CN110396286A - Excellent 3D printing consumptive material and preparation method thereof at a low price - Google Patents
Excellent 3D printing consumptive material and preparation method thereof at a low price Download PDFInfo
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- CN110396286A CN110396286A CN201910668370.5A CN201910668370A CN110396286A CN 110396286 A CN110396286 A CN 110396286A CN 201910668370 A CN201910668370 A CN 201910668370A CN 110396286 A CN110396286 A CN 110396286A
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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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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of 3D printing consumptive materials and preparation method thereof that low price is excellent.3D printing consumptive material of the present invention includes that following mass parts raw material is made: 65-95 parts of polylactic acid (PLA), 5-35 parts of thermoplastic polyurethane (TPU), 0.1-30 parts of PLA base expanding material (PGU) and 5-40 parts of thermoplastic starch (TPS).3D printing consumptive material of the invention has at low cost, environmental protection and energy saving, and the advantage of function admirable.
Description
Technical field
The invention belongs to 3D printing consumptive material technical fields, and in particular to a kind of 3D printing consumptive material that low price is excellent and its preparation
Method.
Background technique
3D printing technique is referred to as increasing material manufacturing again, is the completely new molds, methods of making of the one kind in modern age.3D printing is begun
In the last century 80's, by the continuous development and innovation of recent decades, 3D printing technique be have been relatively mature, and wide
It is general to be applied to multiple fields.Fused glass pellet technology (FDM) is one of the important technology for forming 3D printing technique, with thermoplasticity
Wire rod is primary raw material, is moved, the material of melting is sent to specified along part section profile and filling track by hot melt head
Position simultaneously bonds solidification, ultimately forms product.Material used in 3D printing is generally in the form of powder, long filament coiled material, liquid modeling
Material etc..Commercially available 3D printing consumptive material based on thermoplastic, mainly have acrylonitrile-butadiene-styrene copolymer (ABS),
The nondegradable plastics and PLA, PCL etc. such as polystyrene (PS), nylon (PA), polyvinyl alcohol (PVA), polypropylene (PP) can
Degradative plastics.PLA is after the lactic acid generated after one kind is fermented by biomass resource (such as sugarcane, cassava, beet) polymerize
The high molecular material of formation, not only production process green non-pollution, and can degradable be CO2And H2O is a kind of green
The environmentally friendly material of environment-friendly degradable, while PLA base 3D printing consumptive material is also widely used for FDM technology.With it is traditional
Petroleum-based plastics compare, and this degradable high polymer material of PLA is suitable therewith in processing performance and mechanical property, Neng Gou
In certain degree replace petroleum-based plastics use, regarded as in the industry be conventional plastic materials the first substitute.PLA base
Modified 3D printing consumptive material becomes current research hotspot.Chen Wei etc. using Joncryl ADR 4370S chain extender as modifying agent,
It is prepared for the modified PLA base silk material of chain extender, and forms to obtain the PLA silk material for 3D printing using melting extrusion, is had studied
Hot property, melt strength, mechanical property of modified PLA etc..The result shows that: unmodified PLA is compared, ADR chain extender is added
Heat resistance, melt strength and the mechanical property of modified PLA is improved.When the dosage of ADR is 0.4%, modified PLA
The synthesis print performance of silk material is best.Tang Tongming etc. has been prepared by improving the synthesis condition of polylactic acid with excellent thermostabilization
The novel PLA3D printing consumables of property.Zhang Lanbo etc. is prepared for TPU toughening PLA3D printing wire rod using the method for melt blending,
And different content TPU is had studied to the toughening effect of PLA and the rheological characteristic of TPU/PLA composite material.The result shows that with group
The toughness of the increase composite material of TPU content improves rheological characteristic simultaneously and reduces in point, the composite material when TPU content is 10%
Rheological characteristic is suitable for 3D printing consumptive material.Rafael etc. is prepared for 3D and is beaten with the fiber-reinforced modified PLA of 60 μm of carbon fiber
Print consumptive material.The result shows that the stretch modulus and modulus of shearing of PLA composite material mention respectively when the additive amount of carbon fiber is 15%
High 1.25 times and 1.16 times.Jiang Hui etc. is respectively with polyethylene glycol (PEG), poly-succinic diol ester (PBS) for toughener, with poly-
Ammonium phosphate (APP) is that fire retardant is modified PLA, and is prepared for PLA/PEG/APP/LCP toughening flame-proof system 3D printing consumption
Material.So that the elongation at break of composite material is risen to 72% by 4.2% the result shows that adding 15% PEG, adds 15%
The limit oxygen index of composite material has reached 30.1% after APP, and the rheological property for being added to composite material after LCP significantly improves,
MFR is increased to 14.09g/10min by 7.01g/10min.Delphine etc. [7] uses short bamboo fiber reinforcement polylactic acid, and studies
The mechanical property of polylactic acid base 3D printing consumptive material after short bamboo fiber reinforcement, discovery are 1:4.1-1:4.7 using draw ratio
Short bamboo fiber reinforcement after the modulus highest of polylactic acid base printing consumables can be enhanced the 230% of pure polylactic acid.Panda etc.
