CN105751472A - Method for manufacturing biological bone wires usable for FDM (frequency-division multiplexing) 3D (three-dimensional) printer models - Google Patents

Method for manufacturing biological bone wires usable for FDM (frequency-division multiplexing) 3D (three-dimensional) printer models Download PDF

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Publication number
CN105751472A
CN105751472A CN201610246979.XA CN201610246979A CN105751472A CN 105751472 A CN105751472 A CN 105751472A CN 201610246979 A CN201610246979 A CN 201610246979A CN 105751472 A CN105751472 A CN 105751472A
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bone
biological
fdm
type
pla
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CN105751472B (en
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李勃
朱朋飞
许国军
王进
周济
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Shenzhen International Graduate School of Tsinghua University
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Shenzhen Graduate School Tsinghua University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/12Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/18Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05Filamentary, e.g. strands
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/112Phosphorus-containing compounds, e.g. phosphates, phosphonates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Prostheses (AREA)

Abstract

The invention discloses a method for manufacturing biological bone wires useable for FDM (frequency-division multiplexing) 3D (three-dimensional) printer models.The method includes weighing, by weight, 10-90% of PLA (polylactic acid) and 90-10% of hydroxyapatite and beta-tricalcium phosphate; ultrasonically dispersing artificial bone induction and repair substrates by the aid of solvents to obtain dispersion liquid A; dissolving a binder into the dispersion liquid A by the aid of mechanical stirring processes so as to obtain mixtures B; drying the mixtures B and removing redundant solvents to obtain mixtures B for blocks; extruding the mixtures B for the blocks by the aid of double-screw extruders to obtain wires with the diameters of 1.75 millimeters.The PLA is used as the binder, and the hydroxyapatite and the beta-tricalcium phosphate are used as the artificial bone induction and repair substrates.The wires with the diameters of 1.75 millimeters are the biological bone wires.The method has the advantages that the biological bone wires manufactured by the aid of the method are combined with desktop machines and can be used for directly printing absorbable bone repair models, accordingly, the biological printing ranges can be greatly expanded, and biological printing access threshold can be lowered.

