CN107573660A - A kind of low temperature FDM types biological medical degradable 3D printing material, preparation and application - Google Patents
A kind of low temperature FDM types biological medical degradable 3D printing material, preparation and application Download PDFInfo
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- CN107573660A CN107573660A CN201710828358.7A CN201710828358A CN107573660A CN 107573660 A CN107573660 A CN 107573660A CN 201710828358 A CN201710828358 A CN 201710828358A CN 107573660 A CN107573660 A CN 107573660A
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Abstract
A kind of low temperature FDM types biological medical degradable 3D printing material, preparation and application, belong to 3D printing field.The material is using PCL, starch (farina, cornstarch or soluble starch etc.), EBS, SiO2, magnesium stearate be raw material, preparation method be by by twin-screw by PCL master batches and starch, EBS, SiO2, the filler such as magnesium stearate after melting mixing, crushes and is granulated, then turn into the suitable wire rod of size uniformity by Single screw extrusion, stretching, reuse FDM type 3D printers and printed according to a certain percentage.Present invention process is simple and easy, it is low to prepare cost, printing precision is high, and it is low to 3D printing equipment requirement degree, selectivity is wide, and general family expenses FDM type 3D printers also can be used, and material has degradability, and provided the foundation for exploitation bio-medical FDM type 3D printing materials, there is important value and meaning in 3D printing field.
Description
Technical field
The invention belongs to 3D printing field, and in particular to a kind of biological medical degradable low temperature FDM type 3D printing materials
Prepare and its using print conditions.
Background technology
Fused glass pellet method (FDM, Fused Deposition Modeling), this technique are by by thread material
The fuse of material such as thermoplastic, wax or metal is extruded from the nozzle of heating, according to each layer of desired trajectory of part, with fixation
Speed carry out melt deposition.One layer is often completed, workbench declines a thickness and carries out new one layer of superposition deposition, so repeatedly
The final deposition modeling for realizing part.The key of FDM techniques is to maintain the temperature of half flowing moulding material just on fusing point
(1 DEG C higher than fusing point or so).FDM technology has the advantages of stock utilization is high, the cost of material is low, optional material category is more, fits
Conceptual modelling and shape and functional test together in product.Fused glass pellet has vitally in 3D printing field
Position.This is due to that its molding mode is relatively simple, and formed precision is high, and printer model hardness is good, and generalization is stronger, not against laser
As the shaping energy, the cost of printing device is relatively low, so as to as current most popular 3D printing technique.
But conventional FDM type 3D printings thermoplastic such as PLA, ABS and PC print temperature is more than 200 DEG C, into
Type temperature is higher, and high temperature means high energy consumption and low-security, when being particularly used in a home environment, easily to children
Deng self-protection ability, poor crowd damages.Importantly, higher processing temperature also limit to 3D printing material
Addition types of functionality active material in material, this significantly limit the exploitation of functional material.Meanwhile these material biofacies
Capacitive is poor with degradability, and which has limited 3D printing in the application of bio-medical field, and non-degradable material also easily causes ring
Pollute in border.Such as patent publication No. CN106928671A " a kind of high-strength shape memory 3D printing biological plastics and preparation
More than 180 DEG C, this significantly limit its biological work(for exploitation its processing temperature of 3D printing consumptive material and temperature in use in method "
The further exploitation of energy property.
PCL is a kind of linear aliphatic adoption ester, is at room temperature hypocrystalline state, and its fusing point (59-64 DEG C) is relatively low.
These fundamental propertys assign its good biocompatibility, pliability, processability, and have good biodegradability, this
A little is all that PCL can be as the good basis of the degradable low temperature FDM types 3D printing material of biological functional.But simple PCL
For 3D printing material, exist solidification is slow, melt strength is low, not easy-formation the problems such as, cause not can be used at present
The PCL materials of FDM type 3D printings.Such as patent publication No. CN106474566A " a kind of 3D printing PCL/Hap composites and its
The PCL/Hap composites developed in preparation method, purposes, Method of printing ", although realizing low temperature 3D printing, its material
Matter is slurry, needs special 3D printer to use, and complex operation, is not easy to implement, which greatly limits low temperature 3D printing
The popularization of material.