It is prepared for matching different PCL/PLA3D printing consumables, and finds as PCL:PLA=70:30,3D printing consumptive material has most
Excellent mechanical property.
Although biology base recyclable plastic PLA has a variety of excellent performances, different material ingredient and PLA arrange in pairs or groups
The 3D printing consumptive material being prepared, it is very big to its toughness, rheological characteristic and Effect on Mechanical Properties, it is every a kind of raw material is added all to be difficult to protect
Demonstrate,proving it not influences the toughness of 3D printing consumptive material, rheological characteristic and mechanical property etc..Such as: TPU in the experiment of the toughening effect of PLA,
With the increase of TPU content in component, the toughness of composite material improves rheological characteristic simultaneously and reduces, multiple when TPU content is 10%
The rheological characteristic of condensation material is suitable for 3D printing consumptive material, but PLA and TPU have poor compatibility and dispersibility,
Cause thermal expansion than high, influences the comprehensive performance of 3D printing consumptive material.
Therefore, although biology base recyclable plastic PLA has a variety of excellent performances, low tenacity, high price are limits
Make its major defect further applied.PLA is applied in 3D printing consumptive material, the raw material of preparation 3D printing consumptive material how is reduced
Cost, moreover it is possible to have good toughness, rheological characteristic, melt strength and the lower excellent 3D printing consumptive material for thermally expanding ratio, become
The problem of urgent need to resolve.
Summary of the invention
The present invention in view of the above technical problems, provides a kind of 3D printing consumptive material of function admirable, can reduce cost, environmental protection
Energy conservation, and have good toughness, rheological characteristic and melt strength, than low, surface property is good for thermal expansion.
The present invention provides a kind of 3D printing consumptive material, including following mass parts raw material is made: 65-95 parts of polylactic acid (PLA),
5-35 parts of thermoplastic polyurethane (TPU), 0.1-30 parts of PLA base expanding material (PGU) and 5-40 parts of thermoplastic starch (TPS).
Preferably, the thermoplastic starch (TPS) includes 10-50 parts and tapioca 50-90 parts of glycerol of mass parts,
And glycerol and tapioca are swollen, are taken out through high-speed mixer mixing 5-15min, it places 15-30h and obtains.
Preferably, the PLA base expanding material (PGU) includes following mass parts raw material: dry polylactic acid (PLA) 65-
97 parts, 5-40 parts of thermoplastic polyurethane (TPU), 2-35 parts of glycidyl methacrylate (GMA) and 0.1-1.0wt%
0.1-2.0 parts of cumyl peroxide (DCP)；And step is prepared by the following procedure and obtains:
Step 1: polylactic acid (PLA) elder generation that 65-97 parts are dried internally mix 2- at 50rpm in 180 DEG C of mixers
After 10min, 0.1-2.0 parts of cumyl peroxide (DCP) is added, continues continuous reaction 2-15min, adds 2-35 parts
Glycidyl methacrylate (GMA) takes out material after reacting 3-10min, and PLA-g-GMA is made in washing, dry, crushing；
Step 2: PLA-g-GMA in 180 DEG C of mixers at 50rpm, be added 2-35 parts Glycidyl methacrylate it is sweet
After continuing internally mix 3-10min, 5-40 parts of thermoplastic polyurethane (TPU) is added in grease (GMA), the reaction was continued 4-12min, is made
It obtains TPU and thoroughly replaces GMA, take out material afterwards, PLA-g-TPU copolymer, as PLA base increase-volume is made in washing, dry, crushing
Agent (PGU).