Description

Can be used for FDM 3D and print the biological bone method for manufacturing wire of type
Technical field
The invention belongs to biometric print Bone Defect Repari field, a kind of FDM 3D that can be used for prints the biological bone method for manufacturing wire of type.
Background technology
3D prints also known as numerical DC speed or increases material manufacture, is a kind of based on mathematical model file, forms workpiece by the method for layer by layer deposition, it is not necessary to realizes manufacturing mould.Therefore, 3D prints and has quick, the simple and feature of personalized customization.
FDM (Fused Deposition Modeling) 3D printing technique is one of current main flow 3D technology, but FDM is mainly in desktop field at present, the consumptive material printed is mainly PLF, ABS resin etc., the model printed can not have deeper application, therefore, the range of application of FDM type is also limited.
The widely used business-like Cranial defect of Bone Defect Repari substitutes artificial bone model, but owing to being batch production standard manufacture, its size is same, it is difficult to meet everyone demand.
Summary of the invention
It is an object of the invention to provide a kind of FDM 3D that can be used for and print the biological bone method for manufacturing wire of type.It is intended to expand the range of application that FDM 3D prints, FDM 3D printing type is applied to biometric print field, reduces the access threshold of biometric print, utilize biological bone wire rod as raw material, be combined with 3D scanning modeling, manufacture the Bone Defect Repari model that can personalize.
For achieving the above object, the present invention is by the following technical solutions.
A kind of FDM 3D that can be used for prints the biological bone method for manufacturing wire of type, and this biological bone method for manufacturing wire includes:
By weight, the PLA weighing 10-90% repairs substrate as binding agent, hydroxyapatite and the bata-tricalcium phosphate of 90-10% as artificial bone induction;
With solvent, substrate ultrasonic disperse is repaired in the induction of described artificial bone, obtain dispersion liquid A;
Use mechanical agitation methods to be dissolved in described dispersion liquid A by described binding agent, obtain mixture B;
Described mixture B is dried, removes excess of solvent, obtain the mixture B of block;
Mixture B double screw extruder by described block is extruded into the wire rod of diameter 1.75 millimeters, i.e. prepares described biological bone wire rod.
Preferably, described PLA is biological level L-type PLA or D type PLA, or the mixture of the two.Described hydroxyapatite is biological level nano-grade hydroxy apatite, and described bata-tricalcium phosphate is biological level nanoscale bata-tricalcium phosphate.
Preferably, described solvent uses chloroform, Isosorbide-5-Nitrae dioxane or acetone.Being required to ultrasonic disperse during dissolving avoids hydroxyapatite and bata-tricalcium phosphate to reunite.
Preferably, being processed in the step of wire rod by the mixture B of block, the extrusion rotating speed of double screw extruder is 200-600r/min, and extrusion temperature is 190-250 degree Celsius.
Preferably, the weight ratio of described bata-tricalcium phosphate and hydroxyapatite is 1:3-3:1, such as: 1:3,1:2,1:1,2:1,3:1.Wherein, hydroxyapatite also dissolves as new bone apposition substrate, bata-tricalcium phosphate induction of bone growth simultaneously, and both regulation hydroxyapatite and bata-tricalcium phosphate ratio can realize New born formation deposition and bone scaffold degradation rate balances.
The biological bone wire rod that said method prepares can directly print to print on type at FDM 3D becomes bone model, for defective bone repairing and treating.Visible, that the present invention manufactures biological wire rod, is combined with tabletop machine and can directly print absorbable Bone Defect Repari model, enrich the scope of biometric print greatly, reduce the access threshold of biometric print.
In above-mentioned manufacture method, during dissolving, the most just hydroxyapatite and bata-tricalcium phosphate disperse, and re-dissolved PLA so can make PLA and hydroxyapatite and bata-tricalcium phosphate uniformly mix, it is to avoid solid particle is reunited and blocked printhead.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:
Embodiment 1 can be used for the biological bone method for manufacturing wire of FDM 3D printing type and includes:
By weight, the PLA weighing 70% repairs substrate as binding agent, the biological level nanometer hydroxyapatite of 15% and the biological level nano-β-tricalcium phosphate of 15% as artificial bone induction;
Chloroform is used hydroxyapatite and bata-tricalcium phosphate to be disperseed, ultrasonic 1h, obtain dispersion liquid A;
Using churned mechanically method, be dissolved into by PLA in dispersion liquid A, mixing time is 1h, obtains mixture B;
Said mixture B is removed excess of solvent by drying, obtains the mixture B of block;
Mixture B double screw extruder by block is extruded into the wire rod of diameter 1.75 millimeters, and rate of extrusion is 400r/min, and extrusion temperature is 200 degrees Celsius, and the length of wires of extrusion is 50 meters, and this wire rod is the biological bone wire rod that can be used for FDM 3D printing type.
The wire rod obtained is inserted into FDM 3D and prints the feeding port of type, input bone STL model, generate automatic printing path with software section.Arranging print temperature is 215 DEG C, and packed density is 100%, and slice thickness is 0.2mm, clicks on and starts print button, waits to be printed complete, just obtain final bone repairing model.
Embodiment 2:
By weight, the PLA weighing 50% repairs substrate as binding agent, the biological level nanometer hydroxyapatite of 15% and the biological level nano-β-tricalcium phosphate of 35% as artificial bone induction;
Isosorbide-5-Nitrae dioxane is used hydroxyapatite and bata-tricalcium phosphate to be disperseed, ultrasonic 1h, obtain dispersion liquid A;
Using churned mechanically method, be dissolved into by PLA in dispersion liquid A, mixing time is 1h, obtains mixture B;
Said mixture B is removed unnecessary Isosorbide-5-Nitrae dioxane by drying, obtains the mixture B of block;
Mixture B double screw extruder by block is extruded into the wire rod of diameter 1.75 millimeters, and rate of extrusion is 400r/min, and extrusion temperature is 240 degrees Celsius, and the length of wires of extrusion is 50 meters, and this wire rod is the biological bone wire rod that can be used for FDM 3D printing type.
The wire rod obtained is inserted into FDM 3D and prints the feeding port of type, input bone STL model, generate automatic printing path with software section.Arranging print temperature is 215 DEG C, and packed density is 100%, and slice thickness is 0.2mm, clicks on and starts print button, waits to be printed complete, just obtain final bone repairing model.

Claims (6)