The content of the invention
The purpose of the present invention is the problem of presence for PCL FDM type 3D printings, there is provided one kind FDM types can give birth at low temperature
Thing medical degradable 3D composite and preparation method.This method uses natural degradable material --- and-starch promotes for nucleation
Agent, by way of promoting PCL to crystallize, promote PCL shapings, to improve the 3D printing performance of material, while reserved materials is good
Biocompatibility and degradability.This method is crushed PCL master batches and filler melting mixing after being granulated by twin-screw, then
By Single screw extrusion, stretching turns into 3D printing wire rod.
The technical solution adopted by the present invention is as follows：
A kind of low temperature FDM types biological medical degradable 3D printing material, its raw material composition weight/mass percentage composition include as follows：
Polycaprolactone (PCL) master batch 80-90%, such as 80%, 82%, 84%, 86%, 88%, 90% etc., starch 1-15%, such as
1%th, 3%, 5%, 7%, 9%, 11%, 13%, 15% etc., EBS 1-5%, such as 1%, 2%, 3%, 4%, 5% etc., SiO2
1-5%, such as 1%, 2%, 3%, 4%, 5% etc., magnesium stearate 1-5%, such as 1%, 2%, 3%, 4%, 5% etc., it is above-mentioned
Mass percent sum≤100% of five kinds of raw materials.
Starch is preferably the one or more in farina, cornstarch or soluble starch；
It may further be preferable that polycaprolactone (PCL) master batch 85-90%, farina 7-10% or cornstarch 6-
9% or soluble starch 9-11%, EBS 2-4%, SiO22-3%, magnesium stearate 2-5%.The quality hundred of above-mentioned five kinds of raw materials
Divide than sum≤100%.The wherein too low then material shaping of packing density is slow, and printing is not easy to shape.The too high then material of packing density
Viscosity is excessive, it is difficult to not smooth enough by orifice tip, printing.
The preparation method of above-mentioned low temperature FDM types biological medical degradable 3D printing material, it is characterised in that including following step
Suddenly：
(1) weigh a certain amount of PCL master batches and starch (farina, cornstarch and soluble starch etc.),
EBS (ethylenebisstearamide) and SiO2, magnesium stearate, after mixing, it is stirred, makes it tentatively well mixed, reuses
Double screw extruder melt blending under suitable conditions；After cooling, obtained composite is crushed and is granulated；
(2) by pellet melting extrusion in single screw extrusion machine obtained by step (1), by the traction of hauling machine, chi is formed
Very little suitable homogeneous wire rod.
Preferably, double screw extruder processing temperature is 45-100 DEG C, screw speed 10-30rpm.
Preferably, single screw extrusion machine processing temperature is 65-90 DEG C, screw speed 20-50rpm.
Preferably, gauge or diameter of wire 1.65-1.75mm.
The application of low temperature FDM type 3D printing materials, as FDM type 3D printer consumptive materials, printer model and engineering element.
Composite FDM type 3D printing condition and ranges：80-90 DEG C of nozzle temperature, 20-35 DEG C of baseplate temp, spout movement
Speed and enter a speed and be respectively smaller than 40mm/s, 90mm/s.
The low temperature FDM type 3D printings material of the present invention is used for 3D printing, compared with document report before, has following excellent
Point：
(1) present invention successfully have developed can at low temperature (80-90 DEG C) progress 3D printing composite.The file printing
Temperature is low, and precision is high, and print performance is preferable.
(2) preparation method of the present invention is simple and easy, and condition is controllable, and it is low to prepare cost.
(3) the low temperature 3D printing consumptive material that the present invention makes is low to 3D printing equipment requirement degree, and selectivity is wide, general family expenses
FDM type 3D printers also can be used.