The present invention also provides a kind of preparation method of 3D printing consumptive material, specifically: by the 65-95 parts of polylactic acid after dry
(PLA), 5-35 parts of thermoplastic polyurethane (TPU), 0.1-30 parts of PLA base expanding material (PGU) and 5-40 parts of thermoplastic starch
Powder (TPS) is added in high-speed mixer and mixes 5min-10min, mixed material is added twin-screw extrude, and squeezes out
The area Ji Ge temperature maximum temperature is 190 DEG C, and minimum temperature is 170 DEG C, and melt blending is squeezed out, is granulated, is dry, and pack obtains
3D printing consumptive material.
The present invention is include at least the following beneficial effects:
The present invention by be added it is cheap, from a wealth of sources, can fully bio-degradable tapioca be thermoplastic starch
(TPS) it is consumed with polylactic acid (PLA), thermoplastic polyurethane (TPU) and the mixture prepared 3D printing of PLA base expanding material (PGU)
Material not only reduces cost, but also energy conservation and environmental protection, accelerates the degradation rate of PLA/TPS composite material.In the work of PLA base expanding material (PGU)
Under, the compatibility of PLA phase and TPU phase in composite material is improved, can effectively improve the toughness and extension at break of composite material
Rate is added a certain amount of thermoplastic starch (TPS), is still able to maintain good rheological characteristic, toughness and melt strength, Er Qiere
Expansion ratio is low, and surface property is good, reduces melting temperature, is controlled using the temperature of the 3D printing in later period.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy through the dissolved PLA/PGU/TPU of tetrahydrofuran solution；
Fig. 2 is the stress and strain curve graph of PLA, PLA10 and PLA20；
Fig. 3 is the notch impact strength column diagram of PLA, PLA10 and PLA20；
Fig. 4 is the DSC heating curve figure of PLA, PLA10 and PLA20；
Fig. 5 is that the standard wire of PLA10 and PLA20 prepares effect picture；
Fig. 6 is the printout effect picture of PLA10 and PLA20.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
It should be noted that experimental method described in following embodiments is unless otherwise specified conventional method, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
Embodiment 1
3D printing consumptive material of the invention, including following mass parts raw material are made: 65 parts of polylactic acid (PLA), thermoplastic poly ammonia
5 parts of ester (TPU), 0.1 part of PLA base expanding material (PGU) and 5 parts of thermoplastic starch (TPS).
The excellent 3D printing consumptive material of present invention low price is prepared via a method which, using above-mentioned mass parts raw material, including
Steps are as follows:
By the polylactic acid (PLA) after 65 parts of dryings, 5 parts of thermoplastic polyurethane (TPU), 0.1 part of PLA base expanding material
(PGU) and 5 parts of thermoplastic starch (TPS) it, is added in high-speed mixer and mixes 5min, double spiral shells are added in mixed material
In bar extruder, each area's temperature maximum temperature of extruder is 190 DEG C, and minimum temperature is 170 DEG C, and melt blending is squeezed out, made
Grain, drying, pack obtain 3D printing consumptive material.
Wherein, the thermoplastic starch (TPS) include mass parts 10 parts of glycerol and 50 parts of tapioca, and by glycerol
It with tapioca through high-speed mixer mixing 5min, is swollen, takes out, place 15h and obtain.
PLA base expanding material (PGU) includes following mass parts raw material: dry 65 parts of polylactic acid (PLA), thermoplastic poly ammonia
5 parts of ester (TPU), 2 parts of glycidyl methacrylate (GMA) and 0.1 part of cumyl peroxide (DCP)；And by as follows
Preparation step obtains:
Step 1: by 65 parts of dry polylactic acid (PLA) first in 180 DEG C of mixers at 50rpm after internally mix 2min,
0.1 part of cumyl peroxide (DCP) is added, continues continuous reaction 2min, adds 2 parts of glycidyl methacrylate
(GMA), material is taken out after reacting 3min, PLA-g-GMA is made in washing, dry, crushing；
Step 2: PLA-g-GMA in 180 DEG C of mixers at 50rpm, after continuing internally mix 3min, 5 parts of thermoplastic is added
Property polyurethane (TPU), the reaction was continued 4min takes out material so that TPU thoroughly replaces GMA afterwards, washing, it is dry, crush and be made
PLA-g-TPU copolymer, as PLA base expanding material (PGU).
