WO2020244011A1 - Method for manufacturing novel absorbable bone implant, and bone implant - Google Patents
Method for manufacturing novel absorbable bone implant, and bone implant Download PDFInfo
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- WO2020244011A1 WO2020244011A1 PCT/CN2019/094115 CN2019094115W WO2020244011A1 WO 2020244011 A1 WO2020244011 A1 WO 2020244011A1 CN 2019094115 W CN2019094115 W CN 2019094115W WO 2020244011 A1 WO2020244011 A1 WO 2020244011A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- 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
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Definitions
- the invention relates to a novel method for manufacturing an absorbable bone implant and a bone implant, and belongs to the application field of 3D printing technology in medical treatment.
- PLA Poly Lactic Acid
- FDM Fused Deposition Modeling
- the rate at which PLA is absorbed and degraded cannot completely match the growth rate of its own bones; on the other hand, the biomechanical properties of PLA itself such as tensile and shear resistance are poor, and the PLA obtained through FDM can be Absorbed bone implants have obvious anisotropy.
- the melt-extruded fuses are continuously distributed in the X direction of continuous deposition, and the mechanical properties close to compression molding can be obtained, while the fuse distribution is in the Y direction and the layer-by-layer accumulation of the Z direction. Above, the fuses are not coherent, and there is a fuse interface, as shown in Figure 1. Obviously, the fuse interface is the weakest position of the absorbable bone implant. In short, the degradation rate is not well matched with the bone growth rate, the biomechanical properties such as tensile and shear resistance are poor, and the anisotropy due to the existence of the interface will greatly limit its application in clinical medicine.
- the purpose of the present invention is to provide a novel method for manufacturing absorbable bone implants and bone implants, based on the polymer matrix composite material interface multiphase structure and micromechanical theory, to control the fuse interface structure and improve the melting
- the bonding performance of the silk interface eliminates the anisotropy of FDM additive manufacturing PLA resorbable bone implants, improves the overall tensile and shear resistance and other biomechanical properties, and at the same time improves the compatibility of PLA degradation rate and bone growth rate, and enhances its performance Functional applications in medical treatment.
- a novel method for manufacturing absorbable bone implants including the following steps: a) Obtain the three-dimensional shape of the bone implant, and after data processing, obtain a 3D printing Sectional data; b) Medical-grade nano-hydroxyapatite (Hydroxyapatite, HAP) and medical-grade chopped carbon fiber are pretreated for dispersibility and compatibility, and the two are dissolved into medical-grade polyethylene glycol (Polyethylene glycol, PEG) to obtain the prepreg; c) Use the prepreg to impregnate the medical grade polylactic acid (PLA) bare wire, and dry it to obtain HAP/carbon fiber@PLA composite wire; d ) Using HAP/carbon fiber@PLA composite material wire, driven by the 3D printing slice data of the bone implant, through the Fused Deposition Modeling (FDM) 3D printing process, the absorbable bone implant is obtained; e) Put the absorbable bone implant into a microwave oven for microwave post-processing.
- FDM Fused Deposition Modeling
- bone implants refer to various skeletal organs implanted in humans or animals.
- the three-dimensional shape can be obtained through CT scanning and three-dimensional reconstruction software, and further through 3D printing special data processing software to reduce dimensionality Processing to obtain slice data that can be 3D printed;
- the prepreg is a mixture of medical grade nano HAP with a particle size of 100nm ⁇ 400nm, a length dimension of 100 ⁇ m ⁇ 300 ⁇ m medical grade chopped carbon fiber, and medical grade PEG.
- the parameters of prepreg for high-energy ultrasonic vibration impregnation of medical-grade PLA bare wire can be adjusted to adjust the thickness of the deposited layer.
- PEG is volatilized, medical-grade HAP, medical-grade carbon fiber deposition
- the fused deposition forming 3D printing process has a nozzle diameter of 0.45mm ⁇ 0.55mm, a nozzle moving speed of 40mm/s-80mm/s, and a nozzle melting temperature of 200°C-230°C;
- the microwave post-treatment process uses a microwave frequency of 2.45 GHz, a microwave output power of 80W to 200W, a microwave temperature of 80°C to 150°C, and a microwave action time of 40s to 80s.
