CN105001586A - Electric conduction compound ABS/PLA material for 3D printing wires as well as preparation method and application of electric conduction compound ABS/PLA material - Google Patents
Electric conduction compound ABS/PLA material for 3D printing wires as well as preparation method and application of electric conduction compound ABS/PLA material Download PDFInfo
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- CN105001586A CN105001586A CN201510411122.4A CN201510411122A CN105001586A CN 105001586 A CN105001586 A CN 105001586A CN 201510411122 A CN201510411122 A CN 201510411122A CN 105001586 A CN105001586 A CN 105001586A
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- 238000010146 3D printing Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 title abstract description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 73
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
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- 238000002156 mixing Methods 0.000 claims description 14
- 239000002048 multi walled nanotube Substances 0.000 claims description 14
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- HVHSLVRAAURMGO-UHFFFAOYSA-M P.[Br-].C(CCC)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound P.[Br-].C(CCC)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 HVHSLVRAAURMGO-UHFFFAOYSA-M 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
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- 238000009826 distribution Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
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- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 abstract 1
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- XQMVBICWFFHDNN-UHFFFAOYSA-N 5-amino-4-chloro-2-phenylpyridazin-3-one;(2-ethoxy-3,3-dimethyl-2h-1-benzofuran-5-yl) methanesulfonate Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1.C1=C(OS(C)(=O)=O)C=C2C(C)(C)C(OCC)OC2=C1 XQMVBICWFFHDNN-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention provides an electric conduction compound ABS/PLA material for 3D printing wires. The electric conduction compound ABS/PLA material is prepared from the following raw materials in percentage by weight: 15-30% of a synthetized material ABS by using a bulk method, 15-30% of a synthetized material ABS by an emulsion method, 1-10% of copolymers of styrene -acrylonitrile -2-methylpropenoic acid glycidyl ester, 0.01-0.05% of triphenylphosphonium bromide, 5-15% of metallic nickel powder , 30-50% of polylactic acid , 1-5% of walled carbon nanotubes and 1-5% of graphene microchips. According to the electric conduction compound ABS/PLA material disclosed by the invention, the nickel powder, the graphene microchips and the carbon nano tubes are optimized and collocated, so that the requirements for electrical conductivity by using lower volume resistivity under the low content of an electric conduction additive are met, the ABS material mixed in different particle diameters enables the particle diameters in the compound material to present bimodal distribution, and the toughness is enhanced; the consistency and the cocontinuity of ABS and PLA are good, so that the electric conduction compound ABS/PLA material is particularly suitable for strip-shaped high electric conduction materials required by 3D printing.
Description
Technical field
The invention belongs to 3D and print wire electro-conductive material technical field, more specifically, relate to a kind of 3D and print wire conduction ABS/PLA matrix material and its preparation method and application.
Background technology
The 3D printing ABS material bar sold in China at present has the STRATASYS P400 ABS of import, domestic imvite modified ABS(CN104672755A), fiber glass reinforced ABS (CN104559034A), polycarbonate modified ABS(CN104559023A), the ABS(CN104072935A of rubber particles bimodal distribution, CN103980429A), carbon black conductive modified ABS (CN103788565A), the 3D printing ABS material bar wherein conducted electricity has carbon black conductive modified ABS disclosed in CN103788565A, but carbon black conductive content reaches more than 35 mass parts, the printing effect having a strong impact on ABS material bar because filler content is high (occurs that precision is low, layering).And the volume specific resistance of this conduction ABS preferably can only reach 10
2ohm * centimetre of level, discomfort is used as the guidewire use in ABS matter 3D print member.
At present useful 3D printings ABS material bar prints consuming parts, but the wire in consuming parts still adopts enameled wire, PVC copper-clad wire, PE copper-clad wire, can not integrated molding, poor with the bonding of ABS substrate, and existence is leaked electricity risk.
(Proto-pasta conducts electricity PLA for the 3D printing PLA material strip of existing non-conductive 3D printing PLA material strip and conduction, volume specific resistance is 15 ohm * centimetre and Black Magic 3D conduction PLA, volume specific resistance is 1 ohm of * centimetre) be printed as compact consuming parts through double end, but on the one hand because appliance field use habit, consuming parts is all based on ABS material, do not accept PLA material, there is water suction degraded and mouldy possibility, poor durability in PLA base material electrical appliance on the other hand.
