot be well bonded with the bottom plate due to the low temperature of the printing bottom plate, and dislocation can occur in the printing process, so that the printing quality of the bone plate is poor. And the printing speed is 5 mm/s, although the quality of the printing bone plate can be improved to a certain extent, the speed is too slow, and the efficiency is low.
Comparative example 4
Preparing hydroxyapatite by a coprecipitation method: 185.4 g of calcium chloride and 380 g of sodium phosphate dodecahydrate are dissolved in 1L of water, respectively. Adding sodium phosphate solution into calcium chloride solution under the conditions of water bath at 90 ℃ and stirring, adjusting the pH value to 10 by using sodium hydroxide solution and hydrochloric acid, and continuously stirring for 4 hours. Standing and aging for 12 hours. And after aging, washing to remove a byproduct sodium chloride, and drying to obtain the nano-hydroxyapatite.
The hydroxyapatite and the high molecular plastic are crushed into 200-mesh fine powder. Mixing the following components in a mass ratio of 30%: 70 percent of hydroxyapatite fine powder is mixed with PLA granules and added into an internal mixer 200oC, mixing for 10 min. And putting the mixed materials into an extruder, drawing wires, controlling the melting temperature to be 200-230 ℃, and extruding and drawing wires to form uniform 3D printing consumables with the diameter range of about 1.75 mm.
The consumables are loaded into an FDM type 3D printer, and parameters are adjusted to enable the temperature of a printing nozzle to be controlled at 210 ℃ in the bone plate printing process; the temperature of the printing bottom plate is controlled to be 50 ℃; the printing speed is controlled to be 20 mm/s; the rotating speed of the cooling fan is controlled to be 2000rpm, printing is started after the three-dimensional model of the bone plate is introduced, the shape of the obtained composite material is poor, and polylactic acid cannot have enough time to cool and deposit due to the fact that the temperature of a printing bottom plate is high and the printing speed is high, and finally the printing quality of the bone plate is poor. Table 1 shows mechanical test comparisons of bending strength of the same specification (40 mm 12.5mm 1 mm) bone plate prepared in example 1, comparative example 2, comparative example 3 and comparative example 4 at different printing temperatures and printing speeds using a three-point bending tester.
Table 1 shows the mechanical test comparison of the bending strength of the bone plates prepared in example 1, comparative example 2, comparative example 3 and comparative example 4 measured using a three-point bending tester
Figure 915814DEST_PATH_IMAGE001
。
Fig. 3 shows a bone plate of 40mm 12.5mm 1mm size prepared in this patent, which was implanted into a fracture site of the hind leg of a plurality of subjects (rabbits) in a parallel experimental group for fixation, and was implanted by a physician in the Yangtze animal hospital. Then, various biological indexes of the rabbit after the operation are tracked and investigated, and the bone repair condition of the fracture position of the hind leg of the experimental object after 4, 8 and 12 weeks is recorded and observed by using X-rays. 4. The 8 and 12 week X-ray images correspond to A, B, C in fig. 2, respectively. It can be observed that with the increase of the implantation time, the fracture has been gradually repaired without obvious bone defect, the bone growth condition is good, and the bone plate also gradually consumes metabolism.
Fig. 4 shows bone repair at the fracture site of the hind leg of the subject after the bone plate was implanted into the subject, which was recorded and observed by using mirco-CT after 4, 8, and 12 weeks. 4. The 8 and 12 week mio-CT images correspond to A, B, C in fig. 3, respectively. It was observed that with increasing implantation time, there was a significant increase in new bone at the fracture site, and the bone plate gradually consumed metabolism.
FIG. 5 is a graph showing the number of new bone formation rates exhibited by mirco-CT over time after bone plate transplantation in rabbits, showing that there was a significant increase in new bone growth at 8 and 12 weeks compared to before.
Fig. 6 is a schematic diagram of the three-point bending tester used in the bone plate bending strength test.
FIG. 7 is a comparison of the mechanical bending strength of the same bone plate prepared in comparative example 1 and example 1, wherein the temperature of the printing nozzle is controlled at 230 ℃ during the process of printing the bone plate; the temperature of the printing bottom plate is controlled to be 30 ℃; the printing speed is controlled to be 10 mm/s; the cooling fan speed was controlled at 2000rpm, printing was started after introduction of the three-dimensional model of the bone plate, and the resulting composite bone plate had a rough and somewhat yellow surface, due to the higher printing temperature, poor melt deposition of polylactic acid and some denaturation occurred, so that the flexural strength of PLA/HA bone plates prepared in this condition at various ratios was lower than that of the bone plates prepared in the comparative example condition.
FIG. 8 is a comparison of the mechanical bending strength of the same bone plate prepared in example 1 and comparative example 2, wherein the temperature of the printing nozzle is controlled at 190 ℃ during the process of printing the bone plate; the temperature of the printing bottom plate is controlled to be 30 ℃; the printing speed is controlled to be 10 mm/s; the cooling fan speed should be controlled at 2000rpm, printing is started after the three-dimensional model of the bone plate is introduced, and the obtained composite bone plate is incomplete, because the printing temperature is low, polylactic acid cannot be completely melted, so that the deposition is poor, and the bending strength of PLA/HA bone plates prepared under the conditions is lower than that of bone plates prepared under the comparative example conditions.
FIG. 9 is a comparison of the mechanical bending strength of the same bone plate prepared in example 1 and comparative example 3, wherein the temperature of the printing nozzle is controlled at 210 ℃ during the process of printing the bone plate; the temperature of the printing bottom plate is controlled to be 10 ℃; the printing speed is controlled to be 5 mm/s; the rotating speed of the cooling fan is controlled to be 2000rpm, printing is started after the three-dimensional model of the bone plate is introduced, the obtained composite bone plate is incomplete, polylactic acid cannot be well bonded with the bottom plate due to the fact that the temperature of the printing bottom plate is low, dislocation is easy to occur in the printing process, the printing quality of the bone plate is poor, and therefore the bending strength is reduced. And the printing speed is 5 mm/s, although the quality of the printing bone plate can be improved to a certain extent, the speed is slower and the efficiency is lower. The bending strength of the bone plate produced under these conditions is therefore higher or lower than that of the bone plate produced in example 1.
FIG. 10 is a comparison of the mechanical bending strength of the same bone plate made in example 1 and comparative example 4, wherein the temperature of the print head is controlled at 210 ℃ during the process of printing the bone plate; the temperature of the printing bottom plate is controlled to be 50 ℃; the printing speed is controlled to be 20 mm/s; the cooling fan speed should be controlled at 2000rpm, printing is started after the three-dimensional model of the bone plate is introduced, the shape of the obtained composite material is poor, and due to the fact that the printing bottom plate is high in temperature and the printing speed is high, polylactic acid cannot have enough time to cool and deposit, and the printing quality of the bone plate is poor, so that the bending strength of the PLA/HA bone plate prepared under the condition is lower than that of the bone plate prepared under the comparative example condition.