- a new type of resorbable bone implant obtained by the above method has X-direction tensile properties of 80-90MPa, Y-direction tensile properties of 77-87MPa, Z-direction tensile properties of 74-84MPa, and dimensional accuracy. ⁇ 0.08mm, which fully meets the application requirements of clinical medicine.
- both medical grade HAP and medical grade carbon fiber have good human or animal biocompatibility, and the two stay in the bone gap and can participate in bone growth and healing through bone conduction, and, After the two are pretreated separately, the dispersion and compatibility are improved, the -OH grafting sites are enriched, and the PLA matrix will be strengthened based on particle reinforcement, fiber reinforcement, and lipidation reaction molecular bonding;
- the absorbable bone implant obtained by FDM additive manufacturing is subjected to microwave post-processing, and the carbon fiber at the fuse interface is used to absorb microwaves (HAP does not absorb microwaves at a temperature below the melting point of PLA, and PLA does not absorb microwaves).
- the PLA at the location is remelted to further cross-link and diffuse its molecular chains, the interface stress is fully released, the interface bonding is strengthened again, and the anisotropy caused by the interface is eliminated.
- the static tensile strength of the sample reaches 80MPa, and the all-directional difference is controlled within 3%, which fully meets the mechanical requirements of the absorbable bone medical implant.
- Figure 1 is a schematic diagram of the FDM fuse interface.
- FDM Fused Deposition Modeling
- the nozzle diameter is 0.30mm and the nozzle movement speed 60mm/s, the melting temperature of the nozzle is 210°C; e) Put the resorbable bone implant into a microwave oven for microwave post-processing, the microwave frequency used is 2.45GHz, the microwave output power is 160W, and the microwave temperature is 110°C , The microwave action time is 50s.
- the finally obtained bone implant has a tensile performance of 85 MPa in X-direction, 82 MPa in Y-direction, 79 MPa in Z-direction, and a dimensional accuracy of ⁇ 0.08 mm, which fully meets the requirements of clinical medical applications.
Abstract
Disclosed are a method for manufacturing an absorbable bone implant, and bone implant. The manufacture method comprises: acquiring a three-dimensional model of a bone implant, and performing data processing on the model to obtain adaptive slice data for 3D printing; pre-treating medical grade nano-hydroxyapatite (HAp) and medical grade short carbon fibers, and then dissolving both according to a ratio in a medical grade polyethylene glycol (PEG) to obtain a prepreg; impregnating an uncoated wire of medical grade polylactic acid (PLA) with the prepreg, followed by drying to obtain an HAp/carbon fiber@PLA composite wire; performing a fused deposition modeling 3D printing process using the HAp/carbon fiber@PLA composite wire and driven by the bone implant 3D printing slice data to obtain the absorbable bone implant; and performing microwave post-treatment on the absorbable bone implant. The absorbable bone implant has improved overall biomechanical properties, including stretch resistance and shear resistance; and the speed at which the PLA matrix is absorbed and degraded matches the growth speed of bones in the body of a subject.
Description
本发明涉及一种新型的可吸收骨类植入体制造方法和骨类植入体，属于3D打印技术在医疗中的应用领域。The invention relates to a novel method for manufacturing an absorbable bone implant and a bone implant, and belongs to the application field of 3D printing technology in medical treatment.
PLA(Poly Lactic Acid，聚乳酸)是一种人体及大部分动物生物相容性较好、可生物降解的绿色高分子材料，同时具有与人类及大部分动物骨骼比较接近的弹性模量。FDM(Fused Deposition Modeling，熔融沉积成形)增材制造工艺的成形精度和表面质量日益提高且已经满足了骨类植入体的制造要求。将PLA丝材通过FDM快速制造为个性化的可吸收骨类植入体成为研究热点。PLA (Poly Lactic Acid) is a green polymer material with good biocompatibility and biodegradability for humans and most animals, and has an elastic modulus close to that of human and most animal bones. The forming accuracy and surface quality of FDM (Fused Deposition Modeling) additive manufacturing processes are improving day by day and have met the manufacturing requirements of bone implants. The rapid manufacturing of PLA filaments through FDM into personalized absorbable bone implants has become a research hotspot.