Embodiment 2
The excellent 3D printing consumptive material of low price of the invention is prepared via a method which to obtain:
Step 1: by 97 parts of dry polylactic acid (PLA) first in 180 DEG C of mixers at 50rpm after internally mix 10min,
2.0 parts of cumyl peroxide (DCP) is added, continues continuous reaction 15min, adds 35 parts of methyl propenoic acid glycidyl
Ester (GMA) takes out material after reacting 10min, and PLA-g-GMA is made in washing, dry, crushing；
Step 2: PLA-g-GMA in 180 DEG C of mixers at 50rpm, after continuing internally mix 10min, be added 40 parts
Thermoplastic polyurethane (TPU), the reaction was continued 12min take out material, washing, dry, powder so that TPU thoroughly replaces GMA afterwards
Broken obtained PLA-g-TPU copolymer, as PLA base expanding material (PGU)；
Step 3: swelling takes by 50 parts of the glycerol of mass parts and 90 parts of tapioca through high-speed mixer mixing 15min
Out, it places 15-30h and obtains thermoplastic starch (TPS)；
Step 4: by the polylactic acid (PLA) after 95 parts of dryings, 35 parts of thermoplastic polyurethane (TPU), 30 parts of PLA base
Expanding material (PGU) and 40 parts of thermoplastic starch (TPS) are added in high-speed mixer and mix 10min, mixed material is added
Enter in double screw extruder, each area's temperature maximum temperature of extruder is 190 DEG C, and minimum temperature is 170 DEG C, and melt blending squeezes
Out, it is granulated, is dry, pack obtains 3D printing consumptive material.
Embodiment 3
The excellent 3D printing consumptive material of low price of the invention is prepared via a method which to obtain:
Step 1: by 70 parts of dry polylactic acid (PLA) first in 180 DEG C of mixers at 50rpm after internally mix 5min,
1 part of cumyl peroxide (DCP) is added, continues continuous reaction 10min, adds 15 parts of glycidyl methacrylate
(GMA), material is taken out after reacting 8min, PLA-g-GMA is made in washing, dry, crushing；
Step 2: PLA-g-GMA in 180 DEG C of mixers at 50rpm, after continuing internally mix 5min, be added 5-40 parts
Thermoplastic polyurethane (TPU), the reaction was continued 5min take out material, washing, dry, powder so that TPU thoroughly replaces GMA afterwards
Broken obtained PLA-g-TPU copolymer, as PLA base expanding material (PGU)；
Step 3: swelling takes by 20 parts of the glycerol of mass parts and 60 parts of tapioca through high-speed mixer mixing 10min
Out, it places 15-30h and obtains thermoplastic starch (TPS)；
Step 4: by the polylactic acid (PLA) after 70 parts of dryings, 10 parts of thermoplastic polyurethane (TPU), 10 parts of PLA base
Expanding material (PGU) and 30 parts of thermoplastic starch (TPS) are added in high-speed mixer and mix 10min, mixed material is added
Enter in double screw extruder, each area's temperature maximum temperature of extruder is 190 DEG C, and minimum temperature is 170 DEG C, and melt blending squeezes
Out, it is granulated, is dry, pack obtains 3D printing consumptive material.
Embodiment 4
The excellent 3D printing consumptive material of low price of the invention is prepared via a method which to obtain:
Step 1: first after internally mix 5min, 1 part of DCP is added at 50rpm in 180 DEG C of mixers in 80 parts of PLA,
Continue to continue reaction 10min, add 20 parts of GMA, takes out material after reacting 5min, PLA-g- is made in washing, dry, crushing
GMA；
Step 2: PLA-g-GMA at 50rpm, continues internally mix in 180 DEG C of mixers on the basis of step 1
After 5min, 30 parts of TPU is added, the reaction was continued 10min takes out material so that TPU thoroughly replaces GMA afterwards, washing, it is dry,
It crushes and PLA-g-TPU copolymer, as PLA base expanding material (PGU) is made；
Step 3: swelling takes by 40 parts of the glycerol of mass parts and 80 parts of tapioca through high-speed mixer mixing 10min
Out, it places 20h and obtains thermoplastic starch (TPS)；
Step 4: by the polylactic acid (PLA) after 70 parts of dryings, 20 parts of thermoplastic polyurethane (TPU), 15 parts of PLA base
Expanding material (PGU) and 35 parts of thermoplastic starch (TPS) are added in high-speed mixer and mix 10min, mixed material is added
Enter in double screw extruder, each area's temperature maximum temperature of extruder is 190 DEG C, and minimum temperature is 170 DEG C, and melt blending squeezes
Out, it is granulated, is dry, pack obtains 3D printing consumptive material.