Claims (9)

1. The preparation method of the 3D printed medical composite material bone plate is characterized in that 5-30 parts by weight of hydroxyapatite powder and 70-95 parts by weight of polylactic acid granules are uniformly mixed, then an extruder is used for extruding and drawing the mixture into bone plate wires with uniform diameters, and the uniform bone plate wires are used for preparing the required composite material bone plate by a 3D printer.
2. The method of claim 1, comprising the steps of:
1) preparing hydroxyapatite: preparing hydroxyapatite by coprecipitation of chloride and phosphate;
2) synthetic bone plate material: respectively crushing the hydroxyapatite and the polylactic acid prepared in the step 1), sieving and collecting to obtain hydroxyapatite powder and polylactic acid granules, uniformly mixing 5-30 parts by weight of the hydroxyapatite powder and 70-95 parts by weight of the polylactic acid granules, adding the mixture into an internal mixer for mixing, and then putting the mixture into an extruder for melt extrusion to obtain bone plate wires;
3) 3D printing bone plate: and (3) loading the bone plate wire prepared in the step 2) into a 3D printer, adjusting the printing parameters of the 3D printer, and starting printing after the three-dimensional model of the bone plate is imported to obtain the composite bone plate.
3. The preparation method according to claim 2, characterized in that the step 1) comprises the following steps:
1.1) dissolving a proper amount of calcium salt in deionized water to prepare a calcium salt solution, and then dissolving a proper amount of phosphate in the deionized water to prepare a phosphate solution;
1.2) mixing a calcium salt solution and a phosphate solution under the condition of water bath at the temperature of 80-95 ℃ to ensure that the molar mass ratio of P to Ca is 1: 1.5-2, adding a sodium hydroxide solution to adjust the PH to 9-11, fully reacting for 4-10 h, standing and aging for 12-24 h, washing with deionized water, centrifuging, and drying to obtain the hydroxyapatite.
4. The method according to claim 3, wherein in step 1.1), the calcium salt is calcium chloride or calcium sulfate, and the phosphate is one of sodium hydrogen phosphate, potassium phosphate or diammonium hydrogen phosphate.
5. The method according to claim 1, wherein the polylactic acid is L-polylactic acid and has a weight average molecular weight of 10 to 20 ten thousand.
6. The preparation method according to claim 2, wherein in the step 2), the sieving granularity is 0-200 meshes.
7. The method of claim 2, wherein in step 2), the diameter of the bone plate wire is in the range of 1.75mm ± 0.05 mm.
8. The preparation method according to claim 2, wherein in the step 2), the banburying mixing condition of the banbury mixer is 200-250 ℃ for 10-30 min, and the melting temperature of the extruder is 200-230 ℃.
9. The preparation method according to claim 2, wherein in the step 3), the printing parameters are that the temperature of the spray head is 200-220 ℃, the temperature of the printing bottom plate is 20-40 ℃, the printing speed is 5-10 mm/s, and the rotating speed of the cooling fan is 2000 rpm.
CN202010242218.3A 2020-03-31 2020-03-31 Preparation method of 3D printing medical composite bone plate Pending CN111320847A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010242218.3A CN111320847A (en) 2020-03-31 2020-03-31 Preparation method of 3D printing medical composite bone plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010242218.3A CN111320847A (en) 2020-03-31 2020-03-31 Preparation method of 3D printing medical composite bone plate