然而不能忽视的是，一方面，PLA被吸收降解的速度与自身骨骼的生长速度不能完全匹配；另一方面，PLA自身抗拉、抗剪等生物力学性能较差，而且通过FDM获得的PLA可吸收骨类植入体，存在明显的各向异性。这是由于FDM增材制造原理所决定，熔融挤出的熔丝在连续沉积的X方向连续分布，可以获得接近模压成形的力学性能，而在熔丝分布的Y方向和逐层累积的Z方向上，熔丝之间不连贯，存在熔丝界面，如图1所示。显然，熔丝界面是可吸收骨类植入体最薄弱的位置。总之，降解速度与骨骼生长速度匹配不好，抗拉、抗剪等生物力学性能较差，以及因界面存在而产生的各向异性，将大大限制其在临床医疗中的应用。However, it cannot be ignored that, on the one hand, the rate at which PLA is absorbed and degraded cannot completely match the growth rate of its own bones; on the other hand, the biomechanical properties of PLA itself such as tensile and shear resistance are poor, and the PLA obtained through FDM can be Absorbed bone implants have obvious anisotropy. This is due to the principle of FDM additive manufacturing. The melt-extruded fuses are continuously distributed in the X direction of continuous deposition, and the mechanical properties close to compression molding can be obtained, while the fuse distribution is in the Y direction and the layer-by-layer accumulation of the Z direction. Above, the fuses are not coherent, and there is a fuse interface, as shown in Figure 1. Obviously, the fuse interface is the weakest position of the absorbable bone implant. In short, the degradation rate is not well matched with the bone growth rate, the biomechanical properties such as tensile and shear resistance are poor, and the anisotropy due to the existence of the interface will greatly limit its application in clinical medicine.
发明内容Summary of the invention
本发明的目的是提供一种新型的可吸收骨类植入体制造方法和骨类植入体，基于聚合物基复合材料界面多相结构和细观力学理论，调控熔丝界面结构、改善熔丝界面结合性能，消除FDM增材制造PLA可吸收骨类植入体各向异性，提高整体抗拉、抗剪等生物力学性能，同时改善PLA降解速度与骨骼生长速度的匹配性，增强其在医疗方面的功能性应用。The purpose of the present invention is to provide a novel method for manufacturing absorbable bone implants and bone implants, based on the polymer matrix composite material interface multiphase structure and micromechanical theory, to control the fuse interface structure and improve the melting The bonding performance of the silk interface eliminates the anisotropy of FDM additive manufacturing PLA resorbable bone implants, improves the overall tensile and shear resistance and other biomechanical properties, and at the same time improves the compatibility of PLA degradation rate and bone growth rate, and enhances its performance Functional applications in medical treatment.
本发明的目的是这样实现的：一种新型的可吸收骨类植入体制造方法，包括以下步骤：a)获得骨类植入体的三维造型，并经过数据处理，获得可以进行3D打印的切片数据；b)对医用级纳米羟基磷灰石(Hydroxyapatite，HAP)、医用级短切碳纤维经过分散性、相容性预处理后，将两者按比例溶入医用级聚乙二醇(Polyethylene glycol，PEG)，获得预浸料；c)使用预浸料对医用级聚乳酸(Poly Lactic Acid，PLA)裸丝进行浸渍，经干燥烘干，获得HAP/碳纤维@PLA复合材料丝材；d)利用HAP/碳纤维@PLA复合材料丝材，在骨类 植入体3D打印切片数据的驱动下，通过熔融沉积成形(Fused Deposition Modeling，FDM)3D打印工艺，获得可吸收骨类植入体；e)将可吸收骨类植入体放入微波炉内，进行微波后处理。The purpose of the present invention is achieved as follows: a novel method for manufacturing absorbable bone implants, including the following steps: a) Obtain the three-dimensional shape of the bone implant, and after data processing, obtain a 3D printing Sectional data; b) Medical-grade nano-hydroxyapatite (Hydroxyapatite, HAP) and medical-grade chopped carbon fiber are pretreated for dispersibility and compatibility, and the two are dissolved into medical-grade polyethylene glycol (Polyethylene glycol, PEG) to obtain the prepreg; c) Use the prepreg to impregnate the medical grade polylactic acid (PLA) bare wire, and dry it to obtain HAP/carbon fiber@PLA composite wire; d ) Using HAP/carbon fiber@PLA composite material wire, driven by the 3D printing slice data of the bone implant, through the Fused Deposition Modeling (FDM) 3D printing process, the absorbable bone implant is obtained; e) Put the absorbable bone implant into a microwave oven for microwave post-processing.