Embodiment 5
The excellent 3D printing consumptive material of low price of the invention is prepared via a method which to obtain:
Step 1: first after internally mix 5min, 1 part of DCP is added at 50rpm in 180 DEG C of mixers in 80 parts of PLA,
Continue to continue reaction 10min, add 20 parts of GMA, takes out material after reacting 5min, PLA-g- is made in washing, dry, crushing
GMA；
Step 2: PLA-g-GMA at 50rpm, continues internally mix in 180 DEG C of mixers on the basis of step 1
After 5min, 30 parts of TPU is added, the reaction was continued 10min takes out material so that TPU thoroughly replaces GMA afterwards, washing, it is dry,
It crushes and PLA-g-TPU copolymer, as PLA base expanding material (PGU) is made；
Step 3: swelling takes by 20 parts of the glycerol of mass parts and 90 parts of tapioca through high-speed mixer mixing 10min
Out, it places and obtains thermoplastic starch (TPS) for 24 hours；
Step 4: high-speed mixer is added in 80 parts of PLA, 20 parts of TPU, PGU and 10 of 10 parts part of TPS after dry
Middle mixing 5min, mixed material is added twin-screw extrude, and each area's temperature maximum temperature of extruder is 190 DEG C,
Minimum temperature is 170 DEG C, and melt blending is squeezed out, is granulated, is dry, and pack obtains 3D printing consumptive material.
Embodiment 6
The excellent 3D printing consumptive material of low price of the invention is prepared via a method which to obtain:
Step 1: first after internally mix 5min, 1 part of DCP is added at 50rpm in 180 DEG C of mixers in 80 parts of PLA,
Continue to continue reaction 10min, add 20 parts of GMA, takes out material after reacting 5min, PLA-g- is made in washing, dry, crushing
GMA；
Step 2: PLA-g-GMA at 50rpm, continues internally mix in 180 DEG C of mixers on the basis of step 1
After 5min, 30 parts of TPU is added, the reaction was continued 10min takes out material so that TPU thoroughly replaces GMA afterwards, washing, it is dry,
It crushes and PLA-g-TPU copolymer, as PLA base expanding material (PGU) is made；
Step 3: swelling takes by 20 parts of the glycerol of mass parts and 90 parts of tapioca through high-speed mixer mixing 10min
Out, it places and obtains thermoplastic starch (TPS) for 24 hours；
Step 4: high-speed mixer is added in 80 parts of PLA, 20 parts of TPU, PGU and 20 of 10 parts part of TPS after dry
Middle mixing 5min, mixed material is added twin-screw extrude, and each area's temperature maximum temperature of extruder is 190 DEG C,
Minimum temperature is 170 DEG C, and melt blending is squeezed out, is granulated, is dry, and pack obtains 3D printing consumptive material.
Test case:
Composite material PLA10 is prepared by embodiment 5.
Composite material PLA20 is prepared by embodiment 6.
The step of material PLA is pure polylactic acid PLA material, and preparation method is with embodiment 5 is identical, unique the difference is that not
TPU, PGU and TPS is added, specifically: PLA is added in high-speed mixer and mixes 5min, double spiral shells are added in mixed material
In bar extruder each area's temperature maximum temperature of extruder be 190 DEG C, minimum temperature be 170 DEG C, melt blending squeeze out, be granulated,
Dry, pure PLA material is made in pack.
The preparation method of composite material PLA/PGU/TPU 10 specifically:
Step 1: first after internally mix 5min, 1 part of DCP is added at 50rpm in 180 DEG C of mixers in 80 parts of PLA,
Continue to continue reaction 10min, add 20 parts of GMA, takes out material after reacting 5min, PLA-g- is made in washing, dry, crushing
GMA；
Step 2: PLA-g-GMA at 50rpm, continues internally mix in 180 DEG C of mixers on the basis of step 1
After 5min, 30 parts of TPU is added, the reaction was continued 10min takes out material so that TPU thoroughly replaces GMA afterwards, washing, it is dry,
It crushes and PLA-g-TPU copolymer, as PLA base expanding material (PGU) is made；
Step 3: 80 parts of PLA, TPU and 10 of 10 parts part of PGU after dry to be added in high-speed mixer and mix
5min adds twin-screw extrude mixed material, and each area's temperature maximum temperature of extruder is 190 DEG C, lowest temperature
Degree is 170 DEG C, and melt blending is squeezed out, is granulated, is dry, and pack obtains composite material PLA/PGU/TPU 10.