(4) primary raw material PCL and starch used in the present invention are degradation material, and product is degradable, will not cause
Plastic pollution.And biocompatibility is good, available for medical application.
Brief description of the drawings
Fig. 1 is the low temperature FDM type 3D printing wire rod figures prepared by the present invention；
Fig. 2 is the purer PCL printing effects comparison diagram of low temperature FDM type 3D printing wire rods prepared by the present invention.
Embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Weigh 80g PCL master batches to be placed in 250mL beakers, then weigh respectively, add 5g cornstarch, 5g EBS, 5g
SiO2With 5g magnesium stearates.It is mixed uniformly using agitator.
By mixture in double screw extruder, by way of melt blending, PCL is set fully to be blended with filler.Respectively
The area of double screw extruder one, 2nd area, 3rd area and four area's temperature are set as 50,75,100 and 75 DEG C.Set screw speed as
20rpm.It is blended after terminating, then ready-made material disintegrating is granulated.
The pellet that will be prepared, using single screw extrusion machine melting extrusion, by drawing machine travel, form size uniformity
Wire rod.Setting single screw extrusion machine one area, two area's temperature are respectively 80 and 85 DEG C, screw speed 30rpm, and wire size is
1.70-1.75mm。
When being printed by FDM type 3D printers, setting 3D printer parameter is as follows：85 DEG C of nozzle temperature, bottom plate temperature
35 DEG C of degree, spout translational speed and to enter a speed be respectively 40mm/s, 90mm/s.
Embodiment 2
Weigh 82g PCL master batches to be placed in 250mL beakers, then weigh respectively, add 8g farinas, 2g EBS, 3g
SiO2With 5g magnesium stearates.It is mixed uniformly using agitator.
By mixture in double screw extruder, by way of melt blending, PCL is set fully to be blended with filler.Respectively
The area of double screw extruder one, 2nd area, 3rd area and four area's temperature are set as 60,75,90 and 75 DEG C.Set screw speed as
20rpm.It is blended after terminating, then ready-made material disintegrating is granulated.
The pellet that will be prepared, using single screw extrusion machine melting extrusion, by drawing machine travel, form size uniformity
Wire rod.Setting single screw extrusion machine one area, two area's temperature are respectively 80 and 85 DEG C, screw speed 30rpm, and wire size is
1.70-1.75mm。
When being printed by FDM type 3D printers, setting 3D printer parameter is as follows：85 DEG C of nozzle temperature, bottom plate temperature
35 DEG C of degree, spout translational speed and to enter a speed be respectively 40mm/s, 90mm/s.
Embodiment 3
Weigh 84g PCL master batches to be placed in 250mL beakers, then weigh respectively, add 6g soluble starches, 4g EBS, 3g
SiO2With 3g magnesium stearates.It is mixed uniformly using agitator.
By mixture in double screw extruder, by way of melt blending, PCL is set fully to be blended with filler.Respectively
The area of double screw extruder one, 2nd area, 3rd area and four area's temperature are set as 50,70,90 and 75 DEG C.Set screw speed as
15rpm.It is blended after terminating, then ready-made material disintegrating is granulated.
The pellet that will be prepared, using single screw extrusion machine melting extrusion, by drawing machine travel, form size uniformity
Wire rod.Set the area of single screw extrusion machine one, two area's temperature are respectively 80 and 85 DEG C, screw speed 40rpm, gauge or diameter of wire size
For 1.70-1.75mm.
When being printed by FDM type 3D printers, setting 3D printer parameter is as follows：85 DEG C of nozzle temperature, bottom plate temperature
20 DEG C of degree, spout translational speed and to enter a speed be respectively 40mm/s, 90mm/s.
Embodiment 4
Weigh 86g PCL master batches to be placed in 250mL beakers, then weigh respectively, add 4g farinas, 3g EBS, 3g
SiO2With 4g magnesium stearates.It is mixed uniformly using agitator.