其中骨类植入体，是指植入人体或动物的各类骨骼器官，其三维造型，可以通过CT扫描并经过三维重构软件获得，并进一步经过3D打印专门的数据处理软件，进行降维处理，获得可以进行3D打印的切片数据；Among them, bone implants refer to various skeletal organs implanted in humans or animals. The three-dimensional shape can be obtained through CT scanning and three-dimensional reconstruction software, and further through 3D printing special data processing software to reduce dimensionality Processing to obtain slice data that can be 3D printed;
其中预浸料，由粒径为100nm～400nm的医用级纳米HAP、长度尺寸为100μm～300μm医用级短切碳纤维、医用级PEG三者混合配置，三者的比例按照质量分数为HAP:碳纤维:PEG＝1:1.5:3～1:2:4，医用级纳米HAP、医用级短切碳纤维两者均需要进行分散性、相容性预处理，并获得丰富的-OH接枝位点，且两者可以提供骨骼诱导作用，促进骨骼生长；Among them, the prepreg is a mixture of medical grade nano HAP with a particle size of 100nm～400nm, a length dimension of 100μm～300μm medical grade chopped carbon fiber, and medical grade PEG. The proportion of the three is HAP: Carbon fiber: PEG=1:1.5:3～1:2:4, both medical grade nano HAP and medical grade chopped carbon fiber need to be pretreated with dispersibility and compatibility, and obtain abundant -OH grafting sites, and Both can provide bone induction and promote bone growth;
其中预浸料对医用级PLA裸丝进行高能超声振动浸渍的参数，可以调整，从而可调沉积层的厚度，浸渍后，经干燥烘干，PEG被挥发掉，医用级HAP、医用级碳纤维沉积在医用级PLA裸丝表面，且其中PLA裸丝的直径为0.20mm～0.30mm，获得HAP/碳纤维@PLA复合材料丝材，且三者的比例按照质量分数为HAP:碳纤维:PLA＝1:1.5:50～1:2:80；Among them, the parameters of prepreg for high-energy ultrasonic vibration impregnation of medical-grade PLA bare wire can be adjusted to adjust the thickness of the deposited layer. After dipping, drying and drying, PEG is volatilized, medical-grade HAP, medical-grade carbon fiber deposition On the surface of the medical-grade PLA bare wire, and the diameter of the PLA bare wire is 0.20mm～0.30mm, the HAP/carbon fiber@PLA composite wire is obtained, and the ratio of the three is HAP: carbon fiber: PLA = 1: 1.5:50～1:2:80;
其中熔融沉积成形3D打印工艺，其喷嘴直径为0.45mm～0.55mm，喷嘴移动速度40mm/s-80mm/s，喷嘴熔融温度为200℃-230℃；Among them, the fused deposition forming 3D printing process has a nozzle diameter of 0.45mm～0.55mm, a nozzle moving speed of 40mm/s-80mm/s, and a nozzle melting temperature of 200℃-230℃;
其中微波后处理工艺，其所用微波频率为2.45GHz，微波输出功率为80W～200W，微波温度为80℃～150℃，微波作用时间为40s～80s。Among them, the microwave post-treatment process uses a microwave frequency of 2.45 GHz, a microwave output power of 80W to 200W, a microwave temperature of 80°C to 150°C, and a microwave action time of 40s to 80s.
