CN108822511A - A kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA - Google Patents
A kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of preparation methods of full biomass 3D printing nano combined wire rod of PLA.This method first prepares Cellulose nanocrystal with acid hydrolyzed cellulose raw material, then use alkali process, and polyethylene glycol oxide coating modification is carried out to the Cellulose nanocrystal after alkali process, prepare the Cellulose nanocrystal of the coating modification alkali process of good thermal stability, full biomass 3D printing wire rod is prepared as nanofiller and PLA melt blending extrusion, expanding material is added simultaneously improves the interface compatibility of PLA matrix and CNCs nanoparticle, and the polydactyl acid plastic molten melt after drying is squeezed out.Full biomass 3D printing provided by the invention is stablized with nano combined wire rod performance, and good mechanical properties are of great significance to 3D printing consumptive material type is widened.
Description
Technical field
The invention belongs to 3D printing Material Fields, and in particular to a kind of full biomass 3D printing nano combined wire rod of PLA
Preparation method.
Background technique
3D printing technique is a kind of and traditional material place to go processing method is completely contradicted, and is based on three-dimensional CAD model number
According to generalling use the mode successively manufactured, directly manufacture and the completely the same three dimensional physical examination question model of corresponding mathematics model
Rapid shaping technique.Wherein, fused glass pellet (FDM) because its cost is relatively low, easy to operate the features such as, industrially have
Wide utilization.
Determining 3D printing part quality, there are three aspects：Equipment, software and material.Wherein, material is the factor of most critical, is
3D printing technique development and widely applied bottleneck are restricted at present.Polylactic acid (PLA) not only have good biocompatibility and
Biodegradable also has excellent mechanical property, is suitble to a variety of processing methods, belongs to most competitive biomass high score
One of sub- material.PLA is not easy warpage in FDM forming process, lower shrinking percentage has become applied to a kind of important in FDM
High molecular material；But the molding product of PLA plastics FDM equally exists various problems, if brittleness is larger, thermal stability is poor,
Mechanical performance is obvious lower than conventional machining process, mechanics anisotropy.
It is well known that cellulose is to be distributed a kind of most wide, content is most polysaccharide in nature, it is a kind of reproducible
Biomass resource belongs to natural macromolecular material.The nano-cellulose isolated is extracted from natural fiber has intensity height, mould
Amount is big, it is at low cost, density is small, a series of excellent performances such as renewable, biodegradable and widely utilized.But it receives
The phenomenon that rice cellulose thermal stability is poor, and degradation blackening is easy to appear in high temperature process, therefore constrain nano-cellulose
Application and development.Currently, nano-cellulose thermal stability is mainly improved by improving extraction process, but effect is unobvious.
Therefore, by improving the thermal stability of Cellulose nanocrystal, a kind of biomass reinforcing filler is become, for gathering
In the Deformation In The Fdm Process technique of the biomass high molecular material such as lactic acid, the nano combined wire rod of full biomass 3D printing is prepared,
It is of great significance to 3D printing consumptive material type is widened.
Summary of the invention
The present invention is and to provide a kind of cellulose nanometer to solve the problems, such as that existing 3D printing material comprehensive performance is poor
The method of the modified 3D printing nano combined wire rod of PLA of crystalline substance, to prepare excellent in mechanical performance, heat-resist full biomass
FDM consumptive material.To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA, it is characterised in that include the following steps：
1) supernatant liquor is removed into the water slurry centrifugation of the Cellulose nanocrystal obtained after sour water solution, it is gluey retains lower layer
Object；Sodium hydroxide solution is added dropwise into jelly, the water of ultrasonic disperse, centrifuge washing, repetitive operation to Cellulose nanocrystal is outstanding
Supernatant liquid pH is 7~13；4~48h is stood, centrifuge washing, obtains the water slurry of alkali process Cellulose nanocrystal again；
2) the water slurry concentration of alkali process Cellulose nanocrystal is adjusted to after carrying out ultrasonic disperse after 0.1~5wt%,
It is heated to 40~90 DEG C, polyethylene glycol oxide is added, it is vigorously stirred 4~it is completely dissolved for 24 hours to polyethylene glycol oxide, obtain polyoxyethylene
The water slurry of the Cellulose nanocrystal of alkene coating modification；Freeze-drying, prepares the cellulose nanometer of coating modification alkali process
Crystalline flour end；The mass ratio 4 of the alkali process Cellulose nanocrystal powder and polyethylene glycol oxide:1-1:4；
3) by the PLA of 60~99wt% (polylactic acid) plastics, the cellulose nanometer of 0.1~20wt% coating modification alkali process
Brilliant, 0.1~20wt% expanding material is uniformly mixed, and obtains premix；Premix is subjected to melting extrusion with double screw extruder, is made
Grain, obtains polydactyl acid plastics；
4) the polydactyl acid plastic molten melt after drying is squeezed out, obtains the nano combined line of full biomass 3D printing PLA
Material.