By mixture in double screw extruder, by way of melt blending, PCL is set fully to be blended with filler.Respectively
The area of double screw extruder one, 2nd area, 3rd area and four area's temperature are set as 60,70,90 and 75 DEG C.Set screw speed as
20rpm.It is blended after terminating, then ready-made material disintegrating is granulated.
The pellet that will be prepared, using single screw extrusion machine melting extrusion, by drawing machine travel, form size uniformity
Wire rod.Setting single screw extrusion machine one area, two area's temperature are respectively 70 and 75 DEG C, screw speed 30rpm, and wire size is
1.70-1.75mm。
When being printed by FDM type 3D printers, setting 3D printer parameter is as follows：85 DEG C of nozzle temperature, bottom plate temperature
35 DEG C of degree, spout translational speed and to enter a speed be respectively 40mm/s, 90mm/s.
Embodiment 5
Weigh 88g PCL master batches to be placed in 250mL beakers, then weigh respectively, add 9g soluble starches, 1g EBS, 1g
SiO2With 1g magnesium stearates.It is mixed uniformly using agitator.
By mixture in double screw extruder, by way of melt blending, PCL is set fully to be blended with filler.Respectively
The area of double screw extruder one, 2nd area, 3rd area and four area's temperature are set as 55,75,90 and 75 DEG C.Set screw speed as
25rpm.It is blended after terminating, then ready-made material disintegrating is granulated.
The pellet that will be prepared, using single screw extrusion machine melting extrusion, by drawing machine travel, form size uniformity
Wire rod.Setting single screw extrusion machine one area, two area's temperature are respectively 80 and 85 DEG C, screw speed 30rpm, and wire size is
1.70-1.75mm。
When being printed by FDM type 3D printers, setting 3D printer parameter is as follows：85 DEG C of nozzle temperature, bottom plate temperature
25 DEG C of degree, spout translational speed and to enter a speed be respectively 30mm/s, 60mm/s.
Embodiment 6
Weigh 90g PCL master batches to be placed in 250mL beakers, then weigh respectively, add 5g cornstarch, 3g EBS, 1g
SiO2With 1g magnesium stearates.It is mixed uniformly using agitator.
By mixture in double screw extruder, by way of melt blending, PCL is set fully to be blended with filler.Respectively
The area of double screw extruder one, 2nd area, 3rd area and four area's temperature are set as 55,75,85 and 75 DEG C.Set screw speed as
20rpm.It is blended after terminating, then ready-made material disintegrating is granulated.
The pellet that will be prepared, using single screw extrusion machine melting extrusion, by drawing machine travel, form size uniformity
Wire rod.Setting single screw extrusion machine one area, two area's temperature are respectively 70 and 75 DEG C, screw speed 40rpm, and wire size is
1.70-1.75mm。
When being printed by FDM type 3D printers, setting 3D printer parameter is as follows：90 DEG C of nozzle temperature, bottom plate temperature
20 DEG C of degree, spout translational speed and to enter a speed be respectively 20mm/s, 40mm/s.
Low temperature FDM type 3D printing wire rods prepared by above-mentioned implementation can be found in Fig. 1；Low temperature prepared by the embodiment of the present invention
FDM types 3D printing wire rod printing effect and pure PCL printing effects are shown in Fig. 2.
Claims (9)
1. a kind of low temperature FDM types biological medical degradable 3D printing material, it is characterised in that its raw material forms weight/mass percentage composition
Including as follows：Polycaprolactone (PCL) master batch 80-90%, starch 1-15%, EBS 1-5%, SiO21-5%, magnesium stearate 1-
5%, mass percent sum≤100% of above-mentioned five kinds of raw materials.
2. according to a kind of low temperature FDM types biological medical degradable 3D printing material described in claim 1, it is characterised in that poly-
Caprolactone (PCL) master batch 85-90%, farina 7-10% or cornstarch 6-9% or soluble starch 9-11%, EBS
2-4%, SiO22-3%, magnesium stearate 2-5%.