通过以上方法获得的一种新型的可吸收骨类植入体，X向拉伸性能达到80～90MPa，Y向拉伸性能达到77～87MPa，Z向拉伸性能达到74～84MPa，尺寸精度达到±0.08mm，完全满足了临床医疗的应用要求。A new type of resorbable bone implant obtained by the above method has X-direction tensile properties of 80-90MPa, Y-direction tensile properties of 77-87MPa, Z-direction tensile properties of 74-84MPa, and dimensional accuracy. ±0.08mm, which fully meets the application requirements of clinical medicine.
有益效果：由于采用上述方案，首先医用级HAP和医用级碳纤维均具有较好的人体或动物生物相容性，两者滞留于骨隙间可以通过骨传导的作用参与骨骼生长和愈合，而且，两者分别进行预处理后，改善了分散性、相容性，丰富了-OH接枝位点，还会基于颗粒增强、纤维增强、脂化反应分子键合等，对PLA基体产生强化作用；其次将FDM增材制造获得的可吸收骨类植入体进行微波后处理，利用熔丝界面处的碳纤维吸收微波(HAP在PLA熔点以下温度不吸收微波，PLA不吸收微波)，对熔丝界面处的PLA产生再熔，使其分子链进一步交联和扩散，界面应力获得充分释放，界面结合再次获得增强，同时，界面导致的各向异性获得消除。试样静拉伸强度达到80MPa，各向差异控制在3％内，完全达到可吸收骨类医疗植入体力学要求。Beneficial effects: due to the adoption of the above scheme, first of all, both medical grade HAP and medical grade carbon fiber have good human or animal biocompatibility, and the two stay in the bone gap and can participate in bone growth and healing through bone conduction, and, After the two are pretreated separately, the dispersion and compatibility are improved, the -OH grafting sites are enriched, and the PLA matrix will be strengthened based on particle reinforcement, fiber reinforcement, and lipidation reaction molecular bonding; Secondly, the absorbable bone implant obtained by FDM additive manufacturing is subjected to microwave post-processing, and the carbon fiber at the fuse interface is used to absorb microwaves (HAP does not absorb microwaves at a temperature below the melting point of PLA, and PLA does not absorb microwaves). The PLA at the location is remelted to further cross-link and diffuse its molecular chains, the interface stress is fully released, the interface bonding is strengthened again, and the anisotropy caused by the interface is eliminated. The static tensile strength of the sample reaches 80MPa, and the all-directional difference is controlled within 3%, which fully meets the mechanical requirements of the absorbable bone medical implant.
图1是FDM熔丝界面示意图。Figure 1 is a schematic diagram of the FDM fuse interface.
以下为本发明的最佳实施方式The following is the best embodiment of the present invention
一种新型的可吸收骨类植入体制造方法：a)获得某骨类植入体的三维造型，并经过数据处理，获得可以进行3D打印的切片数据；b)对医用级100nm纳米HAP、医用级150μm短切碳纤维经过预处理，改善分散性、相容性，丰富-OH接枝位点，并将两者溶入医用级PEG，获得预浸料，三者的比例按照质量分数为HAP:碳纤维:PEG＝1:1.5:3.5；c)使用预浸料对医用级PLA裸丝进行高能超声振动浸渍，然后经干燥烘干，将PEG挥发掉，医用级HAP、医用级碳纤维则沉积在医用级PLA裸丝表面，获得HAP/碳纤维@PLA复合材料丝材，且三者的比例按照质量分数为HAP:碳纤维:PLA＝1:1.5:70；d)利用HAP/碳纤维@PLA复合材料丝材，在骨类植入体3D打印切片数据的驱动下，通过熔融沉积成形(Fused Deposition Modeling，FDM)3D打印工艺，获得可吸收骨类植入体，其喷嘴直径为0.30mm，喷嘴移动速度60mm/s，喷嘴熔融温度为210℃；e)将可吸收骨类植入体放入微波炉内，进行微波后处理，其所用微波频率为2.45GHz，微波输出功率为160W，微波温度为110℃，微波作用时间为50s。A new type of manufacturing method for absorbable bone implants: a) Obtain the three-dimensional shape of a bone implant, and after data processing, obtain slice data that can be 3D printed; b) For medical grade 100nm nano HAP, Medical-grade 150μm chopped carbon fiber is pre-treated to improve dispersion and compatibility, enrich -OH grafting sites, and dissolve the two into medical-grade PEG to obtain prepreg. The ratio of the three is HAP according to the mass fraction : Carbon fiber: PEG=1:1.5:3.5; c) Use prepreg to impregnate medical-grade PLA bare wire with high-energy ultrasonic vibration, and then dry and dry to evaporate PEG. Medical-grade HAP and medical-grade carbon fiber are deposited on Medical grade PLA bare wire surface, obtain HAP/carbon fiber@PLA composite wire, and the proportion of the three is HAP: carbon fiber: PLA=1:1.5:70 according to the mass fraction; d) Utilize HAP/carbon fiber@PLA composite wire Driven by the 3D printing slice data of the bone implant, through the Fused Deposition Modeling (FDM) 3D printing process, the absorbable bone implant is obtained. The nozzle diameter is 0.30mm and the nozzle movement speed 60mm/s, the melting temperature of the nozzle is 210℃; e) Put the resorbable bone implant into a microwave oven for microwave post-processing, the microwave frequency used is 2.45GHz, the microwave output power is 160W, and the microwave temperature is 110℃ , The microwave action time is 50s.
最终获得的某骨类植入体，X向拉伸性能达到85MPa，Y向拉伸性能达到82MPa，Z向拉伸性能达到79MPa，尺寸精度达到±0.08mm，完全满足了临床医疗的应用要求。The finally obtained bone implant has a tensile performance of 85 MPa in X-direction, 82 MPa in Y-direction, 79 MPa in Z-direction, and a dimensional accuracy of ±0.08 mm, which fully meets the requirements of clinical medical applications.
Claims (10)
- 一种新型的可吸收骨类植入体制造方法，其特征在于，包括以下步骤：a)获得骨类植入体的三维造型，并经过数据处理，获得可以进行3D打印的切片数据；b)对医用级纳米羟基磷灰石(Hydroxyapatite，HAP)、医用级短切碳纤维进行分散性、相容性预处理后，将两者按比例溶入医用级聚乙二醇(Polyethylene glycol，PEG)，获得预浸料；c)使用预浸料对医用级聚乳酸(Poly Lactic Acid，PLA)裸丝进行浸渍，经干燥烘干，获得HAP/碳纤维@PLA复合材料丝材；d)利用HAP/碳纤维@PLA复合材料丝材，在骨类植入体3D打印切片数据的驱动下，通过熔融沉积成形(Fused Deposition Modeling，FDM)3D打印工艺，获得可吸收骨类植入体；e)将可吸收骨类植入体放入微波炉内，进行微波后处理。A novel method for manufacturing absorbable bone implants, which is characterized by including the following steps: a) Obtain a three-dimensional model of the bone implant, and after data processing, obtain slice data that can be 3D printed; b) After dispersing and compatibility pretreatment of medical grade nano-hydroxyapatite (Hydroxyapatite, HAP) and medical grade chopped carbon fiber, the two are dissolved into medical grade polyethylene glycol (PEG) in proportion, Obtain the prepreg; c) Use the prepreg to impregnate the medical-grade polylactic acid (PLA) bare wire, dry and dry to obtain HAP/carbon fiber@PLA composite material wire; d) Use HAP/carbon fiber @PLA composite material wire, driven by the 3D printing slice data of the bone implant, through the Fused Deposition Modeling (FDM) 3D printing process, the absorbable bone implant is obtained; e) the absorbable The bone implant is placed in a microwave oven for microwave post-processing.
- 根据权利要求1所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述骨类植入体，是指植入人体或动物的各类骨骼器官。The method for manufacturing a novel absorbable bone implant according to claim 1, wherein the bone implant refers to various bone organs implanted in the human body or animal.
- 根据权利要求1所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述骨类植入体的三维造型，通过CT扫描并经过三维重构软件获得。The method for manufacturing a new type of resorbable bone implant according to claim 1, wherein the three-dimensional shape of the bone implant is obtained by CT scanning and three-dimensional reconstruction software.