To further realize the object of the invention, it is preferable that the Cellulose nanocrystal is from microcrystalline cellulose, sugarcane
Any one or more fiber extracts to obtain through sulphuric acid hydrolysis in slag, cotton stalk, wood powder, bamboo powder and rice chaff.
Preferably, it is 1,000,000,2,000,000,3,000,000,4,000,000,5,000,000 and 6,000,000 that the polyethylene glycol oxide, which is molecular weight,
One of or it is a variety of.
Preferably, the acid-hydrolyzed acid is the sulfuric acid solution that mass fraction is greater than or equal to 70%.
Preferably, the concentration of the sodium hydroxide solution is 0.05~5mol/L；The centrifuge washing and again centrifugation are washed
Wash is washed with deionized after being centrifugated.
Preferably, the expanding material is maleic anhydride grafted polylactic acid, maleic anhydride grafted polyethylene, maleic anhydride connect
One of branch polyethylene glycol oxide, maleic anhydride grafted ethene-acetate ethylene copolymer are a variety of.
Preferably, the time of ultrasonic disperse described in step 2) is 10~30min.
Preferably, it is described it is uniformly mixed be 5~20min of mixing in a high speed mixer.
Preferably, the extrusion temperature of the melting extrusion is 160~210 DEG C, the extruder engine speed of melting extrusion
For 40~120 turns/min.
Preferably, full biomass 3D printing described in step 4) is fast by the speed of dragger with the nano combined wire rod of PLA
Slow control extrusion of wire diameter is 1.75mm, and diameter error is within ± 5%.
Compared with the existing technology, the advantage of the invention is that：
1) Cellulose nanocrystal of coating modification alkali process of the invention changes by the cladding of alkali process and polyethylene glycol oxide
Property, thermal stability is remarkably enhanced.
2) compared with conventional fillers, the Cellulose nanocrystal of coating modification alkali process is as PLA plastics 3D printing filler, i.e.,
Make the mechanical performance for remaining to be obviously improved printed sample in the case where additive amount is less, and to the fluency of melt wire vent and
The quality of product surface influences smaller.
3) preparation method of the invention is at low cost, and simple process is effective, environmentally protective, has in 3D printing field wide
Application prospect.
Detailed description of the invention
Fig. 1 is nanocrystalline microcrystalline cellulose, untreated cellulose, alkali process Cellulose nanocrystal and coating modification alkali process
Cellulose nanocrystal thermal gravimetric analysis curve figure.
Fig. 2 nanocrystalline, PLA/ alkali process Cellulose nanocrystal, PLA/ coating modification for pure PLA, PLA/ untreated cellulose
Exterior appearance figure of the Cellulose nanocrystal premix of alkali process after melting extrusion is processed.
Specific embodiment
In order to better understand the present invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this
The embodiment of invention is without being limited thereto.