Composite material PLA/PGU/TPU 20 is identical as the preparation step of composite material PLA/PGU/TPU 10, unique different
Be that the amount that TPU is added is different, be 20 parts.
Composite material PLA/PGU/TPU 30 is identical as the preparation step of composite material PLA/PGU/TPU 10, unique different
Be that the amount that TPU is added is different, be 30 parts.
Test case 1
Early-stage study the result shows that, the tetrahydrofuran solution under 50 DEG C of states has preferable solvability to pure TPU.And
Pure TPU is in 3695cm-1、3336cm-1、1731cm-1、1415cm-1There is apparent characteristic peak, this is respectively the OH freedom in TPU
The characteristic peak of the groups such as base, NH, C=O, CN.By PLA/PGU/TPU 10, PLA/PGU/TPU 20 and PLA/PGU/TPU 30
Respectively after tetrahydrofuran solution dissolves, its infrared spectroscopy is measured respectively as shown in Figure 1, the right box is 1415 in Fig. 1
Amplifier section is drawn at cm-1.PLA/PGU/TPU10, PLA/PGU/TPU10 and PLA/PGU/TPU30 tri- as can be seen from Figure 1
It can find to represent NH, CN characteristic peak in TPU at 3336cm-1,1415cm-1 in a component, this shows TPU
Successfully it is grafted on PLA/GMA.Further prove the structure of PLA-g-TPU.
Test case 2
Pure polylactic acid PLA material, composite material PLA10, composite material PLA20 are subjected to stretching experiment respectively, answered
Power is as shown in Figure 2 with strain curve.Figure it is seen that pure PLA does not have yield point, brittle fracture is shown as.It is added in TPS
At 10 parts, mechanical property keeps excellent, and elongation at break meets the performance requirement of 3D printing consumptive material up to 10%-35%.In
When TPS is added to 20 parts, elongation at break is had declined almost as pure PLA, but to be made into 3D printing consumptive material and not only be wanted
Flexible will also have certain elongation at break, therefore the additional amount of TPS should be limited, and be added to 10 parts of left sides in TPS
The right side is that best elongation at break is still able to maintain the excellent performance of 3D printing consumptive material while reducing cost by the way that TPS is added.
Test case 3
It is as described in Figure 3 that the material of PLA, PLA10, PLA20 are carried out to notch impact strength test result respectively, from Fig. 3's
The results show that impact strength can increase with the increase of TPS, the addition of TPS can improve the brittleness of PLA, and the present invention
The impact strength of the 3D printing consumptive material for PLA10, the PLA20 being prepared is high, and brittleness is low, function admirable.
Test case 4
The material of PLA, PLA10, PLA20 are carried out to DSC heating test respectively, test result is as described in Figure 4, from Fig. 4's
As a result as can be seen that the melting temperature of PLA is 174 DEG C, the melting temperature of the PLA based composites after adding TPS is dropped
Low, PLA10 and PLA20 are respectively 168 DEG C and 164 DEG C, are controlled using the temperature of the 3D printing in later period.Because the 3D in later period is beaten
When print, print temperature is a key factor, print temperature must on melting temperature in decomposition temperature hereinafter, TPS's plus
Melting temperature can be reduced by entering, that is to say, that the temperature also lower than pure PLA can be set in the 3D printing in later period, can save
Energy consumption.
Test case 5
The material of PLA10 and PLA20 is carried out to standard wire preparation test respectively, Fig. 5 (a) is the preparation of PLA10 material
The effect picture of wire rod, Fig. 5 (b) are the wire rod effect picture of PLA20 material preparation.Control line is needed in the preparation process of standard wire
The diameter of material is maintained within the scope of 1.75mm ± 0.15mm, and requires the surface of wire rod smooth, uniform.Wire rod is squeezed out in single screw rod
After machine (or double screw extruder) extrusion by water cooling and after calibrating, coiled material can be wound by coiled material device.Therefore, this just needs to make
There are certain toughness, rheological characteristic and melt strength for the base-material of 3D wire rod.As can be seen from Fig., PLA10 and PLA20 component exists
The preparation process of 3D printing consumptive material can meet the process for being expressed into coiled material.3D printing line after 10 and 20 parts of TPS is added
Material still keeps more uniform diameter, as can be seen that the 3D printing wire rod institute of PLA10 and PLA20 from Fig. 5 (a) and Fig. 5 (b)
The sample printed has relative smooth and uniform surface.