- 根据权利要求1或3所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述骨类植入体的三维造型，需要经过3D打印专门的数据处理软件，进行降维处理，获得可以进行3D打印的切片数据。The method for manufacturing a new type of resorbable bone implant according to claim 1 or 3, wherein the three-dimensional modeling of the bone implant needs to go through 3D printing special data processing software to perform reduction Dimension processing to obtain slice data that can be 3D printed.
- 根据权利要求1所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述预浸料中医用级HAP、医用级碳纤维、医用级PEG三者的比例按照质量分数为医用级HAP:医用级碳纤维:医用级PEG＝1:1.5:3～1:2:4。The method for manufacturing a new type of resorbable bone implant according to claim 1, wherein the ratio of medical grade HAP, medical grade carbon fiber, and medical grade PEG in the prepreg is as follows: Medical grade HAP: medical grade carbon fiber: medical grade PEG=1:1.5:3～1:2:4.
- 根据权利要求1或5所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述预浸料中，医用级HAP为纳米颗粒，粒径为100nm～400nm，医用级碳纤维为短切状，长度尺寸为100μm～300μm，两者均需要进行分散性、相容性预处理，获得丰富的-OH接枝位点，且两者提供骨骼诱导作用，促进骨骼生长。The method for manufacturing a new type of resorbable bone implant according to claim 1 or 5, characterized in that, in the prepreg, medical grade HAP is nano-particles with a particle size of 100nm to 400nm, and medical grade HAP The carbon fiber is chopped and has a length of 100 μm to 300 μm. Both of them need to be pretreated with dispersibility and compatibility to obtain abundant -OH grafting sites, and both provide bone inducing effect and promote bone growth.
- 根据权利要求1所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述预浸料对医用级PLA裸丝进行高能超声振动浸渍，调整浸渍参数，获得的沉积层厚度可调，且其中PLA裸丝的直径为0.20mm～0.30mm；并经干燥烘干后，PEG被挥发掉，医用级HAP、医用级碳纤维沉积在医用级PLA裸丝表面，获得HAP/碳纤维@PLA复合材料丝材，且三者的比例按照质量分数为医用级 HAP:医用级碳纤维:医用级PLA＝1:1.5:50～1:2:80。A new type of resorbable bone implant manufacturing method according to claim 1, wherein the prepreg is impregnated with high-energy ultrasonic vibration on the medical-grade PLA bare wire, and the impregnation parameters are adjusted to obtain the deposited layer The thickness is adjustable, and the diameter of the PLA bare wire is 0.20mm～0.30mm; after drying and drying, the PEG is volatilized, medical grade HAP and medical grade carbon fiber are deposited on the surface of the medical grade PLA bare wire to obtain HAP/carbon fiber @PLA composite material wire, and the ratio of the three according to the mass fraction is medical grade HAP: medical grade carbon fiber: medical grade PLA=1:1.5:50～1:2:80.
- 根据权利要求1所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述熔融沉积成形3D打印工艺，其喷嘴直径为0.25mm～0.35mm，喷嘴移动速度40mm/s-80mm/s，喷嘴熔融温度为200℃-230℃。The method for manufacturing a novel absorbable bone implant according to claim 1, wherein the fused deposition forming 3D printing process has a nozzle diameter of 0.25 mm to 0.35 mm, and a nozzle movement speed of 40 mm/s -80mm/s, the nozzle melting temperature is 200℃-230℃.
- 根据权利要求1所述的一种新型的可吸收骨类植入体制造方法，其特征在于，所述微波后处理工艺，其所用微波频率为2.45GHz，微波输出功率为80W～200W，微波温度为80℃～150℃，微波作用时间为40s～80s。The method for manufacturing a new type of resorbable bone implant according to claim 1, wherein the microwave post-treatment process uses a microwave frequency of 2.45 GHz, a microwave output power of 80W to 200W, and a microwave temperature It is 80℃～150℃, and the microwave action time is 40s～80s.