3. according to a kind of low temperature FDM types biological medical degradable 3D printing material described in claim 1 or 2, it is characterised in that
Starch is the one or more in farina, cornstarch or soluble starch.
4. according to a kind of low temperature FDM types biological medical degradable 3D printing material described in claim 1 or 2, it is characterised in that
Gauge or diameter of wire size is 1.65-1.75mm.
5. the preparation method of the low temperature FDM type biological medical degradable 3D printing materials described in claim any one of 1-4, it is special
Sign is, comprises the following steps：
(1) a certain amount of PCL master batches and starch and SiO are weighed2, magnesium stearate, after mixing, it is stirred, it is tentatively mixed
Uniformly, double screw extruder melt blending under suitable conditions is reused；After cooling, obtained composite is crushed and is granulated；
(2) by pellet melting extrusion in single screw extrusion machine obtained by step (1), by the traction of hauling machine, form size and close
Suitable homogeneous wire rod.
6. according to the method for claim 5, it is characterised in that double screw extruder processing temperature is 45-100 DEG C, screw speed
For 10-30rpm.
7. according to the method for claim 5, it is characterised in that single screw extrusion machine processing temperature is 65-90 DEG C, and screw speed is
20-50rpm。
8. the application of the low temperature FDM type biological medical degradable 3D printing materials described in claim any one of 1-4, its feature exist
In, as FDM type 3D printer consumptive materials, printer model and engineering element.
9. the application of the low temperature FDM type biological medical degradable 3D printing materials described in claim any one of 1-4, its feature exist
In print conditions scope：80-90 DEG C of nozzle temperature, 20-35 DEG C of baseplate temp, spout translational speed and to enter thread speed difference small
In 40mm/s, 90mm/s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108453927A (en) * | 2018-02-08 | 2018-08-28 | 西安交通大学 | A kind of preparation process of biodegradable PCL/Mg composite materials FDM consumptive materials |
| CN110152062A (en) * | 2019-05-22 | 2019-08-23 | 南通大学 | A kind of 3D biometric print hydrogel scaffold and preparation method thereof applied to regeneration |
| CN112721164A (en) * | 2020-12-16 | 2021-04-30 | 山东创瑞增材制造产业技术研究院有限公司 | Preparation device and preparation method for PCL material for 3D printing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400164A (en) * | 2015-12-03 | 2016-03-16 | 深圳光华伟业股份有限公司 | Low-temperature 3D printing material and preparation method thereof |
| CN105482394A (en) * | 2015-12-24 | 2016-04-13 | 江苏道勤新材料科技有限公司 | High-conductivity 3D printing consumable capable of being degraded and preparation method thereof |
| CN107118309A (en) * | 2017-06-26 | 2017-09-01 | 浙江海轩科技有限公司 | A kind of biodegradable polyesters alloy and preparation method thereof |
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2017
- 2017-09-14 CN CN201710828358.7A patent/CN107573660A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400164A (en) * | 2015-12-03 | 2016-03-16 | 深圳光华伟业股份有限公司 | Low-temperature 3D printing material and preparation method thereof |
| CN105482394A (en) * | 2015-12-24 | 2016-04-13 | 江苏道勤新材料科技有限公司 | High-conductivity 3D printing consumable capable of being degraded and preparation method thereof |
| CN107118309A (en) * | 2017-06-26 | 2017-09-01 | 浙江海轩科技有限公司 | A kind of biodegradable polyesters alloy and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108453927A (en) * | 2018-02-08 | 2018-08-28 | 西安交通大学 | A kind of preparation process of biodegradable PCL/Mg composite materials FDM consumptive materials |
| CN110152062A (en) * | 2019-05-22 | 2019-08-23 | 南通大学 | A kind of 3D biometric print hydrogel scaffold and preparation method thereof applied to regeneration |
| CN112721164A (en) * | 2020-12-16 | 2021-04-30 | 山东创瑞增材制造产业技术研究院有限公司 | Preparation device and preparation method for PCL material for 3D printing |
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Application publication date: 20180112 |