The method that may solve above technological deficiency of current appearance utilizes double end 3D printing technique, consuming parts is printed together with the 3D printing PLA material strip of conduction with non-conductive ABS material bar, but in the parts that current file printing goes out, ABS and PLA bonding is poor, the risk of leaking electricity when also there is high humidity.
Therefore, for above technical barrier, the present invention seeks the high connductivity material strip providing a kind of applicable double end 3D printing technique, can with non-conductive ABS material Application of composite in printing consuming parts, conductive filler material content in the 3D printing material strip of high connductivity can be solved high simultaneously, occur that precision is low, the defect of layering, and meet the high connductivity demand of volume specific resistance 1 ohm less than * centimetre.
Summary of the invention
The object of the invention is to the deficiency according to existing 3D printing ABS material bar technology, provide a kind of 3D and print wire conduction ABS/PLA matrix material.
Another object of the present invention is the preparation method and the application that provide described 3D printing wire conduction ABS/PLA matrix material.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
The invention provides a kind of 3D and print wire conduction ABS/PLA matrix material, the raw material that described matrix material comprises the following meter of number is by weight percentage made:
Substance law ABS 15 ~ 30%
Emulsion method ABS 15 ~ 30%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 1 ~ 10%
Butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05%
Metal nickel powder 5 ~ 15%
Poly(lactic acid) 30 ~ 50%
Multi-walled carbon nano-tubes 1 ~ 5%
Graphene microchip 1 ~ 5%.
Preferably, the raw material that described matrix material comprises the following meter of number is by weight percentage made:
Substance law ABS 15 ~ 25%
Emulsion method ABS 15 ~ 25%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 3 ~ 7%
Butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05%
Metal nickel powder 8 ~ 12%
Poly(lactic acid) 32 ~ 45%
Multi-walled carbon nano-tubes 1 ~ 4%
Graphene microchip 1 ~ 4%.
The present invention adopts metal nickel powder, graphene microchip and multi-walled carbon nano-tubes optimization collocation, closely pile up, 1 ohm * centimetre can be realized with the requirement of lower wire conduction under lower conductive additive content, be blended in the good polylactic acid PLA material of mobility, and realize compound with ABS material, the processing fluidity requirement of 3D printer to material strip can be met.
3D of the present invention prints the preparation method of wire conduction ABS/PLA matrix material, comprises the following steps:
S1. multi-walled carbon nano-tubes and graphene microchip are added in solvent, ultrasonic, then add poly(lactic acid), continue ultrasonic, by ultrasonic rear gained mixture heating, obtain PLA/ carbon material master batch;
S2. gained PLA/ carbon material master batch, poly(lactic acid) and metal nickel powder in S1 step are added melt blending in Banbury mixer, obtain PLA/Ni/ carbon material conductive agglomerate;
S3. gained PLA/Ni/ carbon material conductive agglomerate in S2 step is mixed with substance law ABS, emulsion method ABS, styrene-acrylonitrile-glycidyl methacrylate copolymer and butyltriphenylphosphonium bromide phosphine, carry out melt blending through twin screw extruder, then prepare the 3D printing ABS material bar of conductive modified through material strip forming machine.
Preferably, in described S1, the quality of multi-walled carbon nano-tubes and graphene microchip accounts for 15 ~ 25% of PLA/ carbon material master batch.
Preferably, in described S2, the quality of metal nickel powder accounts for 15 ~ 25% of PLA/Ni/ carbon material conductive agglomerate.
Preferably, in described S3, the quality of metal nickel powder accounts for 8 ~ 12% of conduction ABS/PLA matrix material.
Preferably, in described S3, the quality of multi-walled carbon nano-tubes and graphene microchip accounts for 3 ~ 8% of conduction ABS/PLA matrix material.