- 利用权利要求1～9任意一项权利要求所述的方法制造的一种新型的可吸收骨类植入体，其特征在于，所述骨类植入体，X向拉伸性能达到80～90MPa，Y向拉伸性能达到77～87MPa，Z向拉伸性能达到74～84MPa，尺寸精度达到±0.08mm。A new type of absorbable bone implant manufactured by the method of any one of claims 1-9, wherein the bone implant has an X-direction tensile property of 80-90 MPa , Y-direction tensile performance reaches 77-87MPa, Z-direction tensile performance reaches 74-84MPa, and dimensional accuracy reaches ±0.08mm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105031737A (en) * | 2014-12-03 | 2015-11-11 | 北京印刷学院 | 3D printed digital artificial bone and preparation method thereof |
| CN106700041A (en) * | 2015-11-16 | 2017-05-24 | 黑龙江鑫达企业集团有限公司 | Method for preparing carbon fiber reinforced polylactic acid/hydroxyapatite composite material |
| CN108295302A (en) * | 2018-01-19 | 2018-07-20 | 中山职业技术学院 | A kind of preparation method of the medical polylactic acid modified compound 3D printing material of calcium phosphate bone cement |
| CN108407283A (en) * | 2018-03-15 | 2018-08-17 | 中国矿业大学 | A kind of novel melting deposition formation 3D printing method and device |
| US20180296343A1 (en) * | 2017-04-18 | 2018-10-18 | Warsaw Orthopedic, Inc. | 3-d printing of porous implants |
| CN108859127A (en) * | 2017-04-21 | 2018-11-23 | 华沙整形外科股份有限公司 | The 3D printing of bone graft |
| KR20180128227A (en) * | 2017-05-23 | 2018-12-03 | 한국생산기술연구원 | Composition of filaments complex resin for the fdm-3d printer, method of manufacturing filaments for the fdm-3d printer and filaments and scaffolds manufactured thereby |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013006A (en) * | 2015-06-24 | 2015-11-04 | 东莞天天向上医疗科技有限公司 | Bioabsorbable bone repair material and its use and manufacturing method |
| CN106671411A (en) * | 2016-12-28 | 2017-05-17 | 浙江理工大学 | Rapid forming method capable of compounding chopped fibers and thermoplastic resin |
| CN107320221A (en) * | 2017-06-21 | 2017-11-07 | 四川大学 | A kind of lopsided knee joint skeleton model preparation method based on 3D printing technique |
-
2019
- 2019-06-06 CN CN201910489915.6A patent/CN110279898A/en active Pending
- 2019-07-01 WO PCT/CN2019/094115 patent/WO2020244011A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105031737A (en) * | 2014-12-03 | 2015-11-11 | 北京印刷学院 | 3D printed digital artificial bone and preparation method thereof |
| CN106700041A (en) * | 2015-11-16 | 2017-05-24 | 黑龙江鑫达企业集团有限公司 | Method for preparing carbon fiber reinforced polylactic acid/hydroxyapatite composite material |
| US20180296343A1 (en) * | 2017-04-18 | 2018-10-18 | Warsaw Orthopedic, Inc. | 3-d printing of porous implants |
| CN108859127A (en) * | 2017-04-21 | 2018-11-23 | 华沙整形外科股份有限公司 | The 3D printing of bone graft |
| KR20180128227A (en) * | 2017-05-23 | 2018-12-03 | 한국생산기술연구원 | Composition of filaments complex resin for the fdm-3d printer, method of manufacturing filaments for the fdm-3d printer and filaments and scaffolds manufactured thereby |
| CN108295302A (en) * | 2018-01-19 | 2018-07-20 | 中山职业技术学院 | A kind of preparation method of the medical polylactic acid modified compound 3D printing material of calcium phosphate bone cement |
| CN108407283A (en) * | 2018-03-15 | 2018-08-17 | 中国矿业大学 | A kind of novel melting deposition formation 3D printing method and device |
Non-Patent Citations (1)
| Title |
|---|
| SHEN, LIE ET AL.: "Mechanical Properties and Degradation Properties in Vitro of Carbon Fiber Reinforced Hydroxyapatite/Polylactide Composite", ACTA MATERIAE COMPOSITAE SINICA, vol. 24, no. 5, 31 October 2007 (2007-10-31), DOI: 20200306201554Y * |
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