In order to further probe into the precision of 3D printing wire rod, 4 are randomly selected on the 3D printing wire rod made with PLA20
Point, using the diameter of the wire rod of point selected by vernier caliper measurement and with diameter criteria set by 3D printing consumptive material testing machine into
Row comparison, thermal expansion is than low, and the results are shown in Table 1.
1 3D printing wire rod of table randomly selects the comparison of diameter and setting normal diameter a little
Test case 6
The material of PLA10 and PLA20 is subjected to finished product printing test respectively, is depicted using 3D One3 dimension mapping software
Then the model of desk reuses Tontru's 3-dimensional digital Slice Software and 3 dimension modules drawn is carried out digital slices and are arranged
Print parameters finally print various sizes of model, such as the effect picture that Fig. 6 (a) is PLA10 file printing finished product, Fig. 6 (b)
For the effect picture of PLA20 file printing finished product.From the printing effect of Fig. 6, it is apparent that with 3D printing consumptive material of the invention
The product printed is smooth, and without warping, printing effect is preferable, 3D printing consumptive material function admirable of the invention.
Test case 5 and test case 6 are studied from the surface property into silk situation and printed sample of printing wire rod.In
The printing consumables of each component is not found the case where material leakage, plug wire in print procedure, this shows the PLA base of each component
Printing consumables has all reached the basic demand for meeting 3D printing in the process to wire rod rheological characteristic.In addition, the printing sample of each component
The surface of product is not found warping phenomenon.
To sum up test experiments, 3D printing consumptive material of the invention have at low cost, environmental protection and energy saving, and the advantage of function admirable.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (4)
1. a kind of 3D printing consumptive material, which is characterized in that be made including following mass parts raw material: 65-95 parts of polylactic acid (PLA), heat
5-35 parts of plastic polyurethane (TPU), 0.1-30 parts of PLA base expanding material (PGU) and 5-40 parts of thermoplastic starch (TPS).
2. 3D printing consumptive material as described in claim 1, which is characterized in that the thermoplastic starch (TPS) includes mass parts
10-50 parts and tapioca 50-90 parts of glycerol, and glycerol and tapioca are swollen through high-speed mixer mixing 5-15min,
It takes out, places 15-30h and obtain.
3. 3D printing consumptive material as claimed in claim 2, which is characterized in that the PLA base expanding material (PGU) includes following quality
Part raw material: dry 65-97 parts of polylactic acid (PLA), 5-40 parts of thermoplastic polyurethane (TPU), glycidyl methacrylate
(GMA) 2-35 parts and 0.1-2.0 parts of cumyl peroxide (DCP)；And step is prepared by the following procedure and obtains:
Step 1: by 65-97 parts of dry polylactic acid (PLA) first in 180 DEG C of mixers at 50rpm after internally mix 2-10min,
0.1-2.0 parts of cumyl peroxide (DCP) is added, continues continuous reaction 2-15min, adds 2-35 parts of methacrylic acid
Ethylene oxidic ester (GMA) takes out material after reacting 3-10min, and PLA-g-GMA is made in washing, dry, crushing；
Step 2: PLA-g-GMA in 180 DEG C of mixers at 50rpm, after continuing internally mix 3-10min, 5-40 parts of heat is added
Plastic polyurethane (TPU), the reaction was continued 4-12min, so that thermoplastic polyurethane (TPU) thoroughly replaces Glycidyl methacrylate
Glyceride (GMA), takes out material afterwards, and PLA-g-TPU copolymer, as PLA base expanding material is made in washing, dry, crushing
(PGU)。
4. a kind of preparation method of the 3D printing consumptive material as described in claims 1 or 2 or 3, which is characterized in that dry by 65-95 parts
Polylactic acid (PLA), 5-35 parts of thermoplastic polyurethane (TPU), 0.1-30 parts of PLA base expanding material (PGU) and 5-40 after dry
The thermoplastic starch (TPS) of part is added in high-speed mixer and mixes 5min-10min, and mixed material addition twin-screw is squeezed
Out in machine, each area's temperature maximum temperature of extruder is 190 DEG C, and minimum temperature is 170 DEG C, and melt blending is squeezed out, is granulated, is dry
Dry, pack obtains 3D printing consumptive material.
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