The present invention first by solution blended process by PLA, multi-walled carbon nano-tubes (MWCNTs) and the blended master batch being prepared as 15 ~ 25wt% carbon material concentration of graphene microchip (GNP), again by this master batch and PLA, metal nickel powder is prepared carbon material concentration (MWCNTs and GNP) through Banbury mixer melt blending and is about 6 ~ 10%, the conductive agglomerate of metal nickel powder concentration 15 ~ 25%, again by ABS that this master batch and substance law synthesize, the ABS of emulsion synthesize, styrene-acrylonitrile-glycidyl methacrylate copolymer (SAN-GMA), butyltriphenylphosphonium bromide phosphine (TPB) carries out melt blending in twin screw extruder, obtain nickel powder concentration 8 ~ 12%, the conduction ABS/PLA matrix material of carbon material concentration about 3 ~ 8%, again through the 3D printing material strip of material strip shaping mechanism for conductive modified.
Preferably, in described S1, solvent is chloroform, and ultrasonic time is 6 ~ 9h, and continuing ultrasonic time is 3 ~ 5, and described Heating temperature is 100 ~ 140 DEG C.
More preferably, described Heating temperature is 120 DEG C.
Preferably, in described S2, melt blending temperature is 180 ~ 200 DEG C.
Preferably, in described S3, twin screw extruder Heating temperature is 180 ~ 200 DEG C.
In the present invention, ABS and PLA forms co-cable transmission, on material strip top layer, existing ABS phase has again PLA phase, it is compatible good when melting material strip contacts with non-conductive ABS, when melting billot contacts with other conduction ABS/PLA layer, bond because of the existence of top layer PLA also very tight, reach than bond effect between prior art better enhancement layer.
The ABS mixing of the ABS of substance law synthesis and emulsion method synthesis is used to print the main base with ABS/PC alloy as 3D, because the ABS of substance law synthesis contains the larger rubber phase of particle diameter, and the rubber phase that the ABS particle diameter of emulsion method synthesis is less, both mixing can obtain the ABS matrix that rubber phase particle diameter presents bimodal distribution, the toughness of final material can be made better, the method of this melt blending obtains bimodal ABS, obtains that bimodal ABS is more simple, controllability is higher than the method for prior art polymerization.
Compared with prior art, the present invention has following beneficial effect:
The present invention is arranged in pairs or groups by the optimization of metal nickel powder, graphene microchip and carbon nanotube, the conductivity requirement of lower volume specific resistance is realized under obtaining lower conductive additive content, the ABS material of different-grain diameter mixing makes ABS particle diameter in matrix material present bimodal distribution, and toughness strengthens, ABS and the PLA cocontinuity that mixes is good, is particularly useful for the high connductivity material strip material needed for double end 3D printing technique.
Accompanying drawing explanation
The matrix material synthesis step figure that Fig. 1 provides for the embodiment of the present invention 1.
The SEM figure of the matrix material that Fig. 2 provides for the embodiment of the present invention 1.
Embodiment
Further illustrate this technology below in conjunction with specific embodiment, but embodiment does not limit in any form to this technology.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.
The PLA trade mark: NatureWorks 4043D PLA
SAN-GMA:
sAG-002, the rising molecule novel material Science and Technology Ltd. of Nantong day
Methyltriphenylphosphonium bromide (TPB): Shanghai Yu Mei Chemical Co., Ltd.
Substance law ABS: Tao Shi MAGNUM 213
Emulsion method ABS: Taiwan strange U.S. 747, Taiwan strange U.S. 757, Taiwan strange U.S. 756
GNP:KNG-180 Xiamen Knano Graphene Technology Corporation Limited
CNT: CNT-3 Shanghai Ka Jite Chemical Industry Science Co., Ltd
Tensile strength: adopt universal testing machine, according to ASTM-D638 standard testing
Notched Izod impact strength: adopt shock-testing machine, according to GB/T1043 standard testing
Volume specific resistance: adopt EST121 type numeral ultra-high resistance, micro current instrument, according to GB/T1410-2006 test, sample diameter 82mm, thick 2mm, each sample surveys five groups, gets its mean value.
embodiment 1:
1, according to the proportioning raw materials of embodiment in table 11, weigh CNT and GNP and be placed in beaker, add chloroform, limit high-speed stirring, limit ultrasonic (power 120W) after 8 hours, then adds PLA, continue ultrasonic and stir 4 hours, after mixture is air-dry, be placed in 120 degrees Celsius of baking ovens 4 hours, obtain PLA/ carbon material master batch.