Embodiment 1
The water for the Cellulose nanocrystal that microcrystalline cellulose raw material obtains after mass fraction is 70% sulphuric acid hydrolysis is outstanding
Supernatant liquid removes supernatant liquor after centrifugation, retain lower layer's jelly, then washed with the sodium hydroxide solution that concentration is 0.5mol/L
And ultrasonic disperse, centrifuge washing, repetitive operation to pH are 12 again, stand for 24 hours, are washed with deionized water after being centrifugated again
It washs, obtains the water slurry of alkali process Cellulose nanocrystal, it is freeze-dried to obtain alkali process Cellulose nanocrystal powder；
Alkali process Cellulose nanocrystal powder is configured to water slurry, controlled concentration 3wt%, ultrasonic disperse 15min
It is placed in 50 DEG C of water-bath, the polyethylene glycol oxide with the quality such as Cellulose nanocrystal is then added, be vigorously stirred 12h to poly-
Ethylene oxide is completely dissolved, and obtains the alkali process Cellulose nanocrystal water slurry of polyethylene glycol oxide coating modification, finally, is passed through
The Cellulose nanocrystal powder of coating modification alkali process is prepared in freeze-drying.
Fig. 1 is nanocrystalline microcrystalline cellulose, untreated cellulose, alkali process Cellulose nanocrystal and coating modification alkali process
Cellulose nanocrystal thermal gravimetric analysis curve figure.It will be seen from figure 1 that comparing and untreated Cellulose nanocrystal
(uCNCs), the Cellulose nanocrystal (aCNCs) of alkali process Cellulose nanocrystal (aCNCs) and coating modification alkali process is heat-resisting
Performance is obviously improved.
Table 1 is to test gained microcrystalline cellulose (MCC), Cellulose nanocrystal according to national standard GB/T 14837-1993
(uCNCs), the starting of the Cellulose nanocrystal (aCNCs) of alkali process Cellulose nanocrystal (aCNCs) and coating modification alkali process
Decomposition temperature (in terms of weightlessness 10%) and decomposition mechanism temperature.From table 1 it follows that being received compared to untreated cellulose
The Cellulose nanocrystal (oCNCs) of meter Jing (uCNCs), alkali process Cellulose nanocrystal (aCNCs) and coating modification alkali process
Initial decomposition temperature and decomposition mechanism temperature, which have, significantly to be promoted, and the Cellulose nanocrystal of coating modification alkali process
(oCNCs) thermal stability is better than alkali process Cellulose nanocrystal (aCNCs), and initial decomposition temperature has reached 356.9 DEG C,
Decomposition mechanism temperature is 403.1 DEG C.
The Cellulose nanocrystal of 5wt% coating modification alkali process, 5wt% maleic anhydride grafted polylactic acid and 90wt% are gathered
Lactic acid modeling mixes 20min in high-speed mixer, obtains premix after mixing；Premix is carried out with double screw extruder
Melting extrusion, granulation, pellet is dry, the nano combined wire rod of full biomass 3D printing PLA is obtained through melting extrusion.By leading
The speed speed control extrusion of wire diameter for drawing machine is 1.75mm, and diameter error is within ± 5%.Extrusion temperature is 160~210
DEG C, engine speed is 100 turns/min.
Table 1
Note：MCC- microcrystalline cellulose, uCNCs- untreated cellulose is nanocrystalline, aCNCs- alkali process Cellulose nanocrystal,
The Cellulose nanocrystal of oCNCs- coating modification alkali process.
Standard mechanics test bars then are fabricated to 3D printer, wherein nozzle temperature is 210 DEG C, and thickness 0.1mm is beaten
Print-out rate is 30mm/min.
It stretches and bend test carries out on the Z010 type electronic universal tester of German Zwick/Roell company,
Middle rate of extension is 5mm/min, is executed according to GB/T 1040.2-2006 standard；Bending head velocity is 5mm/min, according to
GB/T 9341-2008 standard executes；Impact test carries out on radial-boom impact tester, marks according to GB/T 1843-2008
Standard executes.
Table 2 is Cellulose nanocrystal/maleic anhydride grafted polylactic acid recombination line of PLA and its PLA/ coating modification alkali process
The sample mechanical experimental results that material 3D printing goes out.As can be seen that suitable modified cellulose is added in polylactic resin
Nanocrystalline and expanding material, the mechanical property for the polylactic acid that can be significantly improved.
Table 2
| Sample | Tensile strength (MPa) | Bending strength (MPa) | Impact strength (kJ/m2) |
| PLA | 31.2 | 53.6 | 3.64 |
| PLA/oCNCs/PLA-gMAH | 41.5 | 58.4 | 5.12 |
Note：PLA/oCNCs/PLA-gMAH- polylactic acid/coating modification alkali process Cellulose nanocrystal/maleic anhydride connects
Branch lactic acid composite material.