1. the biological bone method for manufacturing wire that can be used for FDM 3D printing type, it is characterised in that this biological bone wire rod system The method of making includes:
By weight, the PLA of 10-90% is weighed as binding agent, the hydroxyapatite of 90-10% and bata-tricalcium phosphate conduct Substrate is repaired in artificial bone induction;
With solvent, substrate ultrasonic disperse is repaired in the induction of described artificial bone, obtain dispersion liquid A;
Use mechanical agitation methods to be dissolved in described dispersion liquid A by described binding agent, obtain mixture B;
Described mixture B is dried, removes excess of solvent, obtain the mixture B of block;And
Mixture B double screw extruder by described block is extruded into the wire rod of diameter 1.75 millimeters, i.e. prepares described life Thing bone wire rod.
The FDM 3D that can be used for the most according to claim 1 prints the biological bone method for manufacturing wire of type, and its feature exists In: described PLA is one or both in biological level L-type PLA and biological level LD type PLA, and described hydroxyapatite is Biological level nano-grade hydroxy apatite, described bata-tricalcium phosphate is biological level nanoscale bata-tricalcium phosphate.
The FDM 3D that can be used for the most according to claim 1 prints the biological bone method for manufacturing wire of type, and its feature exists In: described solvent is chloroform, 1,4 dioxane or acetone.
The FDM 3D that can be used for the most according to claim 1 prints the biological bone method for manufacturing wire of type, and its feature exists In: being processed in the step of wire rod by the mixture B of block, the extrusion rotating speed of double screw extruder is 200-600r/min, Extrusion temperature is 190-250 degree Celsius.
The FDM 3D that can be used for the most according to claim 1 prints the biological bone method for manufacturing wire of type, and its feature exists In: the weight ratio of described bata-tricalcium phosphate and hydroxyapatite is 1:3-3:1.
The FDM 3D that can be used for the most according to claim 1 prints the biological bone method for manufacturing wire of type, and its feature exists In: described biological bone wire rod can directly print to print on type at FDM 3D becomes bone model, for defective bone reparation Treatment.
CN201610246979.XA 2016-04-20 2016-04-20 Biological bone method for manufacturing wire available for FDM 3D printing types Active CN105751472B (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107875450A (en) * 2017-11-17 2018-04-06 河北点云生物科技有限公司 A kind of method of 3D printing artificial bone manufacture drying type preparation
CN108159500A (en) * 2017-12-27 2018-06-15 天津宝坻紫荆科技有限公司 A kind of artificial bone renovating material of 3D printing and preparation method thereof
CN109010924A (en) * 2018-07-10 2018-12-18 扬州大学 The preparation method of BMP2-PLA/HAP composite material bone repairing support
CN109260522A (en) * 2018-11-22 2019-01-25 四川大学 A kind of biodegradable hard tissue repair compound rest and preparation method thereof of 3D printing technique preparation
CN110101914A (en) * 2019-05-04 2019-08-09 西北工业大学 A kind of Prevascularized two-phase artificial bone scaffold and preparation method thereof
CN111202870A (en) * 2020-03-20 2020-05-29 扬州大学 Preparation method of strontium ranelate-loaded HAP/PLA composite material bone repair scaffold
CN111214700A (en) * 2020-03-20 2020-06-02 扬州大学 Preparation method of anti-bone tumor composite material stent
CN113500759A (en) * 2021-07-08 2021-10-15 同光(昆山)生物科技有限公司 Preparation device and method of high-bioceramic-content 3D printing wire
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103707507A (en) * 2013-12-13 2014-04-09 吉林大学 Polyether-ether-ketone biomimetic artificial bone 3D printing manufacturing method
CN104147641A (en) * 2014-07-11 2014-11-19 深圳职业技术学院 Bone-repairing material for customizing and preparation method thereof
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103707507A (en) * 2013-12-13 2014-04-09 吉林大学 Polyether-ether-ketone biomimetic artificial bone 3D printing manufacturing method
CN104147641A (en) * 2014-07-11 2014-11-19 深圳职业技术学院 Bone-repairing material for customizing and preparation method thereof
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

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107875450A (en) * 2017-11-17 2018-04-06 河北点云生物科技有限公司 A kind of method of 3D printing artificial bone manufacture drying type preparation
CN108159500A (en) * 2017-12-27 2018-06-15 天津宝坻紫荆科技有限公司 A kind of artificial bone renovating material of 3D printing and preparation method thereof
CN109010924A (en) * 2018-07-10 2018-12-18 扬州大学 The preparation method of BMP2-PLA/HAP composite material bone repairing support
CN109260522A (en) * 2018-11-22 2019-01-25 四川大学 A kind of biodegradable hard tissue repair compound rest and preparation method thereof of 3D printing technique preparation
CN110101914A (en) * 2019-05-04 2019-08-09 西北工业大学 A kind of Prevascularized two-phase artificial bone scaffold and preparation method thereof
CN111202870A (en) * 2020-03-20 2020-05-29 扬州大学 Preparation method of strontium ranelate-loaded HAP/PLA composite material bone repair scaffold
CN111214700A (en) * 2020-03-20 2020-06-02 扬州大学 Preparation method of anti-bone tumor composite material stent
CN113500759A (en) * 2021-07-08 2021-10-15 同光(昆山)生物科技有限公司 Preparation device and method of high-bioceramic-content 3D printing wire
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

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