2, pure PLA, PLA/ carbon material master batch and metal nickel powder are added in 185 degrees Celsius of lower melt blendings in Banbury mixer, preparation PLA/Ni/ carbon material conductive agglomerate.
In step 1, the quality of CNT and GNP accounts for 15 ~ 25% of PLA/ carbon material master batch.
In step 2, the quality of metal nickel powder accounts for 15 ~ 25% of PLA/Ni/ carbon material conductive agglomerate.
3, PLA/Ni/ carbon material conductive agglomerate mixes with substance law ABS (Tao Shi MAGNUM 213), emulsion method ABS (Taiwan strange U.S. 747), styrene-acrylonitrile-glycidyl methacrylate copolymer (SAN-GMA), butyltriphenylphosphonium bromide phosphine (TPB), under 185 degrees Celsius, melt blending is carried out through twin screw extruder, prepare carbon material and the composite modified common continuous ABS/PLA alloy of nickel powder, then manufacture the 3D printing ABS material bar of conductive modified through material strip forming machine.
The matrix material synthesis step figure that Fig. 1 provides for embodiment 1, the SEM figure of the matrix material that Fig. 2 provides for embodiment 1.
embodiment 2
Preparation method is with embodiment 1, and emulsion method ABS raw material is Taiwan strange U.S. 757, and raw material proportion of composing is in table 1.
embodiment 3:
Preparation method is with embodiment 1, and emulsion method ABS raw material is Taiwan strange U.S. 756, and raw material proportion of composing is in table 1.
embodiment 4:
Preparation method is with embodiment 1, and raw material proportion of composing is in table 1.
embodiment 5:
Preparation method is with embodiment 1, and raw material proportion of composing is in table 1.
embodiment 6:
Preparation method is with embodiment 1, and raw material proportion of composing is in table 1.
embodiment 7:
Preparation method is with embodiment 1, and raw material proportion of composing is in table 1.
comparative example 1::
Preparation method with embodiment 1, unlike the substance law ABS purchasing of raw materials from Sinopec Shanghai branch office 8391.
comparative example 2:
Preparation method with embodiment 1, unlike the emulsion method ABS purchasing of raw materials from German BASF GP-22.
comparative example 3:
The same embodiment of preparation method, unlike the substance law ABS purchasing of raw materials from Sinopec Shanghai branch office 8391, the emulsion method ABS purchasing of raw materials from German BASF GP-22.
Table 1 is embodiment 1 ~ 7 raw material and consumption, is mass percent concentration (wt%).
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Substance law ABS | 21.49 | 22.99 | 20.74 | 19.74 | 23.49 | 21.39 | 21.19 |
| Emulsion method ABS | 21.49 | 22.99 | 20.74 | 19.74 | 23.49 | 22.39 | 21.19 |
| SAN-GMA | 5 | 4 | 5 | 6 | 4 | 5 | 5 |
| PLA | 38 | 36 | 40 | 42 | 35 | 36 | 37 |
| GNP | 2 | 2.5 | 2 | 2.5 | 1.5 | 2.7 | 2.2 |
| CNT | 2 | 1.5 | 2.5 | 2 | 1.5 | 1.5 | 1.4 |
| Ni | 10 | 10 | 9 | 8 | 11 | 12 | 10 |
| TPB | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
Table 2 is the machinery that records of embodiment 1 ~ 7 and comparative example 1 ~ 3 and conductivity data:
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tensile strength MPa | 44.1 | 43.3 | 45.7 | 43.9 | 42.8 | 40.7 | 46.0 | 42.0 | 45.3 | 42.3 |
| Notched Izod impact strength J/M | 107 | 124 | 113 | 126 | 135 | 125 | 119 | 83 | 82 | 91 |
| Volume specific resistance Ω * cm | 0.69 | 0.74 | 0.83 | 0.84 | 0.57 | 0.55 | 0.78 | 0.92 | 0.90 | 0.89 |
Wherein, in commercially available material, it is that to conduct electricity the volume specific resistance of PLA be 1 Ω * cm for 15 Ω * cm, Black Magic 3D that Proto-pasta conducts electricity the volume specific resistance of PLA.