Fig. 2 is that pure PLA, PLA/ untreated cellulose is nanocrystalline, PLA/ alkali process Cellulose nanocrystal, PLA/ coating modification
Exterior appearance figure of the Cellulose nanocrystal premix of alkali process after melting extrusion is processed.From figure 2 it can be seen that with pure
The extruded material of PLA is compared, and composite material presents yellow after untreated Cellulose nanocrystal is directly squeezed out with PLA blended melting
Brown, and alkali process Cellulose nanocrystal, the Cellulose nanocrystal of coating modification alkali process and answering after PLA blended melting extrusion
Condensation material remains as milky, this is because cellulose thermal stability modified has obtained apparent improvement, it can be very
Meet the requirement of material extrusion process well.
Embodiment 2
The water slurry for the Cellulose nanocrystal that stalk powder raw material obtains after mass fraction is 98% sulphuric acid hydrolysis,
Remove supernatant liquor after centrifugation, retain lower layer's jelly, then washs simultaneously ultrasound with the sodium hydroxide solution that concentration is 5mol/L
Dispersion, centrifuge washing, repetitive operation to pH are 11 again, stand 48h, are washed with deionized, obtain after being centrifugated again
The water slurry of alkali process Cellulose nanocrystal, it is freeze-dried to obtain alkali process Cellulose nanocrystal powder；
Alkali process Cellulose nanocrystal powder is configured to water slurry, controlled concentration 5wt%, ultrasonic disperse 30min
It is placed in 80 DEG C of water-bath, polyethylene glycol oxide is then added, control alkali process Cellulose nanocrystal powder and polyoxyethylene
The mass ratio 1 of alkene:2, it is vigorously stirred and is completely dissolved for 24 hours to polyethylene glycol oxide, obtain the alkali process of polyethylene glycol oxide coating modification
Cellulose nanocrystal water slurry finally prepares the Cellulose nanocrystal powder of coating modification alkali process by freeze-drying.
By the Cellulose nanocrystal of 10wt% coating modification alkali process, 10wt% maleic anhydride grafted polylactic acid and 80wt%
Polylactic acid modeling mixes 10min in high-speed mixer, obtains premix after mixing；By premix double screw extruder into
Row melting extrusion is granulated, and after pellet drying, obtains the nano combined wire rod of full biomass 3D printing PLA through melting extrusion.It is logical
The speed speed control extrusion of wire diameter for crossing dragger is 1.75mm, and diameter error is within ± 5%.Extrusion temperature is 160
~210 DEG C, engine speed is 120 turns/min.
Embodiment 3
The water slurry for the Cellulose nanocrystal that wood powder obtains after mass fraction is 98% sulphuric acid hydrolysis, after centrifugation
Remove supernatant liquor, retain lower layer's jelly, then washs simultaneously ultrasonic disperse with the sodium hydroxide solution that concentration is 1mol/L, then
Secondary centrifuge washing, repetitive operation to pH are 12, stand 36h, are washed with deionized after being centrifugated again, obtain alkali process fibre
The nanocrystalline water slurry of dimension element, it is freeze-dried to obtain alkali process Cellulose nanocrystal powder；
Alkali process Cellulose nanocrystal powder is configured to water slurry, controlled concentration 1wt%, ultrasonic disperse 20min
It is placed in 80 DEG C of water-bath, polyethylene glycol oxide is then added, control alkali process Cellulose nanocrystal powder and polyoxyethylene
The mass ratio 2 of alkene:1, it is vigorously stirred and is completely dissolved for 24 hours to polyethylene glycol oxide, obtain the alkali process of polyethylene glycol oxide coating modification
Cellulose nanocrystal water slurry finally prepares the Cellulose nanocrystal powder of coating modification alkali process by freeze-drying.