Publications (1)

Publication Number Publication Date
CN111320847A true CN111320847A (en) 2020-06-23

Family

ID=71169474

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010242218.3A Pending CN111320847A (en) 2020-03-31 2020-03-31 Preparation method of 3D printing medical composite bone plate

Country Status (1)

Country Link
CN (1) CN111320847A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115105630A (en) * 2022-08-08 2022-09-27 池州学院 3D printing material embedded with chitosan/gelatin composite hydrogel and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170136133A1 (en) * 2006-06-07 2017-05-18 Apatech Limited Biomedical Materials
CN109010924A (en) * 2018-07-10 2018-12-18 扬州大学 The preparation method of BMP2-PLA/HAP composite material bone repairing support

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170136133A1 (en) * 2006-06-07 2017-05-18 Apatech Limited Biomedical Materials
CN109010924A (en) * 2018-07-10 2018-12-18 扬州大学 The preparation method of BMP2-PLA/HAP composite material bone repairing support

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAROLA ESPOSITO CORCIONE 等: "The feasibility of printing polylactic acid–nanohydroxyapatite composites using a low-cost fused deposition modeling 3D printer", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115105630A (en) * 2022-08-08 2022-09-27 池州学院 3D printing material embedded with chitosan/gelatin composite hydrogel and preparation method thereof
CN115105630B (en) * 2022-08-08 2023-08-18 池州学院 3D printing material embedded with chitosan/gelatin composite hydrogel and preparation method thereof

Similar Documents

Publication Publication Date Title
Kanno et al. Overview of innovative advances in bioresorbable plate systems for oral and maxillofacial surgery
US6117456A (en) Methods and products related to the physical conversion of reactive amorphous calcium phosphate
JP4781494B2 (en) Process for producing imperfect crystalline calcium phosphate and its use
KR101742017B1 (en) Resorbable and biocompatible fibre glass compositions and their uses
Saijo et al. Maxillofacial reconstruction using custom-made artificial bones fabricated by inkjet printing technology
US7517539B1 (en) Method of preparing a poorly crystalline calcium phosphate and methods of its use
JP5323354B2 (en) Multipurpose biomaterial composition
US20030049329A1 (en) Method of preparing a poorly crystalline calcium phosphate and methods of its use
JPH0363901B2 (en)
Enislidis et al. Fixation of zygomatic fractures with a new biodegradable copolymer osteosynthesis system: Preliminary results
US7150879B1 (en) Neutral self-setting calcium phosphate paste
CN104546103A (en) Absorbable intraosseous fixing device with biological activity and plasticity and forming method
CN104523325A (en) Device for repairing bone shortcomings and manufacturing method thereof
CN110962318A (en) Preparation method of 3D-printed polylactic acid/nano-hydroxyapatite composite bone nail
Qi et al. Development and characterization of an injectable cement of nano calcium-deficient hydroxyapatite/multi (amino acid) copolymer/calcium sulfate hemihydrate for bone repair
Sukegawa et al. Feasible advantage of bioactive/bioresorbable devices made of forged composites of hydroxyapatite particles and poly-L-lactide in alveolar bone augmentation: A preliminary study
KR20090112760A (en) Method for preparing a composite material, resulting material and use thereof
Saijo et al. Clinical experience of full custom-made artificial bones for the maxillofacial region
CN111320847A (en) Preparation method of 3D printing medical composite bone plate
KR101686343B1 (en) Bio-resorbable polymer composites comprising hyaluronic acid-chitosan composite, the manufacturing method thereof and medical implant material comprising the same
CN108686269B (en) Preparation method of hydroxyapatite/ABS composite dental implant
Hayakawa et al. In vivo evaluation of composites of PLGA and apatite with two different levels of crystallinity
Asano et al. Preparation of thermoplastic poly (L-lactic acid) membranes for guided bone regeneration.
CN108324994B (en) Preparation method of artificial bone of pearl powder
Opris et al. Characterization of eggshell as a bio-regeneration material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200623