As can be seen from the above data, adopt the optimization collocation of metal nickel powder, graphene microchip and carbon nanotube, the materials conductive additive level prepared is low, and realize the conductivity requirement of lower volume specific resistance, reach 1 Ω below * cm, also lower than the volume specific resistance of existing two kinds of commercially available high connductivity Proto-pasta conduction PLA and Black Magic 3D conduction PLA.
In addition, adopt two kinds of specific ABS provided by the invention as base material, the ABS composite material be mixed with, its toughness and conductivity comparatively other ABS substrate better effects if, show the blended characteristic that it is good.
Claims (10)
1. 3D prints a wire conduction ABS/PLA matrix material, it is characterized in that, the raw material that described matrix material comprises the following meter of number is by weight percentage made:
Substance law ABS 15 ~ 30%
Emulsion method ABS 15 ~ 30%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 1 ~ 10%
Butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05%
Metal nickel powder 5 ~ 15%
Poly(lactic acid) 30 ~ 50%
Multi-walled carbon nano-tubes 1 ~ 5%
Graphene microchip 1 ~ 5%.
2. 3D according to claim 1 prints wire conduction ABS/PLA matrix material, it is characterized in that, the raw material that described matrix material comprises the following meter of number is by weight percentage made:
Substance law ABS 15 ~ 25%
Emulsion method ABS 15 ~ 25%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 3 ~ 7%
Butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05%
Metal nickel powder 8 ~ 12%
Poly(lactic acid) 32 ~ 45%
Multi-walled carbon nano-tubes 1 ~ 4%
Graphene microchip 1 ~ 4%.
3. the 3D described in claim 1 or 2 prints a preparation method for wire conduction ABS/PLA matrix material, it is characterized in that, comprises the following steps:
S1. multi-walled carbon nano-tubes and graphene microchip are added in solvent, ultrasonic, then add poly(lactic acid), continue ultrasonic, by ultrasonic rear gained mixture heating, obtain PLA/ carbon material master batch;
S2. gained PLA/ carbon material master batch, poly(lactic acid) and metal nickel powder in S1 step are added melt blending in Banbury mixer, obtain PLA/Ni/ carbon material conductive agglomerate;
S3. gained PLA/Ni/ carbon material conductive agglomerate in S2 step is mixed with substance law ABS, emulsion method ABS, styrene-acrylonitrile-glycidyl methacrylate copolymer and butyltriphenylphosphonium bromide phosphine, melt blending is carried out through twin screw extruder, obtain conduction ABS/PLA matrix material, then prepare the 3D printing ABS material bar of conductive modified through material strip forming machine.
4. preparation method according to claim 3, is characterized in that, in described S1, the quality of multi-walled carbon nano-tubes and graphene microchip accounts for 15 ~ 25% of PLA/ carbon material master batch.
5. preparation method according to claim 3, is characterized in that, in described S2, the quality of metal nickel powder accounts for 15 ~ 25% of PLA/Ni/ carbon material conductive agglomerate.
6. preparation method according to claim 3, is characterized in that, in described S3, the quality of metal nickel powder accounts for 8 ~ 12% of conduction ABS/PLA matrix material.
7. preparation method according to claim 3, is characterized in that, in described S3, the quality of multi-walled carbon nano-tubes and graphene microchip accounts for 3 ~ 8% of conduction ABS/PLA matrix material.
8. preparation method according to claim 3, is characterized in that, in described S1, solvent is chloroform, and ultrasonic time is 6 ~ 9h, and continuation ultrasonic time is 3 ~ 5h, and described Heating temperature is 100 ~ 140 DEG C.
9. preparation method according to claim 3, is characterized in that, in described S2, melt blending temperature is 180 ~ 200 DEG C.
10. preparation method according to claim 3, is characterized in that, in described S3, twin screw extruder Heating temperature is 180 ~ 200 DEG C.
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| CN106633718A (en) * | 2016-11-17 | 2017-05-10 | 南宁梦幻三体环保科技有限公司 | Graphene 3D (Three Dimensional) printing material with high cantilever notch impact strength |
| CN106589865A (en) * | 2016-11-17 | 2017-04-26 | 广西筑梦三体科技有限公司 | Graphene 3D printing material with high thermal deformation temperature |
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| WO2021089920A1 (en) * | 2019-11-05 | 2021-05-14 | Arctic Biomaterials Oy | Conductive polymer composition |
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