By the Cellulose nanocrystal of 10wt% coating modification alkali process, 5wt% maleic anhydride grafting polyethylene glycol oxide and
The modeling of 85wt% polylactic acid mixes 20min in high-speed mixer, obtains premix after mixing；Premix is squeezed with twin-screw
Machine carries out melting extrusion, is granulated out, and after pellet drying, it is nano combined to obtain full biomass 3D printing PLA through melting extrusion
Wire rod.Controlling extrusion of wire diameter by the speed speed of dragger is 1.75mm, and diameter error is within ± 5%.Squeeze out temperature
Degree is 160~210 DEG C, and engine speed is 120 turns/min.
Embodiment 4
The water slurry for the Cellulose nanocrystal that bamboo powder obtains after mass fraction is 98% sulphuric acid hydrolysis, after centrifugation
Remove supernatant liquor, retain lower layer's jelly, then washs simultaneously ultrasonic disperse with the sodium hydroxide solution that concentration is 2mol/L, then
Secondary centrifuge washing, repetitive operation to pH are 11, stand 36h, are washed with deionized after being centrifugated again, obtain alkali process fibre
The nanocrystalline water slurry of dimension element, it is freeze-dried to obtain alkali process Cellulose nanocrystal powder；
Alkali process Cellulose nanocrystal powder is configured to water slurry, controlled concentration 2wt%, ultrasonic disperse 20min
It is placed in 60 DEG C of water-bath, polyethylene glycol oxide is then added, control alkali process Cellulose nanocrystal powder and polyoxyethylene
The mass ratio 4 of alkene:1, it is vigorously stirred and is completely dissolved for 24 hours to polyethylene glycol oxide, obtain the alkali process of polyethylene glycol oxide coating modification
Cellulose nanocrystal water slurry finally prepares the Cellulose nanocrystal powder of coating modification alkali process by freeze-drying.
By the Cellulose nanocrystal of 15wt% coating modification alkali process, 15wt% maleic anhydride grafted ethene-vinyl acetate
30min is mixed in high-speed mixer with the modeling of 70wt% polylactic acid, obtains premix after mixing；By premix twin-screw
Extruder carries out melting extrusion, is granulated, and after pellet drying, obtains PLA nanometers of full biomass 3D printing again through melting extrusion
Zygonema material.Controlling extrusion of wire diameter by the speed speed of dragger is 1.75mm, and diameter error is within ± 5%.It squeezes out
Temperature is 160~210 DEG C, and engine speed is 120 turns/min.
The thermal gravimetric analysis curve figure and the basic phase of Fig. 1 of the Cellulose nanocrystal of coating modification alkali process obtained by embodiment 2-4
Seemingly；Exterior appearance figure of the Cellulose nanocrystal premix of PLA/ coating modification alkali process after melting extrusion is processed and Fig. 2 base
This is similar, does not provide attached drawing one by one.
The thermal stability and the basic phase of table 1 of the Cellulose nanocrystal (oCNCs) of coating modification alkali process obtained by embodiment 2-4
Together；The mechanical property and table 2 of the embodiment 2-4 resulting full biomass 3D printing nano combined wire rod of PLA are essentially identical.
Above embodiments are served only for helping to understand method and effect of the invention；For those of ordinary skill in the art,
According to an embodiment of the present invention, it much can change place in upper have of specific embodiment and application, it is thus understood that all exist
In protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA, it is characterised in that include the following steps：
1) supernatant liquor is removed into the water slurry centrifugation of the Cellulose nanocrystal obtained after sour water solution, retains lower layer's jelly；
Sodium hydroxide solution, ultrasonic disperse, centrifuge washing, the water slurry of repetitive operation to Cellulose nanocrystal are added dropwise into jelly
PH is 7~13；4~48h is stood, centrifuge washing, obtains the water slurry of alkali process Cellulose nanocrystal again；
2) the water slurry concentration of alkali process Cellulose nanocrystal is adjusted to after carrying out ultrasonic disperse after 0.1~5wt%, heating
To 40~90 DEG C, polyethylene glycol oxide is added, it is vigorously stirred 4~it is completely dissolved for 24 hours to polyethylene glycol oxide, obtain polyethylene glycol oxide packet
Cover the water slurry of modified Cellulose nanocrystal；Freeze-drying, prepares the Cellulose nanocrystal powder of coating modification alkali process
End；The mass ratio 4 of the alkali process Cellulose nanocrystal powder and polyethylene glycol oxide:1-1:4；
3) by the PLA plastics of 60~99wt%, the Cellulose nanocrystal of 0.1~20wt% coating modification alkali process, 0.1~
20wt% expanding material is uniformly mixed, and obtains premix；Premix is subjected to melting extrusion with double screw extruder, is granulated, is obtained
Polydactyl acid plastics；
4) the polydactyl acid plastic molten melt after drying is squeezed out, obtains the nano combined wire rod of full biomass 3D printing PLA.
2. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, the fiber
Element it is nanocrystalline be from microcrystalline cellulose, bagasse, cotton stalk, wood powder, bamboo powder and rice chaff any one or more fiber through sulphur
Sour water solution is extracted to obtain.
3. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, the polyoxy
Change ethylene is that molecular weight is one of 1,000,000,2,000,000,3,000,000,4,000,000,5,000,000 and 6,000,000 or a variety of.
4. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, the sour water solution
Acid be mass fraction be greater than or equal to 70% sulfuric acid solution.
5. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, the hydroxide
The concentration of sodium solution is 0.05~5mol/L；The centrifuge washing and again centrifuge washing are washed with deionized water after being centrifugated
It washs.
6. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, the increase-volume
Agent is maleic anhydride grafted polylactic acid, maleic anhydride grafted polyethylene, maleic anhydride is grafted polyethylene glycol oxide, maleic anhydride is grafted
One of ethylene-vinyl acetate copolymer is a variety of.
7. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, step 2) is described
Ultrasonic disperse time be 10~30min.
8. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, the mixing
It is uniformly to mix 5~20min in a high speed mixer.
9. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, the melting
The extrusion temperature of extrusion is 160~210 DEG C, and the extruder engine speed of melting extrusion is 40~120 turns/min.
10. the preparation method of the full biomass 3D printing nano combined wire rod of PLA according to claim 1, step 4) institute
The full biomass 3D printing stated controls extrusion of wire diameter by the speed speed of dragger with the nano combined wire rod of PLA
1.75mm, diameter error is within ± 5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574813A (en) * | 2019-06-11 | 2020-08-25 | 南京林业大学 | Polylactic acid-based biomass composite material and 3D printing forming thereof |
| CN113604018A (en) * | 2021-09-06 | 2021-11-05 | 新余学院 | Polylactic acid-based nanocomposite material for 3D printing and preparation method thereof |
| CN114571693A (en) * | 2022-03-16 | 2022-06-03 | 北京纳通医学研究院有限公司 | Composite 3D printing wire and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170009427A (en) * | 2015-07-17 | 2017-01-25 | 충남대학교산학협력단 | Filament composition for 3 dimensional print comprising nanocrystalcellulose and red algae fiber |
| CN106589894A (en) * | 2016-12-19 | 2017-04-26 | 华南理工大学 | Preparing method for heat-resisting cellulose nanocrystal |
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2018
- 2018-06-05 CN CN201810568417.6A patent/CN108822511A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170009427A (en) * | 2015-07-17 | 2017-01-25 | 충남대학교산학협력단 | Filament composition for 3 dimensional print comprising nanocrystalcellulose and red algae fiber |
| CN106589894A (en) * | 2016-12-19 | 2017-04-26 | 华南理工大学 | Preparing method for heat-resisting cellulose nanocrystal |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574813A (en) * | 2019-06-11 | 2020-08-25 | 南京林业大学 | Polylactic acid-based biomass composite material and 3D printing forming thereof |
| CN111574813B (en) * | 2019-06-11 | 2022-06-10 | 南京林业大学 | Polylactic acid-based biomass composite material and 3D printing forming thereof |
| CN113604018A (en) * | 2021-09-06 | 2021-11-05 | 新余学院 | Polylactic acid-based nanocomposite material for 3D printing and preparation method thereof |
| CN114571693A (en) * | 2022-03-16 | 2022-06-03 | 北京纳通医学研究院有限公司 | Composite 3D printing wire and preparation method thereof |
| CN114571693B (en) * | 2022-03-16 | 2024-02-23 | 北京纳通医学研究院有限公司 | Composite 3D printing wire and preparation method thereof |
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Application publication date: 20181116 |
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